JP2009539719A - Pullulan films and their use in edible packaging - Google Patents

Abstract

  The edible article comprises a food and a film that wraps the food. In one embodiment, the film comprises a major amount of pullulan on a dry solid basis and a small amount of at least two of glycerol, propylene glycol, sorbitol and polyethylene glycol. In other embodiments, the film comprises a major amount of pullulan, gelatin and at least two of glycerol, propylene glycol, sorbitol and polyethylene glycol on a dry solid basis, and may also contain a salt. In another embodiment, the film comprises a first layer comprising a major amount of at least one food wax; a second layer comprising a major amount of pullulan and further comprising at least one plasticizer; and A third layer comprising at least one surfactant that is substantially immiscible with the aqueous pullulan composition but adheres to the pullulan surface. In other embodiments, the film comprises a major amount of pullulan, at least one salt (in some cases at least two salts) and at least one plasticizer on a dry solid basis. In another embodiment, the film comprises an edible film adhered to a peelable flexible substrate, the edible film comprising a major amount of pullulan and at least one plasticizer on a dry solid basis. Become. An edible article is produced by preparing a film-forming composition as described above, forming the film-forming composition into a film, and wrapping food in the film.

Description

Background of the Invention

  Several types of packaging materials are soluble in water. For example, water-soluble pouches made of polyvinyl alcohol (PVOH) film have been used to package weighed pesticides and concrete additives. These PVOH pouches are added to a tank or mixer where the packaging material dissolves and the contents are released. PVOH pouches are also used in weighed laundry soaps and dishwashing detergents. However, since PVOH is not a foodstuff, PVOH technology has so far been limited to the non-food field.

  Edible films have been made from other film-forming polymers such as pullulan. For example, edible strips containing pullulan and mouth fresheners have been sold for human consumption. Cough medicines, vitamins and dietary supplements have also been supplied in the form of edible strips.

  Pullulan has several properties that make it suitable for use in edible compositions. However, one problem with pullulan films is their limited ability to stretch without breaking. This problem limits the ability of pullulan films to encapsulate other materials as opposed to interspersing other materials with the film itself. Examination of the tensile strength and elongation characteristics of the packaging film shows that strengths of over 1000 grams and elongation of over 50% appear to give pullulan base films suitable for commercial packaging.

  There is a need for improved methods of encapsulating or packaging other materials with pullulan base films or compositions.

Summary of the Invention

  One aspect of the present invention is an edible article comprising a food and a water-soluble film surrounding the food. The film consists essentially of a major amount of pullulan on a dry solid basis and a small amount of two or more components selected from the group consisting of glycerol, propylene glycol, sorbitol and polyethylene glycol. “Consisting essentially of” in this context means that the composition is essentially free of polysaccharides other than those listed.

  In some embodiments of the invention, the film comprises about 35-80% by weight pullulan on a dry solids basis. In some embodiments, the film comprises no more than about 40% by weight of the plasticizer mixture. As a plasticizer mixture, in some embodiments, a combination of glycerol, propylene glycol and sorbitol is used. The film can optionally further contain citric acid, starch or starch derivatives (eg, dextrin or maltodextrin), alginate, xanthan gum, modified cellulose, polydextrose or a combination of two or more thereof.

  In other embodiments of the edible article, the water-soluble film surrounding the food product comprises a major amount of pullulan, gelatin, and at least two of glycerol, propylene glycol, sorbitol and polyethylene glycol on a dry solid basis. Optionally, the film can also contain at least one salt, such as NaCl. The film can optionally also contain at least one internal film release agent.

  Another aspect of the present invention is a water-soluble edible film comprising the above components.

  Yet another aspect of the present invention is a method for producing a water-soluble edible film. The method comprises (a) preparing a film-forming composition as described in the various embodiments above, and (b) treating the substrate with a solution or suspension comprising at least one surfactant. Coating and (c) casting the film-forming composition onto a substrate.

  Another aspect of the invention is a method for manufacturing an edible article. The method comprises preparing a film-forming composition as described in the various embodiments above, forming the film-forming composition into a water-soluble film, and wrapping a food product with the film. The various components of the film-forming composition are as described above.

  In some embodiments of the invention, the film can be stretched in the machine direction at least about 50% or at least about 100% without breaking. In one aspect, the food product is wrapped by placing the food product between two films and heat sealing the two films to form a sealed enclosure around the food product. On the other hand, food may be wrapped by placing the food between two films and applying moisture and pressure to at least a portion of the film to form a sealed enclosure around the food. Another special encapsulation method used is to vacuum form the film around the food.

  Another aspect of the invention is a first layer comprising a major amount of at least one food grade wax, a second layer comprising a major amount of pullulan and further comprising at least one plasticizer, An edible film comprising a third layer that is substantially immiscible with the aqueous pullulan composition but comprises at least one surfactant that adheres to the pullulan surface. The at least one surfactant is at least partially crystalline. In one embodiment, the at least one surfactant comprises sodium stearoyl lactate. In one embodiment, the second layer further comprises particles of food grade wax.

  Another aspect of the present invention is an edible article comprising a food and an edible film that wraps the food. The film comprises first, second and third layers as described in the previous paragraph. A first layer comprising a major amount of at least one food grade wax is in contact with the food product.

  Another aspect of the present invention is a method for producing an edible film. In the method, a solution or suspension comprising a major amount of at least one surfactant that is substantially immiscible with the aqueous pullulan composition is applied to a substrate and is at least partially crystalline. The solution or suspension is dried or concentrated to form a first layer comprising a major amount of a dry surfactant and comprises pullulan, at least one plasticizer and at least one food grade wax. An aqueous solution or suspension consisting of is applied to the dry surfactant layer and the aqueous solution or suspension is dried or concentrated, thereby forming a second layer and a third layer. The second layer is on the first layer and the third layer is on the second layer. The second layer comprises a plasticizer and a major amount of pullulan, and the third layer comprises a major amount of food grade wax.

Yet another aspect of the present invention is an edible film comprising a major amount of pullulan on a dry solid basis, at least one salt, and at least one plasticizer. In some embodiments, the film, for example, such as NaCl and MgCl _2, comprising at least two salts.

  Another aspect of the present invention is an edible article comprising a food product and an edible film that wraps the food product, as described in the previous paragraph.

  Another aspect of the present invention is a film structure comprising an edible film adhered to a peelable flexible substrate. The edible film comprises a major amount of pullulan on a dry solid basis and at least one plasticizer. In some embodiments, the flexible substrate comprises a polymer film, such as a polyester film.

Description of specific aspects

  One aspect of the present invention relates to an edible article containing food, which can be consumed in the mouth or can be dissolved (fully or partially) in water. These articles have an outer layer or surface made of a film-forming composition and food is wrapped in the outer layer.

  The film-forming composition comprises a major amount of pullulan on a dry solids basis (in this context “major amount” means that the composition contains more pullulan on a dry solids basis than the other ingredients). means). In one embodiment of the invention, the film-forming composition comprises about 35-80% by weight pullulan on a dry solid basis. Optionally, in some embodiments of the present invention, other film forming materials such as alginates, xanthan gum, modified cellulose, polydextrose, starch or starch derivatives (eg, dextrin or maltodextrin) and two or more such materials Combinations can also be included in the film-forming composition. Inclusion of one or more of these polymers can increase film strength and reduce costs compared to pullulan-only compositions.

  The film-forming composition also contains a small amount of plasticizer, especially at least two plasticizers glycerol, propylene glycol, sorbitol and polyethylene glycol (in this context, “small amount” means that the composition is less than pullulan on a dry solid basis). Meaning that it contains all plasticizers). One commercially available polyethylene glycol suitable for use in the present invention is a polyethylene glycol molecular weight of 200 (PEG 200). In one embodiment of the invention, the film-forming composition comprises the plasticizers glycerol, propylene glycol and sorbitol. For example, the film-forming composition comprises about 1-30% by weight glycerol, about 1-30% propylene glycol and about 1-30% sorbitol on a dry solid basis. Each of these materials is commercially available. Optionally, in some embodiments, the composition may also contain other plasticizers. In one embodiment of the invention, the film-forming composition comprises up to about 40% by weight of the plasticizer mixture.

  20% in water without any plasticizer d. s. The pullulan solution becomes a transparent film that can be peeled off from Mylar after being cast on Mylar, dried to a residual moisture of 10% or less. The film exhibits high tensile strength, but can only stretch and stretch about 10% in length before it breaks.

  In general, pullulan-containing films that also contain a plasticizer exhibit, to some extent, higher strength and elongation than pullulan films that do not contain a plasticizer. However, increasing the plasticizer content of the pullulan film beyond this level often leads to a significant decrease in tensile strength. For example, the addition of individual food plasticizers to the pullulan polymer solution prior to casting and drying gives the film an elongation greater than 10%, but at the cost of a significant reduction in tensile strength.

  Surprisingly, pullulan compositions containing at least two plasticizers glycerol, propylene glycol, sorbitol and polyethylene glycol produce pullulan films with high elongation and high tensile strength, even at relatively high plasticizer concentrations. It was found that it can be used to In at least some embodiments of the invention, the film can be stretched at least about 50% and in some cases at least about 100% without breaking. In some embodiments, the elongation at break is at least about 200%, or at least about 300%. In some embodiments of the invention, these enhancements on the elongation properties of the film are obtained without a substantial decrease in tensile strength.

  The composition may also contain one or more additives suitable for use in foods, such as fillers, surfactants, stabilizers, organic acids (eg, citric acid) and seasonings.

  One embodiment of the present invention is a water-soluble composition consisting essentially of a major amount of pullulan on a dry solid basis and a small amount of two or more components selected from glycerol, propylene glycol, sorbitol and polyethylene glycol. It is an edible film forming composition. The composition is formed into a film having a thickness of less than 2.2 mils (0.0022 inches or 0.056 mm) that exhibits a tensile strength greater than 1000 grams weight and an elongation at break greater than 50%.

