Natural packaging composition

Abstract

To provide a packaging material composition which can be biodegradable and water-soluble.SOLUTION: The packaging material can comprise a biodegradable nonionic polysaccharide, a biodegradable ionic polysaccharide, and a plasticizer. Optionally, additional ingredients may be added to the packaging material for desired purposes. Additional components may include biocides, clays, metal oxides (i.e. titanium dioxide and zinc oxide), modified nanoclays, one or more crosslinking agents, other functional agents, and residual solvents from the packaging material manufacturing process.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] REFERENCE TO RELATED APPLICATIONS This application is filed November 27, 2019, and is incorporated herein by reference in its entirety. This application claims the benefit of U.S. Provisional Application No. 62 / 941,015. [Background technology]

[0002] Currently, we are seeing an explosion in packaging materials, driven by demand for convenient delivery, single-use doses, and They provide a safe and sterile handling solution. This has been exacerbated by the rapid expansion of the courier industry. The challenges of sorting and recycling plastics, and the impact on the environment, particularly in e-commerce applications, are becoming more prevalent. Due to the increasing diversity of mixed package streams found in applications, There are currently difficulties in optimizing the final fate of food. Most conventional packaging materials They are made from petroleum-based thermoplastic resins for their convenience and low cost. The large use of plastics means that they are non-degradable and come from non-renewable resources. It is one of the widely used environmentally persistent polymers. The first is polyvinyl alcohol (PVA), whose market size exceeded $700 million in 2016. , and is projected to exceed $1.2 billion by 2025.

[0003] PVA is a synthetic water-soluble resin, generally produced by hydrolysis of polyvinyl acetate. The various properties of VA depend on its degree of hydrolysis and, to some extent, on the degree of polymerization. For example, fully hydrolyzed PVA (having less than 2% acetyl groups by weight) is a highly crystalline polymer that is soluble only in water above about 60°C, while the acetyl groups PVA with a higher weight percent of is less crystalline and can be easily dissolved in water at room temperature. The melting point and mechanical properties can also be adjusted in a similar manner.

[0004] Due to its properties, PVA is one of the most widely studied water-soluble film-forming polymers. One exemplary application is for laundry detergent pods and other no-contact unit dose concentrates. However, the rapid solubility of PVA formulations in such applications is Despite their suitability, PVA and PVA blends are known to be degradable using common environmental organisms. are not shown to be biodegradable and they are generally not used in industrial composting or wastewater facilities. ASTM D6400 for plastics designed to be aerobically composted These formulations do not meet labeling standards such as pod delivery systems. Lumulaminate, micro scrub, capsules, water-soluble films, and "invisible" pa Other challenging plastic situations are also targeted, including capsules that allow for packaging. These films are designed to disappear "in the water" or "before your eyes" However, these "invisible" plastics do not decompose and remain in the environment. They persist in the environment and have the potential to threaten the food chain through ingestion by small organisms.

[0005] Applications include as a safe coating for laundry pods and require a water-soluble film. Biodegradable with tunable properties that allow for use in specific commercial applications. There is a need for a highly biodegradable PVA alternative that is also biodegradable in wastewater and soil environments. The functionality of petroleum-derived synthetic or semi-synthetic commercial materials that are functional but persist in the environment after their end of life The underlying benefits must still be provided.

[0006] All references cited herein, including U.S. patents and U.S. patent application publications, are hereby incorporated by reference in their entirety. is incorporated by reference in its entirety.

[0007] Any mention of trade names or commercial products herein is for the purpose of providing specific information only. and does not imply recommendation or endorsement by the U.S. Department of Agriculture. Summary of the Invention

[0008] According to the present invention, the packaging material composition may be biodegradable and may also be water-soluble or water-dispersible. The packaging material may be a biodegradable nonionic polysaccharide, a biodegradable ionic polysaccharide, and a soluble polysaccharide. Optionally, additional ingredients may be added to the packaging material for desired purposes. Additional ingredients include biocides, clay, metal oxides (i.e., titanium dioxide and Zinc oxide), modified nanoclay, fibers, dyes, pigments, fragrances, one or more crosslinkers, other functional agents , and residual solvents from the packaging manufacturing process.