  In another specific embodiment of the present invention, the water-soluble edible film-forming composition comprises a group consisting of a major amount of pullulan on a dry solid basis and a minor amount of (i) alginates, cellulose ethers, modified starches and combinations thereof. An auxiliary polysaccharide selected from (ii) two or more components selected from the group consisting of glycerol, propylene glycol, sorbitol and polyethylene glycol (in this context, “small amount” means composition Means that the product contains less plastic than pullulan on a dry solid basis and less total puller polysaccharide on a dry solid basis than pullulan). The composition is formed into a film having a thickness of less than 2.2 mils, exhibiting a tensile strength greater than 1000 gram weight and an elongation at break greater than 50%.

  In another embodiment of the present invention, the film-forming composition used to form the water-soluble edible film comprises a major amount of pullulan on a dry solid basis, with less gelatin and glycerol, propylene glycol And at least two of sorbitol and polyethylene glycol. The use of gelatin as a secondary polymer can maintain or improve elongation while maintaining film strength. Gelatin provides a smooth surface to the film without increased stickiness and blocking. In certain embodiments, the film-forming composition comprises about 35-80% by weight pullulan and about 0.5-22.5% by weight gelatin on a dry solids basis. Optionally, the composition comprises the plasticizers glycerol, propylene glycol and sorbitol. For example, in some embodiments of the invention, the film-forming composition comprises about 1-30% by weight glycerol, about 1-30% propylene glycol and about 1-30% sorbitol on a dry solid basis.

  Optionally, the composition also comprises at least one salt. It has been found that the addition of salt to the film improves the film elongation. Typically, surface properties such as blocking and tackiness are sacrificed to improve elongation. However, surface properties are often improved when salts are included in the composition to increase elongation. Films containing salt and appropriate levels of traditional plasticizers are neither blocking nor sticky and can therefore more easily roll themselves. Examples of suitable salts are NaCl and KCl. In some embodiments of the invention, the concentration of salt in the film-forming composition is about 0.3 to 15% by weight on a dry solid basis. Films having a salt content of -10% or more become turbid with a powder finish as a small amount of salt precipitate from the film to the surface upon drying. Films having a salinity of ˜5% or less below it have good elongation and surface properties without any residual salt precipitating from the film.

  As another option, the film-forming composition may contain at least one internal film release agent to facilitate peeling of the film from the substrate surface on which it is cast. Suitable examples of internal film release agents include, but are not limited to, polyoxyethylene sorbitan monooleate, sodium lauryl sulfate, and combinations thereof. Polyoxyethylene (20) sorbitan monooleate is commercially available as Polysorbate 80.

  Other details of the film-forming composition in this aspect of the invention and its use for wrapping food are as described above for other aspects.

  Techniques for forming films using pullulan compositions are well known in the art. For example, an aqueous pullulan solution is cast to a flat surface and then heated and dried to form a film. Methods for controlling film thickness are also well known.

  In one aspect of the invention, a film-forming composition is prepared as described above, and a substrate (eg, a stainless steel surface) is coated with a solution or suspension comprising at least one surfactant, and A water soluble edible film is formed by a method comprising casting the film forming composition onto a substrate. After appropriate heating and / or drying, the film is peeled from the substrate.

  Film gels cast directly onto stainless steel substrates, especially films with 75-125% elongation at break, often do not leave the steel well. These types of films often become easily stretched and distorted when they are moved away from the untreated steel. In order to eliminate or alleviate this problem, the steel substrate is treated with a solution or suspension comprising a release agent.

  Coating the substrate with a solution or suspension of a food surfactant (ie, an external film release agent) facilitates peeling of the film from the substrate. Suitable surfactants for this purpose include propylene glycol monostearate, sodium stearoyl lactate, polyoxyethylene sorbitan monooleate (eg Polysorbate 80), sodium lauryl sulfate, a salt of stearic acid or combinations thereof, It is not limited to them. Suitable surfactants are used in water and / or alcohol (ie, isopropyl alcohol) solutions or other suitable solvent systems in amounts up to 10% by weight.

  There are many different approaches in which film-forming compositions are used to wrap food. For example, a form is formed into a pouch, food is placed into the pouch, and then the opening of the pouch is sealed, for example by application of heat and / or moisture. One specific technique used is to vacuum form the film around the food. Vacuum forming has the advantage that there is less extreme bending of the film web under tension compared to some other methods of wrapping the product with film.

  The food film of the present invention can have the tensile strength and elongation characteristics necessary to successfully produce an edible package in a commercial vacuum forming apparatus. They also have the ability to make many different shapes and can be used in complex molds more successfully than at least some other commercial film forming materials. In some embodiments, the film exhibits a tensile strength greater than 1000 gram weight and an elongation at break greater than 50%. In some embodiments, the film has an elongation at break of 75-125%.

  A variety of food products are packaged, including those that need to be dissolved or dispersed in cooking water and those that are provided in a single-use package for human consumption. Examples of such foods are powdered beverage mixes (eg cocoa drink products, soft drink products and cider drink products), powdered cheese products, powdered egg products, candy, dried soup and casserole mixes, food colors and spices However, it is not limited to them. The food itself may be water-soluble, but this is not necessarily the case.

  For example, the film is used for packaging dry foods or oil-based liquid foods. The film is also used for packaging food that requires addition to water or water-containing foods. This includes, for example, drink mixes, vitamin and mineral additives, colorants, seasonings and any other ingredients that are added to food in batch production at food production plants or even in food preparation by individuals prior to consumption.

  The edible film of the present invention has a high elongation without stickiness in at least many embodiments. The use of such films in food packaging reduces waste, can be consumed as a whole package, and leaves nothing to throw away. When utilized to package the ingredients required for batch cooking, the exact amount of ingredients added is known. Since the entire package is cooked into the product, there is no loss of material due to sticking inside the package.

  In another embodiment of the invention, the multilayer edible film comprises a first layer comprising a major amount of at least one food grade wax, a major amount of pullulan, and further comprising at least one plasticizer. It comprises a second layer and a third layer. The third layer is substantially immiscible with the aqueous pullulan composition but comprises at least one surfactant that adheres to the pullulan surface. The at least one surfactant is at least partially crystalline in form. The surfactant is, for example, sodium stearoyl lactate. In some embodiments, the concentration of at least one surfactant in the entire film is about 0.001 to 0.1% by weight, or in some cases about 0.001 to 0.05%. The second layer optionally also includes food grade wax particles.

In some other embodiments of the invention, the second layer comprises about 35-80 wt% pullulan on a dry solid basis, and the plasticizer comprises at least two of glycerol, propylene glycol, sorbitol and polyethylene glycol in the second layer. Comprising. In one specific embodiment, the second layer comprises glycerol, propylene glycol, and sorbitol, such as about 1-30% by weight glycerol, about 1-30% propylene glycol, and about 1-30% sorbitol on a dry solid basis. As another option, in addition to pullulan, the second layer may be a secondary film-forming material such as about 0.5-22.5 wt% gelatin, starch, starch derivatives, alginate, xanthan gum, collagen, poly, on a dry solid basis. It may further contain dextrose or a combination of two or more thereof. As yet another option, the second layer may also contain at least one salt, such as NaCl, MgCl ₂ or combinations thereof. If present, it is preferably present in the second layer at a concentration of about 0.3 to 15% by weight on a dry solid basis.

  Another aspect of the present invention is an edible article comprising a food and an edible film surrounding the food, wherein the film comprises the first, second and third layers as described above. The first layer is in contact with food.

Another aspect of the present invention is a method for producing an edible film. The method
Applying to the substrate a solution or suspension comprising a major amount of at least one surfactant that is substantially immiscible with the aqueous pullulan composition;
Drying or concentrating the solution or suspension to form a first layer comprising a major amount of a dry surfactant that is at least partially crystalline;
Applying an aqueous solution or suspension comprising pullulan, at least one plasticizer and at least one food grade wax to the dry surfactant layer, and drying or concentrating the aqueous solution or suspension; Forming a second layer and a third layer. The second layer is on the first layer and the third layer is on the second layer. The second layer comprises a plasticizer and a major amount of pullulan, and the third layer comprises a major amount of food grade wax.

  This three-layer structure is formed in a single pass through a continuous film casting process. In one embodiment, the operation first requires the application of a surfactant such as sodium stearoyl lactate (SSL, 2% in isopropanol) to the stainless steel casting surface as a release agent. The solvent evaporates rapidly so as to form a dry release layer of SSL before casting. A pullulan casting aqueous solution containing a food grade wax emulsion as one of the formulation components is then applied to the casting surface as a thin uniform film. The film is then subjected to controlled drying conditions and dried to less than 15 weight percent moisture in a few minutes. During the drying process, the wax particles tend to move toward the open surface of the film due to their relatively low surface energy. After the film is dried, a layer of partially crystalline SSL is seen on the film surface that was in contact with the stainless steel casting substrate. In addition, a layer of wax particles is seen on the surface of the film that is open to the air during the drying process. Between these two surface layers is an intermediate layer containing mainly pullulan and other water soluble materials in the casting formulation.

  FIG. 1 shows an embodiment of this three-layer film in schematic form. The SSL crystal layer 10 is located at the interface between the film and the substrate on which it is cast. The central layer of the film is a matrix 16 comprising pullulan. There is also an SSL rich diffusion layer 12 between the pullulan matrix 16 and the SSL crystal layer 10. There are a plurality of wax particles 14 in the pullulan matrix 16 and a thin wax layer 18 on the film surface.

  Pullulan film formulations may contain up to about 10% by weight wax, although a wax content of less than about 5% is usually preferred. Suitable waxes include paraffin wax and other food grade waxes such as carnauba, candelilla or beeswax. The surfactant SSL is immiscible with the aqueous cast gel but is replaced with any surfactant that exhibits good adhesion to the pullulan film surface.

  The surface (eg, SSL) layer not only provides improved release of the dry film from the stainless steel casting belt, but also imparts a slightly hydrophobic character to the side of the film used outside the edible package. This slight hydrophobicity reduces the film's sensitivity to changes in environmental humidity. The pouch is not so hydrophobic that it becomes insoluble in water.

  The wax layer is used on the side of the film that contacts the food filling material contained in the edible pouch. The wax layer reduces moisture transfer between the filling material and the film layer of the pouch itself. The wax layer also provides significant antiblocking properties to the film. Another additional advantage of this wax layer is that it increases the sliding of the film in contact with the packaging machine during high speed processing operations.

  The middle layer of pullulan can provide the required strength and flexibility of a three-layer film structure.

  Thus, the various aspects of this three-layer film have improved functionality, such as increased resistance to environmental humidity, increased resistance to moisture transfer from food filling materials to packaging film, and more with high speed packaging equipment. It can provide improved sliding that slides easily. These enhancements give the packaged food an improved shelf life and expand the range of equipment used to process the film into edible packaging.

Another aspect of the invention is an edible film comprising a major amount of pullulan, at least one salt and at least one plasticizer on a dry solid basis. In some embodiments, the film comprises at least two salts, for example, a combination of NaCl and MgCl _2. In some embodiments, at least one salt is present in the film at a concentration of about 0.3 to 15% by weight on a dry solid basis. The plasticizer and other components of the film are as described above for other embodiments of the invention. The film of this embodiment is used to produce an edible article comprising a food product wrapped in an edible film.

  Another aspect of the present invention is a film structure comprising an edible film adhered to a peelable flexible substrate. The edible film comprises a major amount of pullulan and at least one plasticizer on a dry solid basis. In some embodiments, the flexible substrate comprises a polymer film, such as a polyester film. In one embodiment, the flexible substrate comprises a biodegradable polymer film, such as polylactic acid, polyglycolic acid, a copolymer of lactic acid and glycolic acid, or a mixture of two such polymers. The plasticizer and other components are as described above for other embodiments of the invention. The film of this embodiment is used to produce an edible article comprising a food product wrapped in an edible film.

  FIG. 2 shows one embodiment of this film structure. The pullulan film 20 as described above is releasably adhered to the polyester film 22 from which it is peeled off when desired.

  This two-layer film structure is particularly useful in high speed packaging operations. A potential problem with using edible films in conventional packaging equipment is that all film surfaces must be kept clean because the packaging film is part of the edible product. This is different from conventional packaging strategies where one surface of the packaging film is in contact with food and the other surface is exposed to protect the food from the environment. In one embodiment of the present invention, the outer surface of the edible film is protected with a polyester layer during packaging and can be easily removed before using the food contained in the edible package.

  Any of the films described herein can be used to package food, for example by forming a pouch as shown in cross section in FIG. 3, where the film 30 surrounds an internal storage area 32, A food item 34 is placed there. Film end 36 is sealed to form an encapsulated package.

  The following experimental methods were used in the following examples.

Preparation of pullulan and other polymer solutions Polymer solutions having a viscosity of 10,000 centipoise or less were prepared. Water was added to the vessel and stirred, and then the dry polymer powder was added over time to the vortex of the stirring liquid. Stirring was continued at 100-1000 rpm for 30-60 minutes and then the solution was allowed to stand for at least 2 hours before use.

Blending plasticizers and other additives Blend the polymer solution as needed to achieve the desired ratio and concentration, then add neat to the polymer solution over time while mixing the oligomers, plasticizers and other additives It was.

Film Casting and Drying The aqueous solution was cast onto Mylar film by machine or hand using a drawdown bar with a gap of 20-40 mils at a speed of about 1 meter / second. The Mylar film was attached to a 0.50 inch thick glass sheet before solution casting. To dry the pullulan film, the entire assembly (cast, Mylar and glass) was placed in a controlled drying chamber set at 140 ° F. and 30% relative humidity (RH) for 2-3 hours.

Film Conditioning and Testing Prior to testing, films were conditioned for 1-5 (average 3) days in a controlled environment chamber set at 70 ° F. and 50% RH. The sample was transferred to the test area in the Zip-Loc ^R bag. Samples were tested and evaluated for tensile strength (gram weight) and% elongation using a small laboratory Instron physical test unit. In the test, the metal probe at the elliptical tip is pressed against the surface of one firmly held film. The amount of force required to break the film and the distance traveled by the probe to break the film are used to calculate the physical properties.

Pouch production by vacuum forming A die was selected and placed on a table under a vertically movable frame. A piece of film (7 in x 11 in) was placed at the bottom of the frame. The top of the frame was lowered and locked to the bottom. The die was evacuated and the film was lowered to the die and allowed to suck to form a pouch, which was then filled with the selected material.

Heat sealing The second film was gently placed on the pouch. A hot iron (200-300 ° F.) was manually pressed onto both films at the end of the filling area. The iron was held in place for 2-5 seconds.

Moisture sealing A second film was wrapped around the block and quickly pressed onto a wet paper towel. The lightly wet film was pressed onto a preformed pouch for 2-5 seconds.

Example 1
Hayashibara's commercial pullulan (PI-20) was used to produce films with one or more of the following additives: glycerol, propylene glycol (PPG), Sorbitol Special (SorbS; SPI Pharma; 40-55% sorbitol 15-30% anhydrous sorbitol and 1-10% mannitol), Nu-Col 2004 (NC2004; Tate & Lyle modified starch), Star-Dri 5 (Tate & Lyle maltodextrin), MiraSperse 2000 (MS2000; Tate & Lyle modified) Starch), DuraGel (Tate & Lyle modified starch), TenderJel C (Tate & Lyle modified starch) and sodium alginate. Specific compositions are shown in Table 1A.

３種可塑剤（グリセロール、プロピレングリコールおよびSorbitol Special）の組合せを含有するフィルムは、サンプル１‐２および１‐３において高強度で５０％超の伸びを示した。 The results of the film properties test are shown in Table 1B.

Films containing a combination of the three plasticizers (glycerol, propylene glycol and Sorbitol Special) showed high strength and greater than 50% elongation in Samples 1-2 and 1-3.

Example 2
Films were prepared containing pullulan and the additional materials shown in Table 2A.

Tests were conducted to examine the properties of these films and the results are shown in Table 2B.

  Films made of pullulan and STAR-DRI 5 maltodextrin and sodium alginate (and possibly Nu-Col 2004) as the main polymer showed high tensile strength. High elongation was seen with films containing pullulan and glycerol, propylene glycol and sorbitol (and possibly citric acid) as the main polymer. Various thicknesses resulted in films with tensile strengths exceeding 1000 gram weight and elongation at break exceeding 50%.

Example 3
The following films were prepared for testing in an experimental vacuum forming and packaging machine:

Tests were performed to evaluate film properties and the results are shown in Table 3B.

The following dies were used for the vacuum packaging test:
Die 1) Half egg shape: L 2.50 in × W 1.88 in × D 0.69 in—Maximum depth descending taper from end Die 2) Rectangular: L 4.50 in × W 2.75 in × D 0 50in-uniform depth descending straight from the end Die 3) Half tube: L 1.88in x W 0.75in x D 0.50in-Maximum depth descending from end Die 4) 7 pieces Half cylinder: L 2.00in x W 0.75in x D 0.50in-Maximum depth descending from end, each cylinder is 0.38 "apart Die 5) Tapered square: L 1.88in x W 1.88 in x D 0.75 in-maximum depth descending from the end

Various foods were wrapped in the following films to form an edible water-soluble package.
Using Examples 3-1- die # 1 successfully vacuum formed film # 6, he was charged with finely powdered ALLEGGRA ^R FS74 egg product of about 12g in the pouch. Film # 1 was successfully used to close the package with heat sealing.

Example 3-2- Film # 5 was successfully vacuum formed using die # 1, and about 20 g of fine powder Swiss Miss ^R Hot Cocoa Mix was filled in the pouch. Film # 1 was used to close the package, but was unsuccessful due to breakage during heat sealing.

Using Examples 3-3 Die # 1 successfully vacuum formed film # 5, was charged with finely powdered ALLEGGRA ^R FS74 egg product of about 12g in the pouch. Film # 5 was successfully used to close the package with heat sealing.

Example 3-4- Film # 3 was successfully vacuum formed using die # 1 and about 20 g of fine powder Swiss Miss ^R Hot Cocoa Mix was filled in the pouch. Film # 3 was successfully used to close the package with heat sealing.

Using Examples 3-5-die # 1 successfully vacuum formed film # 4, it was filled with fine powder ALLEGGRA ^R FS74 egg product of about 12g in the pouch. Film # 4 was successfully used to close the package with heat sealing.

Example 3-6 Film # 4 was successfully vacuum formed using die # 2, and about 28 g of fine powder Swiss Miss ^R Hot Cocoa Mix was filled in the pouch. Film # 4 was successfully used to close the package with heat sealing. It was later found that this package has micropores in the deep corners of the vacuum forming area.

Example 3-7—Film # 3 was successfully vacuum formed using Die # 2, and about 40 g of fine powder Swiss Miss ^R Hot Cocoa Mix was filled into the pouch. Film # 3 was successfully used to close the package with heat sealing.

Example 3-8—Film # 4 was successfully vacuum formed using Die # 2 and approximately 28 g of fine powder Swiss Miss ^R Hot Cocoa Mix was filled into the pouch. Film # 4 was successfully used to close the package with heat sealing. This package was a reproduction of Examples 5-6 and showed no defects.

  Example 3-9 Film # 1 was unsuccessfully vacuum formed using Die # 2. The film broke into small pieces.

Example 3-10- from a die # 2 successfully vacuum formed film # 2 was filled with fine powder ALLEGGRA ^R FS74 egg product of about 24g in the pouch. Film # 4 was successfully used to close the package with heat sealing. This package was later found to have leaks due to heat sealing defects.

Using Examples 3-11- die # 3 successfully vacuum formed film # 5, he was charged with finely powdered Crystal Light ^R Soft Drink Mix about 5g in the pouch. Film # 4 was successfully used to close the package with heat sealing.

Example 3-12- die # 4 was used to successfully vacuum formed film # 5, was charged with finely powdered Crystal Light ^R Soft Drink Mix about 5 g 7 pieces pouch each. Film # 5 was successfully used to close the package with heat sealing. This film was able to fill a number of adjacent cavities in a single vacuum forming operation.

Example 3-13—Film # 6 was successfully vacuum formed using Die # 4 and approximately ⁷ grams of fine powder Alpine® Spiced Cider Sugar Free Drink Mix was filled into each of the seven pouches. Film # 6 was successfully used to close the package with heat sealing. This film was able to fill a number of adjacent cavities in a single vacuum forming operation.

Using Examples 3-14- die # 4 successfully vacuum formed film # 4, it was filled with finely powdered Easy Mac ^R Cheese Powder of about 5 g 7 pieces pouch each. Film # 4 was successfully used to close the package with heat sealing. This film had a long standing, but it seemed to be at the limit of its elongation and showed audible signs of stress during vacuum forming.

Using Examples 3-15- die # 1 successfully vacuum formed film # 3, he was charged with finely powdered Easy Mac ^R Cheese Powder of about 17g in the pouch. Film # 3 was successfully used to close the package with heat sealing.

Example 3-16- from a die # 1 successfully vacuum formed film # 2 was filled with finely powdered Easy Mac ^R Cheese Powder of about 17g in the pouch. Film # 3 was successfully used to close the package with heat sealing. This package was later found to have leaks due to heat sealing defects.

Using Examples 3-17- die # 2 successfully vacuum formed film # 4, it was filled with finely powdered Easy Mac ^R Cheese Powder of about 40g in the pouch. Film # 4 was successfully used to close the package with heat sealing. This package was later found to have leaks due to heat sealing defects.

Using Examples 3-18- die # 1 successfully vacuum formed film # 3, he was charged with finely powdered Easy Mac ^R Cheese Powder of about 17g in the pouch. Film # 3 was successfully used to close the package with water sealing.

Using Examples 3-19- die # 5 successfully vacuum formed film # 5, he was charged with finely powdered Easy Mac ^R Cheese Powder of about 8g in the pouch. Film # 5 was successfully used to close the package with water sealing.

Using Examples 3-20- die # 5 successfully vacuum formed film # 3 (6 mils), it was charged with finely powdered Easy Mac ^R Cheese Powder of about 8g in the pouch. Film # 3 (6 mil) was successfully used to close the package with water sealing.

Example 3-2 A 2 mil thick blue peppermint flavor film was made using the following materials (all% w / w, ds base): 50% pullulan (PI-20), tapioca dextrin ( F4-800) 13%, glycerol 6%, propylene glycol 13% and sorbitol 19%. Films were formed into small 1/2 inch square pouches using a laboratory impulse sealer. Each pouch was filled with about 0.25 g of strawberry flavored Pop Rocks ^R candy and sealed. Thus, when an edible two-part confection was made in this test, as soon as the film melted in the mouth, the direct flavor of the film was replaced with the flavor and taste characteristics of Pop Rocks ^R candy.

Example 4
A 100 g film solution is prepared by dissolving 15.46 g pullulan in 80 g deionized water. To this is added 1.142 g glycerin, 2.28 g sorbitol, 0.572 g propylene glycol, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate with stirring. Finally, 0.5 g gelatin-1385P was added with stirring. The solution is heated to 70 ° C. for 30 minutes to completely dissolve the gelatin. It is continuously stirred so that the solution cools to room temperature where the gelatin remains in solution. The gel is degassed by standing overnight or centrifuging. The gel is then cast on treated stainless steel and dried to a moisture level of 7.5-9.5%. The film can then be peeled from the steel.

Example 5
A 100 g film solution is prepared by dissolving 14.76 g pullulan in 80 g deionized water. To this is added 1.334 g glycerin, 2.66 g sorbitol, 0.2 g propylene glycol, 1 g NaCl, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate with stirring. The gel is degassed by standing overnight or centrifuging. The gel is then cast on treated stainless steel and dried to a moisture level of 7.5-9.5%. The film can then be peeled from the steel.

Example 6
A 100 g film solution is prepared by dissolving 14.96 g pullulan in 80 g deionized water. To this are added 1.6 g sorbitol, 1.4 g polyethylene glycol, 2 g NaCl, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate with stirring. The gel is degassed by standing overnight or centrifuging. The gel is then cast on treated stainless steel and dried to a moisture level of 7.5-9.5%. The film can then be peeled from the steel.

Example 7
Film samples prepared according to Examples 4-6 (labeled Samples 4a, 5a, and 6a in the table below) were tested to determine their tensile strength and percent elongation at break. The same test was also performed on comparative film samples (labeled as Samples 4b, 5b and 6b in the table below) containing the same material but containing no gelatin or salt.

Film Test Protocol To measure tensile strength and elongation at break, place a sample of film between two aluminum blocks and hold it firmly together with screws and wing nuts. The blocks have five holes of the same pattern drilled in them. A cylindrical probe is attached to the arm of the Instron test unit. The test is performed by driving the probe into the film. Repeat 5 times with 1 test per hole without reloading the sample. Simply reposition the block to align the new hole with the probe. For the calculation, data averaged from all the runs are used.

  Instron software is programmed to start the measurement when 1 gf is recorded in the load cell, and the distance the probe has traveled further through the hole in the bottom plate is recorded. As the probe moves through the hole in the bottom plate, the film expands and finally breaks. The device records not only the deformation, but also the resistance that the film undergoes during the deformation as a gram weight applied to the load cell. Even if the film is pushed rather than pulled in this test, the data can be treated as a conventional tensile test.

Film distortion is examined as follows. The film is stretched between the probe tip and the support end of the block. The initial “length” of the test sample is defined as the hole radius (“a”). The extended length is calculated from this initial length and the distance traveled by the probe. The extended length is essentially the hypotenuse of a right triangle, with the hole radius a as one side of the triangle and the distance b traveled by the probe as the second side. The extended length c (the hypotenuse) of the film is calculated as follows:
c ² = a ² + b ²
c = (a ² + b ² ) ^1/2
The diameter of each hole is 13 mm, so the radius is 6.5 mm. The distortion is calculated as follows:
Strain = (expanded length, c−6.5) /6.5
Elongation is a strain expressed as a percentage rather than a fraction.

The cross-sectional area of the probe tip is 0.0085 cm ² . To calculate the tensile strength, the breaking force or maximum load force is divided by the cross-sectional area. Since the force is recorded in grams, it is divided by 1000 to get the result in Kgf / cm ² . The calculation is as follows:
Tensile strength = maximum force (gf) /0.0085cm ^2/1000

A subjective test is used to measure the blocking properties of the blocking analysis film. For this test, three films are cut out and placed face-to-face on one Mylar and then covered with another Mylar. To press the film, a 1/2 inch thick sheet of glass is placed on the stack. After one week, the film is peeled off and scored for ease of peeling on the following scale:
0: No blocking property 1: Easy separation 2: Separation when a slight force is applied 3: Separation occurs when a considerable amount of force is applied, but it is torn or only one sheet is peeled off.
4: Stick completely. It will not peel off.
The results of these tests are summarized in Table 4 below:

  The data shows that both gelatin and salt can improve elongation. Gelatin films usually require other additives to counteract blocking properties, but gelatin does not degrade as well as similar films, but reduces elongation. The data also show that salt can dramatically improve elongation, and when combined with low levels of plasticizer, it can also greatly improve blocking properties.

Example 8
A 100 g surfactant solution is prepared by dissolving 5 g sodium stearoyl lactate in 95 g isopropyl alcohol. This is then sprayed or applied in a uniform thin layer on stainless steel to evaporate the liquid. The film gel is then cast on the treated surface and allowed to dry.

Example 9
A 100 g surfactant solution is prepared by dissolving 5 g of propylene glycol monostearate in 95 g isopropyl alcohol. This is then sprayed or applied in a uniform thin layer on stainless steel to evaporate the liquid. The film gel is then cast on the treated surface and allowed to dry.

Example 10
A 100 g surfactant solution is prepared by dissolving 5 g sodium lauryl sulfate in 95 g deionized water. This is then sprayed or applied in a uniform thin layer on stainless steel to evaporate the liquid. The film gel is then cast on the treated surface and allowed to dry.

Example 11
A 100 g surfactant solution is prepared by dissolving 5 g Polysorbate-80 in 95 g deionized water. This is then sprayed or applied in a uniform thin layer on stainless steel to evaporate the liquid. The film gel is then cast on the treated surface and allowed to dry.

Example 12
To test the solutions prepared in Examples 8-11, another sheet of stainless steel is wiped with each surfactant solution to evaporate the liquid. This leaves a uniformly coated surface on each stainless steel piece. Six different film gels found difficult to peel with untreated steel were prepared and cast on four different steel surfaces. The film gel was formulated as follows:

Film sample 12-1
A 100 g film solution is prepared by dissolving 14.96 g pullulan in 80 g deionized water. To this is added 2.26 g diglycerol, 2.26 g polyethylene glycol, 0.5 g NaCl, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate with stirring. The gel is degassed by standing overnight or centrifuging. The gel is then cast on four different treated stainless steel sheets and dried to a moisture level of 7.5-9.5%.

Film sample 12-2
A 100 g film solution is prepared by dissolving 14.96 g pullulan in 80 g deionized water. To this is added 1 g diglycerol, 1 g polyethylene glycol, 3 g NaCl, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate with stirring. The gel is degassed by standing overnight or centrifuging. The gel is then cast on four different treated stainless steel sheets and dried to a moisture level of 7.5-9.5%.

Film sample 12-3
A 100 g film solution is prepared by dissolving 14.96 g pullulan in 80 g deionized water. To this is added 2 g diglycerol, 2 g polyethylene glycol, 1 g KCl, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate with stirring. The gel is degassed by standing overnight or centrifuging. The gel is then cast on four different treated stainless steel sheets and dried to a moisture level of 7.5-9.5%.

Film sample 12-4
A 100 g film solution is prepared by dissolving 14.96 g pullulan in 80 g deionized water. To this is added 2 g diglycerol, 2 g polyethylene glycol, 1 g Na ₂ SO ₄ , 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate with stirring. The gel is degassed by standing overnight or centrifuging. The gel is then cast on four different treated stainless steel sheets and dried to a moisture level of 7.5-9.5%.

Film sample 12-5
A 100 g film solution is prepared by dissolving 14.96 g pullulan in 80 g deionized water. To this, 2.26 g diglycerol, 2.26 g sorbitol, 0.5 g NaCl, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate are added with stirring. The gel is degassed by standing overnight or centrifuging. The gel is then cast on four different treated stainless steel sheets and dried to a moisture level of 7.5-9.5%.

Film sample 12-6
A 100 g film solution is prepared by dissolving 14.96 g pullulan in 80 g deionized water. To this, 1.5 g diglycerol, 1.5 g sorbitol, 2 g NaCl, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate are added with stirring. The gel is degassed by standing overnight or centrifuging. The gel is then cast on four different treated stainless steel sheets and dried to a moisture level of 7.5-9.5%.

実施例８および９の溶液が、スチール基材からフィルムの最も容易な剥離を行えた。しかしながら、実施例１０および１１の溶液も全く容易に剥がれ、商業向けセッティングでスチールベルトからの除去にも用いられた。 After drying, all films were cured in an environmental chamber for 18 hours at 22.5 ° C. and 45% relative humidity. The films were then peeled from the stainless steel and ranked for ease of peeling with each film, with 1 being the easiest and 4 being the most difficult. The results are shown in Table 5.

The solutions of Examples 8 and 9 provided the easiest release of the film from the steel substrate. However, the solutions of Examples 10 and 11 also peeled off quite easily and were also used for removal from steel belts in a commercial setting.

Example 13
Films similar to those shown in Examples 1-3 were made. These films were as follows:
Film 13-1. A 100 g film solution is prepared by dissolving 15.26 g pullulan in 80 g deionized water. The solution is heated to 70 ° C. for 30 minutes to completely dissolve the gelatin. The solution is continually stirred so that the gelatin cools to room temperature where it remains in solution. The gel is degassed by standing overnight or centrifuging. The gel is then cast on treated stainless steel and dried to a moisture level of 7.5-9.5%. The film can then be easily peeled from the steel for use.

Film 13-2. A 100 g film solution is prepared by dissolving 15.76 g pullulan in 80 g deionized water. The gel is degassed by standing overnight or centrifuging. The gel is then cast on treated stainless steel and dried to a moisture level of 7.5-9.5%. The film can then be easily peeled from the steel for use.

Film 13-3. A 100 g film solution is prepared by dissolving 15.14 g pullulan in 80 g deionized water. The gel is degassed by standing overnight or centrifuging. The gel is then cast on treated stainless steel and dried to a moisture level of 7.5-9.5%. The film can then be easily peeled from the steel for use.

Film 13-4. A 100 g film solution is prepared by dissolving 16.14 g pullulan in 80 g deionized water. The gel is degassed by standing overnight or centrifuging. The gel is then cast on treated stainless steel and dried to a moisture level of 7.5-9.5%. The film can then be easily peeled from the steel for use.

Film 13-5. Prepare a 100 g film solution by dissolving 17.14 g pullulan in 80 g deionized water. The gel is degassed by standing overnight or centrifuging. The gel is then cast on treated stainless steel and dried to a moisture level of 7.5-9.5%. The film can then be easily peeled from the steel for use.

These five films were subjected to a tensile test with an Instron 5542 tester by ASTM D882 method using Bluehill 2 software. The gauge length, film thickness and strain rate used for each test are shown in the table below. Multiple samples are run on each film and the resulting data is calculated by the software. The tensile strength and elongation at break of each film are determined from these calculations. The results are shown in Table 6 below.

  As can be seen in the table above, both gelatin and salt greatly improve pullulan film elongation. Films 13-1 and 13-2, both containing 21% plasticizer, showed significantly different elongation values. In the absence of gelatin (film 2) the film has a breaking elongation of only 8.4% and in the presence of gelatin the breaking elongation increases to 150.3%. Films 13-3, 13-4 and 13-5, all containing only 14% plasticizer, also exhibit widely different elongations. At this low plasticizer level, little increase in elongation is seen when only 5% salt is added. However, when 10% salt is added, the breaking elongation jumps to 110%. These high levels of salt greatly reduced strength. The addition of 5% salt with a slightly higher level of traditional plasticizer film also exhibits fairly good elongation, as seen in the previous examples.

Example 14
A 100 g film solution is prepared by dissolving 15.56 g pullulan in 80 g deionized water. To this solution is added 1.20 g glycerin, 3.2 g polyethylene glycol (PEG) 200, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate with stirring. Stirring is continued at room temperature until the gel is uniform consistency. The gel is degassed by standing overnight or centrifuging. The gel is then cast onto a stainless steel surface treated with 2% sodium stearoyl lactate (SSL) dissolved in isopropanol. The cast film is dried to a moisture level of 7.5-9.5%. The film can then be easily peeled from the steel for evaluation and use.

Example 15
A 100 g film solution is prepared by dissolving 15.36 g pullulan in 79.72 g deionized water. To this solution is added 1.20 g glycerin, 3.2 g PEG200, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80, 0.02 g sodium benzoate and 0.48 g of 41.5% paraffin wax emulsion with stirring. . Stirring is continued at room temperature until the gel is uniform consistency. The gel is degassed by standing overnight or centrifuging. The gel is then cast on a stainless steel surface treated with 2% SSL dissolved in isopropanol. The cast film is dried to a moisture level of 7.5-9.5%. The film can then be easily peeled from the steel for evaluation and use.

Example 16
A 100 g film solution is prepared by dissolving 15.16 g pullulan in 79.44 g deionized water. To this solution is added 1.20 g glycerin, 3.2 g PEG200, 0.01 g sodium lauryl sulfate, 0.01 g Polysorbate-80, 0.02 g sodium benzoate and 0.96 g of 41.5% paraffin wax emulsion with stirring. . Stirring is continued at room temperature until the gel is uniform consistency. The gel is degassed by standing overnight or centrifuging. The gel is then cast on a stainless steel surface treated with 2% SSL dissolved in isopropanol. The cast film is dried to a moisture level of 7.5-9.5%. The film can then be easily peeled from the steel for evaluation and use.

Example 17
A 100 g film solution is prepared by dissolving 20.447 g pullulan in 72.190 g deionized water. To this solution was added 1.080 g glycerin, 2.160 g PEG200, 2.700 g sorbitol, 0.054 g 10% food grade silicone emulsion, 0.014 g Polysorbate-80, 0.027 g sodium benzoate and 1.301 g 41.5. % Paraffin wax emulsion is added with stirring. Stirring is continued at room temperature until the gel is uniform consistency. The gel is degassed by standing overnight or centrifuging. The gel is then cast on a stainless steel surface treated with 2% SSL dissolved in isopropanol. The cast film is dried to a moisture level of 7.5-9.5%. The film can then be easily peeled from the steel for evaluation and use.

Example 18
A 100 g film solution is prepared by dissolving 15.36 g pullulan in 79.96 g deionized water. To this solution is added 1.00 g glycerin, 2.40 g PEG200, 1.20 g sorbitol, 0.04 g 10% food grade silicone emulsion, 0.01 g Polysorbate-80 and 0.02 g sodium benzoate with stirring. Stirring is continued at room temperature until the gel is uniform consistency. The gel is degassed by standing overnight or centrifuging. The gel is then cast on a stainless steel surface treated with 2% SSL dissolved in isopropanol. The cast film is dried to a moisture level of 7.5-9.5%. The film can then be easily peeled from the steel for evaluation and use.
These five formulations (Examples 14-18) are examples of wax-containing pullulan film formulations and their wax-free analogs.

Example 19
Polymer thin films may exhibit a tendency to self-adhere or “block” under pressure. Films that do not show this tendency are cast and rolled themselves without backing or support. To test self-adhesion on pullulan film, a relatively quick and easy analytical procedure has been developed: 3 "cut out from 3" cast pullulan film in all directions, from closed side to open side in staggered arrangement Stacked on a Mylar sheet, to prevent the square film from sticking to other surfaces, the stacked sample was covered with a second Mylar sheet, in order to apply a pressure similar to that when the film was rolled up by itself, Five 22 ″ × 14 ″ × 0.5 ″ sheets of glass were placed on the stacked sample lot. Samples were examined after 24 hours to assess the level of surface blocking or the degree to which each of the three square samples adhered to each other. Samples that did not irreversibly adhere to each other after 24 hours were re-evaluated after 1 week.

プルランフィルム処方中ワックス含有率の増加が自己接着する傾向を減少させることは、表７のデータから明らかである。 Test results were displayed by scoring on a 5-point scale:
0-No surface adhesion 1-Film sticks, but all three squares peel with minimal force 2- Film sticks, but all three squares peel with moderate force 3- Film sticks All three squares peel off with considerable force and damage the film. 4-3 All squares adhere completely and do not separate. Using this test procedure, detailed in Examples 14-16. The blocking scores of the films are as follows:

It is clear from the data in Table 7 that increasing wax content in the pullulan film formulation reduces the tendency to self-adhere.

Example 20
In many commercial packaging operations, film packages are heat sealed to close them. In order to measure the ability of a pullulan film that can be sealed with heat, the following test was conducted. For this purpose, 2 "x 0.5" film pieces were sealed together in three different directions and then pulled apart by hand. The film was sealed with open face to open face (front to front), closed face to closed face (back to back) and open face to closed face (front to back).

The seal was evaluated on a 5-point scale:
0-The film breaks before the seal is peeled 1-The seal is partially peeled before the film is broken-2-The seal is completely peeled off by force; the film is not broken-3-The seal is peeled completely by the least force; 4- Film does not form any seals Using this test method, the heat seal scores of the films detailed in Examples 14-16 are as follows:

  The data in Table 8 shows that the presence of wax in the pullulan film formulation increases the ability of the film to form a strong seal. Secondly, the results also show that the seal on the closed surface of the film indicated by “B” was not as good as the seal formed by the open and open surfaces. In Example 14, the only difference between the closed and open surfaces of the film is the presence of SSL on the closed surface. SSL therefore appears to be involved in reducing the seal strength when the treated surface is involved. The decrease in seal strength that occurs only when the closed surface is involved is an indication that SSL is immiscible with the aqueous cast gel and remains present on the closed surface.

Example 21
In the commercial packaging field, the film is passed through the machine in such a way that the film exhibits a certain level of slip so that the packaging proceeds correctly. The degree of slip is displayed as a coefficient of friction.

This test is performed on an Instron 5542 using a coefficient of friction attachment (Model # 2810-005). The test follows ASTM D1894 and utilizes Bluehill 2 software for method control and analysis. In this manner, a thread (2.5 in ² , 200 g) is wrapped with the film to be tested and placed on a test bench. Cover the test bench with the desired test substance. The film is covered with a film to test the film slip with film, and it is also covered with a stainless steel sheet (4.5 ″ × 15 ″) to test the film slip with steel. The thread is then pulled along the platform by a tow line at a speed of 150 mm / min. Connect the toe line to the Instron load cell with a hook assembly and measure the force required to pull the sled.

  Three runs are made for each complete test and the results are averaged for final calculation. The coefficient of friction is calculated by dividing the force required to pull the thread by the weight of the thread. The coefficient of static friction is the amount of force required to initiate sled movement and is calculated using the maximum force from the first peak. The dynamic coefficient of friction is defined as the force required to maintain sled movement and is calculated by averaging the force in the next 10 inch test and dividing it by the sled weight. All calculations are done with Bluehill 2 software.

A summary of friction coefficient test results for wax-containing pullulan films and petrochemical-based films for use in commercial packaging operations is as follows:

  The data shown in Table 9 shows that the waxless pullulan film has a higher coefficient of friction and thus much less slip than the wax-containing film or the film obtained from a commercial packer. Second, even though the waxless film has less slip in all front surface related tests, the test involving only the back surface has a CoF value similar to the equivalent test for the wax-containing film. This suggests that SSL is involved in the slip properties of the back of the film. Third, the CoF value of the wax-containing film is similar to that in most cases and better than that for films currently used in commercial packers.

Example 22
Visual evidence for the three-layer structure of the film produced as described above was obtained using an Olympic BX-51 optical microscope. The film surface was viewed at 40 × magnification under reflected partially and fully cross-polarized light. The surface of the pullulan film without wax, which was not cast on the surface treated with SSL, was smooth and relatively featureless when viewed under both reflected and slightly cross-polarized reflected light. There was no evidence of any crystalline material on the film surface.

  The open or top surface of a pullulan film containing wax cast on a surface treated with SSL had coarse grain wax domains that were clearly visible when viewed under reflective fully crossed polarized light. The absence of SSL fine crystals was also noticed on this surface.

  The closed surface of the film described in the previous paragraph was viewed again under similar light conditions. There was no visual evidence of rough wax domains on this surface of the film, but SSL microcrystals could be seen. From these observations, it can be seen that the SSL particles remain on the closed surface of the film while the wax particles collect on the open surface of the film, leaving a simple plasticized pullulan layer therebetween. This tri-layer structure was obtained with a single coating on the treated surface, but with multiple coatings as required by the processing conditions and the planned coating method.

Example 23
Six different water soluble proteins were tested for their use in film. These films consist of 18.575 g pullulan, 1.875 g glycerol, 3.625 g sorbitol, 0.25 g propylene glycol, 0.025 g sodium lauryl sulfate, 0.025 g sodium benzoate and 0.625 g of one of the following water soluble proteins: All were made by dissolving the seeds in 75 g of water:
a) Gelatin 1385P made by Nitta Gelatin
b) Instagel made by PB Gelatins
c) Hydrolyzed pea protein Promois WJ from Seiwa Kasei Co., LTD
d) Hydrolyzed soy protein Promois WS from Seiwa Kasei Co., LTD
e) Hydrolyzed sesame protein Promois SIG from Seiwa Kasei Co., LTD
f) Promois Hydromilk from Seiwa Kasei Co., LTD
The resulting gel was degassed, cast onto stainless steel and dried in an environmental chamber for 1 hour and 15 minutes at 65 ° C. and 25% relative humidity. The chamber was then reset to 22.5 ° C. and 45% relative humidity for overnight curing. The film was then removed from the steel and tested. Tensile strength and elongation were all tested by probe method with Instron apparatus and moisture by Karl Fischer oven method analysis.

The previous examples show that gelatin acts to improve elongation without a significant decrease in tensile strength. These other proteins were tested to see if other water soluble proteins had the same type of effects on mechanical properties. The results are shown in Table 10 below.

  None of the proteins tested worked as well as gelatin. They all reduced elongation and most of them also reduced tensile strength. However, these proteins were successfully added to the gel without gelling.

Edible film formulations containing various salts The previous examples show that the addition of table salt NaCl significantly improves the elongation with pullulan films. Other salts were also tested at various concentration levels to see if they had a similar effect on pullulan film. The films of Examples 24-28 were made as described and then tested. Tests included mechanical testing by Instron probe method, Karl Fischer moisture analysis and dissolution testing.

  In order to quickly investigate the solubility of pullulan film, a test method called “rapid dissolution analysis” was developed. The method simply uses a stopwatch, stir plate, beaker, stir bar and thermometer. The temperature of the water used in the cold water test is in the range of 5-15 ° C, and in the hot water test it is in the range of 65-75 ° C. Place hot or cold water beaker on stir plate and stir at medium pace. Measure and record the temperature with a thermometer. Cut out a film about 1 inch square and drop it in water. Start the timer as soon as the film enters the water. Record the time the film is completely dissolved. Clean the equipment and obtain fresh water before starting the next test.

Example 24
A film containing no salt was first prepared for use as a control. This film was made by dissolving 19.7125 g pullulan, 0.75 g glycerol, 2.5 g sorbitol, 2 g polyethylene glycol (200 MW), 0.0125 g sodium lauryl sulfate and 0.025 g sodium benzoate in 75 g water. . The gel was cast on stainless steel and dried in an environmental chamber for 1 hour and 15 minutes at 65 ° C. and 25% relative humidity. The chamber was then reset to 22.5 ° C. and 45% relative humidity for overnight curing. The film was then removed from the steel and tested.

Example 25
Three films containing 1.25% (dsb) of three different salts were made. These films consist of 19.4 g pullulan, 0.75 g glycerol, 2.5 g sorbitol, 2 g polyethylene glycol (200 MW), 0.0125 g sodium lauryl sulfate, 0.025 g sodium benzoate and 0.3125 g of one of the following salts: Was dissolved in 75 g of water.
NaCl
MgCl ₂
CaCl ₂
All gels were cast on stainless steel and dried in an environmental chamber at 65 ° C. and 25% relative humidity for 1 hour and 15 minutes. The chamber was then reset to 22.5 ° C. and 45% relative humidity for overnight curing. The film was then removed from the steel and tested.

Example 26
Six films containing 2.5% of six different salts were made. These films consist of 19.0875 g pullulan, 0.75 g glycerol, 2.5 g sorbitol, 2 g polyethylene glycol (200 MW), 0.0125 g sodium lauryl sulfate, 0.025 g sodium benzoate and 0.625 g of the following salts: Was dissolved in 75 g of water.
NaCl
MgCl ₂
CaCl ₂
KCl
LiCl
Na ₂ SO ₄
All gels were cast on stainless steel and dried in an environmental chamber at 65 ° C. and 25% relative humidity for 1 hour and 15 minutes. The chamber was then reset to 22.5 ° C. and 45% relative humidity for overnight curing. The film was then removed from the steel and tested.

Example 27
Four films were made containing 5% of four different salts. These films consisted of 18.4625 g pullulan, 0.75 g glycerol, 2.5 g sorbitol, 2 g polyethylene glycol (200 MW), 0.0125 g sodium lauryl sulfate, 0.025 g sodium benzoate and 1.25 g of one of the following salts: Was dissolved in 75 g of water.
NaCl
KCl
LiCl
Na ₂ SO ₄
All gels were cast on stainless steel and dried in an environmental chamber at 65 ° C. and 25% relative humidity for 1 hour and 15 minutes. The chamber was then reset to 22.5 ° C. and 45% relative humidity for overnight curing. The film was then removed from the steel and tested.

Example 28
Films containing combinations of salt NaCl and MgCl _{2 in} different proportions were made. These films were made as follows:
a) This film consists of 19.0875 g pullulan, 0.75 g glycerol, 2.5 g sorbitol, 2 g polyethylene glycol (200 MW), 0.0125 g sodium lauryl sulfate, 0.025 g sodium benzoate, 0.3125 g NaCl and 0.3125 g. It was prepared by dissolving MgCl ₂ in 75 g of water. The gel was cast on stainless steel and dried in an environmental chamber for 1 hour and 15 minutes at 65 ° C. and 25% relative humidity. The chamber was then reset to 22.5 ° C. and 45% relative humidity for overnight curing. The film was then removed from the steel and tested.

b) This film consists of 18.775 g pullulan, 0.75 g glycerol, 2.5 g sorbitol, 2 g polyethylene glycol (200 MW), 0.0125 g sodium lauryl sulfate, 0.025 g sodium benzoate, 0.625 g NaCl and 0.3125 g. It was prepared by dissolving MgCl ₂ in 75 g of water. The gel was cast on stainless steel and dried in an environmental chamber for 1 hour and 15 minutes at 65 ° C. and 25% relative humidity. The chamber was then reset to 22.5 ° C. and 45% relative humidity for overnight curing. The film was then removed from the steel and tested.

注記：すべてのフィルム厚は２．１〜３．１ミルの範囲であった。 A summary of the results from the previous examples is shown below:

Note: All film thicknesses ranged from 2.1 to 3.1 mils.

  In Table 11, examples are categorized by salt content. In most cases, the addition of salt improves elongation while maintaining strength at all levels. The only exception to this is for films containing high levels of calcium chloride and sodium sulfate. It is also clear that the addition of total salt improves the cold water dissolution time. One example of KCl is high because of sample aggregation in water, leading to long dissolution times. It is also important to note that some salt films have significantly higher levels of moisture. Salts tend to retain water and act as a humectant and help improve film elongation.

  It has been found that adding high levels of salt to the film does not always lead to high levels of elongation. Some salts are more susceptible to brittleness in the film at higher levels. For this reason, it is useful to optimize the amount of salt added based on what the salt is added to. Each salt has its own optimal level as determined by routine experimentation. In the case of NaCl, this level is about 2.5%. It should also be noted that the inclusion of high levels of salt does not significantly affect dissolution time with salt. The inclusion of salt improves the dissolution time; however, it is not proportional to the amount of salt added. Calcium chloride and sodium sulfate are two salts that have the least effect on mechanical properties among those tested. Lithium chloride had the greatest influence on the mechanical properties.

Sodium chloride and magnesium chloride appear to give the most consistent results and are routinely used in food. In order to determine the best possible film, the two were combined to see if the two mixtures gave a better film. As shown by the data in Table 12, they improve elongation. However, the addition of high sodium chloride reduces strength and leads to film brittleness. When the film 28a was in a low moisture condition, the film 28a was a good film with good touch, no tackiness and almost no brittleness. A film containing both sodium chloride and magnesium chloride at a concentration of 1.25% was found to give the best results among all the salt-containing films tested so far. However, other salts alone give good results.

Example 29
A pullulan film was cast and dried on a sheet of 2 mil polyester film. The dried pullulan film layer was about 4 mils thick and remained adhered to the polyester substrate. Two 4.5 inch wide rolls of this two-layer structure were placed in a Transwrap vertical fill seal packaging machine with the pullulan layer on the inside (in contact with the filler material) and the polyester layer on the outside. The machine's heat sealing jaws were set at a constant temperature of 125 ° C. The machine was turned on and the bilayer film structure was successfully formed into a 4.5 inch x 5.5 inch pouch containing food filling material. Sealing the pullulan layer to form a food pouch was successfully done by heating through the protective polyester layer. The protective polyester film layer remained adhered to the final pouch, but was easily removed from the pouch before using the edible pouch and its contents for cooking.

  The preceding description of certain aspects of the invention is not an exhaustive list of all possible aspects. Those skilled in the art will recognize that modifications may be made to the specific embodiments described herein that fall within the scope of the following claims.

1 is a schematic view of a multilayer film according to one embodiment of the present invention. 1 is a schematic view of a film on a peelable flexible substrate, according to one embodiment of the invention. FIG. 1 is a schematic view of a pouch made of a film according to one embodiment of the present invention containing food.

Claims (114)

  An edible article comprising a food and a water-soluble film surrounding the food, wherein the film is a major amount of pullulan on a dry solid basis and a small amount of two or more selected from glycerol, propylene glycol, sorbitol and polyethylene glycol An edible article consisting essentially of:   The edible article according to claim 1, wherein the film comprises about 35-80 wt% pullulan on a dry solids basis.   The edible article according to claim 1, wherein the film comprises glycerol, propylene glycol and sorbitol.   4. The edible article according to claim 3, wherein the film comprises about 1-30% by weight glycerol, about 1-30% propylene glycol and about 1-30% sorbitol on a dry solid basis.   The edible article according to claim 1, wherein the film further comprises citric acid.   The edible article according to claim 1, wherein the film further comprises starch or a starch derivative.   The edible article according to claim 6, wherein the starch derivative is dextrin or maltodextrin.   The edible article according to claim 1, wherein the film further comprises alginate, xanthan gum, collagen, polydextrose, or a combination of two or more thereof.   The edible article according to claim 1, wherein the food is selected from powdered beverage mixes, candy, powdered cheese products, powdered egg products, dried soups and casserole mixes, food colors and spices. Preparing a film-forming composition consisting essentially of a major amount of pullulan on a dry solid basis and a small amount of two or more components selected from glycerol, propylene glycol, sorbitol and polyethylene glycol;
A method for producing an edible article comprising forming a film-forming composition into a water-soluble film and wrapping food in the film.   11. The method of claim 10, wherein the film can be stretched in the machine direction at least about 50% without breaking.   11. The method of claim 10, wherein the film can be stretched in the machine direction at least about 100% without breaking.   The method of claim 10, wherein the film-forming composition is formed into a film by casting.   11. The method of claim 10, wherein the food product is wrapped by placing the food product between two films and heat sealing the two films to form a sealed enclosure around the food product.   11. The food product of claim 10, wherein the food product is encased by placing the food product between two films and applying moisture and pressure to at least a portion of the film to form a sealed enclosure around the food product. Method.   The method of claim 10, wherein the food product is wrapped by vacuum forming a film around the food product.   11. The method of claim 10, wherein the film forming composition comprises about 35-80% by weight pullulan on a dry solid basis.   The method of claim 10, wherein the film comprises glycerol, propylene glycol, and sorbitol.   19. The method of claim 18, wherein the film forming composition comprises about 1-30% by weight glycerol, about 1-30% propylene glycol and about 1-30% sorbitol on a dry solid basis.   The method of claim 10, wherein the film-forming composition further comprises citric acid.   The method of claim 10, wherein the film-forming composition further comprises starch or a starch derivative.   The method according to claim 21, wherein the starch derivative is dextrin or maltodextrin.   11. The method of claim 10, wherein the film forming composition further comprises alginate, xanthan gum, collagen, polydextrose, or a combination of two or more thereof.   11. A method according to claim 10, wherein the food is selected from powdered beverage mixes, candy, powdered cheese products, powdered egg products, dried soups and casserole mixes, food colors and spices.   The method of claim 10, wherein the film exhibits a tensile strength greater than 1000 gram weight and an elongation at break greater than 50%.   The film-forming composition further comprises a small amount of an auxiliary polysaccharide selected from the group consisting of alginates, cellulose ethers, modified starches and combinations thereof, wherein the film has a tensile strength exceeding 1000 gram weight and an elongation at break exceeding 50%. The method of claim 10, wherein the rate is indicated.   It consists essentially of a major amount of pullulan on a dry solid basis and a small amount of two or more components selected from glycerol, propylene glycol, sorbitol and polyethylene glycol, and the composition has a tensile strength exceeding 50 gram weight and 50 A water-soluble edible film-forming composition that can be formed into a film having a thickness of less than 2.2 mils exhibiting an elongation at break of greater than%.   Consisting essentially of a major amount of pullulan on a dry solid basis and a small amount of two or more components selected from glycerol, propylene glycol, sorbitol and polyethylene glycol, having a thickness of less than 2.2 mils; A water-soluble edible film wherein the film exhibits a tensile strength exceeding 1000 gram weight and an elongation at break exceeding 50%.   A major amount of pullulan on a dry solid basis and a small amount of (i) an auxiliary polysaccharide selected from the group consisting of alginates, cellulose ethers, modified starches and combinations thereof, and (ii) glycerol, propylene glycol, sorbitol and polyethylene A thickness of less than 2.2 mils consisting essentially of two or more components selected from the group consisting of glycols, wherein the composition exhibits a tensile strength greater than 1000 gram weight and an elongation at break greater than 50%. A water-soluble edible film-forming composition that can be formed into a film.   A major amount of pullulan on a dry solid basis and a minor amount of (i) an auxiliary polysaccharide selected from the group consisting of alginates, cellulose ethers, modified starches and combinations thereof, and (ii) glycerol, propylene glycol, sorbitol and polyethylene Consisting essentially of two or more components selected from the group consisting of glycols, having a thickness of less than 2.2 mils, a tensile strength exceeding 1000 gram weight and an elongation at break exceeding 50% A water-soluble edible film.   An edible article comprising a food and a water-soluble film surrounding the food, wherein the film is a major amount of pullulan on a dry solid basis and a small amount of two or more selected from glycerol, propylene glycol, sorbitol and polyethylene glycol An edible article wherein the film has a thickness of less than 2.2 mils and exhibits a tensile strength greater than 1000 gram weight and an elongation at break greater than 50%.   32. The edible article according to claim 31, wherein the film further comprises a small amount of auxiliary polysaccharide selected from the group consisting of alginates, cellulose ethers, modified starches and combinations thereof. A major amount of pullulan on a dry solid basis;
With gelatin,
A water-soluble edible film comprising at least two of glycerol, propylene glycol, sorbitol and polyethylene glycol.   34. The film of claim 33, wherein the film comprises about 35-80% by weight pullulan on a dry solid basis.   34. The film of claim 33, wherein the film comprises about 0.5-22.5 wt% gelatin on a dry solid basis.   34. A film according to claim 33, wherein the film comprises glycerol, propylene glycol and sorbitol.   38. The film of claim 36, wherein the film comprises about 1-30% by weight glycerol, about 1-30% propylene glycol, and about 1-30% sorbitol on a dry solid basis.   34. A film according to claim 33, further comprising at least one salt.   40. The film of claim 38, wherein the at least one salt comprises NaCl.   40. The film of claim 38, wherein the at least one salt is present in the film at a concentration of about 0.3 to 15% by weight on a dry solid basis.   40. The film of claim 38, further comprising at least one internal film release agent.   42. The film of claim 41, wherein the at least one internal film release agent comprises polyoxyethylene sorbitan monooleate, sodium lauryl sulfate, or combinations thereof.   43. An edible article comprising a food and the water-soluble film according to any one of claims 33 to 42, which wraps the food.   44. The edible article according to claim 43, wherein the food is selected from powdered beverage mixes, candy, powdered cheese products, powdered egg products, dried soups and casserole mixes, food colors and spices. (A) a major amount of pullulan on a dry solid basis;
With gelatin,
Preparing a film-forming composition comprising at least two of glycerol, propylene glycol, sorbitol and polyethylene glycol;
(B) coating the substrate with a solution or suspension comprising at least one surfactant; and (c) casting the film-forming composition onto the substrate. A method for producing a film.   The at least one surfactant comprises propylene glycol monostearate, sodium stearoyl lactate, polyoxyethylene sorbitan monooleate, sodium lauryl sulfate, at least one salt of stearic acid, or a combination thereof. 45. The method according to 45.   46. The method of claim 45, wherein the film-forming composition comprises about 35-80% by weight pullulan on a dry solid basis.   46. The method of claim 45, wherein the film-forming composition comprises about 0.5-22.5% gelatin by weight on a dry solid basis.   46. The method of claim 45, wherein the film forming composition comprises glycerol, propylene glycol and sorbitol.   50. The method of claim 49, wherein the film-forming composition comprises about 1-30% by weight glycerol, about 1-30% propylene glycol and about 1-30% sorbitol on a dry solid basis.   46. The method of claim 45, wherein the film-forming composition further comprises at least one salt.   52. The method of claim 51, wherein the at least one salt comprises NaCl.   52. The method of claim 51, wherein the at least one salt is present in the film-forming composition at a concentration of about 0.3 to 15% by weight on a dry solid basis.   46. The method of claim 45, wherein the film forming composition further comprises at least one internal film release agent.   55. The method of claim 54, wherein the at least one internal film release agent comprises polyoxyethylene sorbitan monooleate, sodium lauryl sulfate, or a combination thereof. A water-soluble film is formed according to the method according to any one of claims 45 to 55,
A method for producing an edible article comprising wrapping food in the film.   57. The method of claim 56, wherein the film can be stretched in the machine direction by at least about 50% without breaking.   57. The method of claim 56, wherein the food is wrapped by placing the food between two films and heat sealing the two films to form an encapsulated seal around the food.   57. The food product is wrapped by placing the food product between two films and applying moisture and pressure to at least a portion of the film to form an encapsulated seal around the food product. Method.   57. The method of claim 56, wherein the food product is wrapped by vacuum forming a film around the food product.   57. The method of claim 56, wherein the food is selected from powdered beverage mixes, candy, powdered cheese products, powdered egg products, dried soups and casserole mixes, food colors and spices. A first layer comprising a major amount of at least one food wax;
A second layer comprising a major amount of pullulan and further comprising at least one plasticizer;
A third that is substantially immiscible with the aqueous pullulan composition, but comprises at least one surfactant that adheres to the pullulan surface, wherein the at least one surfactant is at least partially crystalline. An edible film comprising a layer.   64. The film of claim 62, wherein the at least one surfactant comprises sodium stearoyl lactate.   64. The film of claim 62, wherein the second layer further comprises food wax particles.   64. The film of claim 62, wherein the second layer comprises about 35-80 wt% pullulan on a dry solids basis.   64. The film of claim 62, wherein the plasticizer in the second layer comprises at least two of glycerol, propylene glycol, sorbitol and polyethylene glycol.   64. The film of claim 62, wherein the second layer comprises about 0.5-22.5% gelatin by weight on a dry solid basis.   64. The film of claim 62, wherein the second layer further comprises starch, starch derivatives, alginate, xanthan gum, collagen, polydextrose, or a combination of two or more thereof.   64. The film of claim 62, wherein the second layer comprises glycerol, propylene glycol and sorbitol.   70. The film of claim 69, wherein the second layer comprises, on a dry solid basis, about 1-30% by weight glycerol, about 1-30% propylene glycol, and about 1-30% sorbitol.   64. The film of claim 62, wherein the second layer further comprises at least one salt. At least one salt comprises NaCl, the MgCl ₂ or a combination thereof The film of claim 71.   72. The film of claim 71, wherein the at least one salt is present in the second layer at a concentration of about 0.3 to 15% by weight on a dry solid basis.   64. The film of claim 62, wherein the at least one surfactant is about 0.001 to 0.1% by weight of the film.   75. An edible article comprising a food and the edible film according to any one of claims 62 to 74, which wraps the food.   76. The edible article according to claim 75, wherein the food is selected from powdered beverage mixes, candy, powdered cheese products, powdered egg products, dried soups and casserole mixes, food colors and spices. A method for producing an edible film comprising:
Applying to the substrate a solution or suspension comprising a major amount of at least one surfactant that is substantially immiscible with the aqueous pullulan composition;
Drying or concentrating the solution or suspension to form a first layer comprising a major amount of a dry surfactant that is at least partially crystalline;
Applying an aqueous solution or suspension comprising pullulan, at least one plasticizer, and at least one food grade wax to the dry surfactant layer, and drying or concentrating the aqueous solution or suspension Thereby forming a second layer and a third layer, the second layer being on the first layer, the third layer being on the second layer, the second layer being a plasticizer and a major amount of pullulan. And the third layer comprises a major amount of food grade wax.   78. The method of claim 77, wherein the at least one surfactant comprises sodium stearoyl lactate.   78. The method of claim 77, wherein the second layer further comprises food wax particles.   78. The method of claim 77, wherein the second layer comprises about 35-80% by weight pullulan on a dry solids basis.   78. The method of claim 77, wherein the plasticizer in the second layer comprises at least two of glycerol, propylene glycol, sorbitol and polyethylene glycol.   78. The method of claim 77, wherein the second layer comprises about 0.5-22.5% gelatin by weight on a dry solid basis.   78. The method of claim 77, wherein the second layer further comprises starch, starch derivatives, alginate, xanthan gum, collagen, polydextrose, or a combination of two or more thereof.   78. The method of claim 77, wherein the second layer comprises glycerol, propylene glycol, and sorbitol.   85. The method of claim 84, wherein the second layer comprises about 1-30% by weight glycerol, about 1-30% propylene glycol and about 1-30% sorbitol on a dry solid basis.   78. The method of claim 77, wherein the second layer further comprises at least one salt. At least one salt comprises NaCl, the MgCl ₂ or a combination thereof The method of claim 86.   87. The method of claim 86, wherein the at least one salt is present in the second layer at a concentration of about 0.3-15% by weight on a dry solid basis. A major amount of pullulan on a dry solid basis;
At least one salt;
An edible film comprising at least one plasticizer.   90. A film according to claim 89, wherein the film comprises at least two salts. At least two salts comprising NaCl and MgCl _2, the film of claim 90.   90. The film of claim 89, wherein the at least one salt is present in the film at a concentration of about 0.3 to 15% by weight on a dry solid basis.   90. The film of claim 89, wherein the at least one plasticizer is selected from glycerol, propylene glycol, sorbitol, polyethylene glycol, and combinations thereof.   94. The film of claim 93, wherein the film comprises at least two of glycerol, propylene glycol, sorbitol and polyethylene glycol.   90. The film of claim 89, wherein the film comprises about 35-80% by weight pullulan on a dry solids basis.   90. The film of claim 89, wherein the film comprises about 0.5-22.5% gelatin by weight on a dry solid basis.   90. The film of claim 89, further comprising at least one internal film release agent.   98. The film of claim 97, wherein the at least one internal film release agent comprises polyoxyethylene sorbitan monooleate, sodium lauryl sulfate, or a combination thereof.   99. An edible article comprising a food and the edible film according to any one of claims 89 to 98, which wraps the food. A film structure comprising an edible film bonded to a peelable flexible substrate, the edible film comprising:
A major amount of pullulan on a dry solid basis;
A film structure comprising at least one plasticizer.   101. The film structure of claim 100, wherein the flexible substrate is a polymer film.   The film structure according to claim 100, wherein the flexible substrate is a polyester film.   101. The film structure of claim 100, wherein the edible film comprises at least one salt.   104. The film structure of claim 103, wherein the edible film comprises at least two salts. At least two salts, comprising the NaCl and MgCl _2, the film structure of claim 104.     104. The film structure of claim 103, wherein the at least one salt is present in the edible film at a concentration of about 0.3-15% by weight on a dry solid basis.   101. The film structure of claim 100, wherein the at least one plasticizer is selected from glycerol, propylene glycol, sorbitol, polyethylene glycol, and combinations thereof.   108. The film structure of claim 107, wherein the film comprises at least two of glycerol, propylene glycol, sorbitol and polyethylene glycol.   101. The film structure of claim 100, wherein the edible film comprises about 35-80% by weight pullulan on a dry solid basis.   101. The film structure of claim 100, wherein the edible film comprises about 0.5-22.5 wt% gelatin on a dry solid basis.   101. The film structure of claim 100, further comprising at least one internal film release agent.   112. The film structure of claim 111, wherein the at least one internal film release agent comprises polyoxyethylene sorbitan monooleate, sodium lauryl sulfate, or combinations thereof.   112. The film structure of claim 111, wherein the flexible substrate comprises a biodegradable polymer film.   114. The film structure of claim 113, wherein the biodegradable polymer film comprises polylactic acid, polyglycolic acid, a copolymer of lactic acid and glycolic acid, or a mixture of two or more thereof.

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