[0009] According to a further aspect, the non-ionic polysaccharide is pullulan, pullulan derivatives, inulin, Guar, cellulose, konjac, agar, agarose, curdlan, hydroxypropyl Methylcellulose, hydroxyethylcellulose, methylcellulose, hydroxypropyl Cellulose, Hydroxypropyl Guar, Cellulose Acetate, Cellulose Aldehyde , carboxymethyl starch, hydroxypropyl starch, hydroxyethyl starch The ionic polysaccharides can be cellulose, starch, starch acetate, and starch aldehyde. Carboxymethylcellulose, alginate, xanthan gum, gum arabic, tragacanth Starch, locust bean gum, tara gum, carboxymethyl starch, cationic starch chitosan, gelatin, gellan, pectin, and carrageenan. The plasticizers are sorbitol, glycerin, polyethylene glycol, 1,2-propane Diol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol Tandanediol, 1,3-pentanediol, C6-C10 diols, maltodextrin, xylitol thritol, maltitol, mannitol, erythritol, trehalose, isomalt, The resulting composition may be one of: pectin, dextran. Depending on the desired properties of the composition, a plurality of biodegradable nonionic polysaccharides, biodegradable ionic polysaccharides, A combination of different polymers, polymers, and / or plasticizers may be desirable.

[0010] According to another aspect of the present invention, the packaging material comprises a first polysaccharide, a second polysaccharide, and a plasticizer. wherein the first polysaccharide is one of pullulan and pullulan derivatives. The polysaccharides are inulin, guar, cellulose, hydroxypropyl methylcellulose, Hydroxyethyl cellulose, Hydroxypropyl guar, Cellulose acetate, Cellulose a aldehyde, carboxymethyl starch, hydroxypropyl starch, hydroxyethyl Starch, starch acetate, starch aldehyde, carboxymethyl cellulose, alginate starch, xanthan gum, carboxymethyl starch, cationic starch, and chitosan It can be one of the following:

[0011] According to a further embodiment, the packaging composition may be in a solid state. may be biodegradable in at least one environment.

[0012] According to another embodiment, the packaging composition may be attached to a substrate. , water-soluble, water-dispersible, and / or biodegradable. Examples of such substrates include: and water-soluble paper.

[0013] According to a further aspect of the invention, the nonionic polysaccharide is present in an amount of about 20-70% by weight on a dry basis. The ionic polysaccharide may be present at about 1 to 15% by weight on a dry basis, and the plasticizer may be present at about 1 to 15% by weight on a dry basis. In certain embodiments, the hydroxybenzoates may be present in an amount of about 15-30% by weight for a particular application or for a particular purpose in the final product. For specific properties, a narrower range of amounts of each component may be desired.

[0014] According to a further embodiment of the present invention, all components of the packaging material are of food grade quality. Therefore, the packaging material itself may be food grade.

[0015] In accordance with another embodiment of the present invention, a method for making a packaging composition comprises the steps of: and a plasticizer and forming a film from an aqueous solution. The formation of a film from an aqueous solution can be carried out by any known method, such as solvent casting, lamination, or the like. This can be done by extrusion.

[0016] Advantages of embodiments of the present invention will become apparent from the following detailed description of exemplary embodiments.

[0017] The following detailed description should be considered in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0018] [Figure 1] An exemplary Figure 1 shows the structure of cellulose and derivatives.

[0019] [Figure 2] Exemplary Figure 2 shows a schematic diagram of waste cellulose after its lifespan.

[0020] [Figure 3] An exemplary Figure 3 shows the biodegradation of PVA compared to natural polymers in both soil compost and aerobic wastewater.

[0021] [Figure 4] An illustrative Figure 4 shows the biodegradation of cellulose compared to semi-synthetic derivatives in both soil compost and aerobic wastewater.

[0022] [Figure 5] Exemplary Figures 5A-5C plot the effect of different weight percent cellulose aldehyde fiber added to a film structure on modulus (5A), tensile strength (5B), and percent elongation (5C). DETAILED DESCRIPTION OF THE INVENTION

[0023] Aspects of the present invention are set forth in the following description of specific embodiments of the invention and the associated drawings. Alternate embodiments may be devised without departing from the spirit or scope of the invention. Furthermore, well-known elements of the exemplary embodiments of the present invention may be omitted to provide meaningful details of the present invention. In order to avoid obscuring the details, they are not described or omitted. To facilitate resolution, a discussion of some of the terms used herein is provided below.

[0024] As used herein, the word "exemplary" means "serving as an example, instance, or illustration." The embodiments described herein are not intended to be limiting. The described embodiments are not to be construed as preferred or exemplary over other embodiments. It should be understood that this should not necessarily be construed as an advantage. The terms "embodiments," "embodiments," or "invention" refer to all embodiments of the present invention. It is not intended to require that the invention include all of the discussed features, advantages or modes of operation.

[0025] Unless otherwise defined, all technical and scientific terms used herein are defined by the It has the same meaning as commonly understood by a person skilled in the art to which the invention pertains. When used herein, the term "about" means a reference to a quantity, level, value, or amount. The quantity, level, value, etc., fluctuating by about 20%, preferably about 10%, more preferably about 5%. Any methods and materials similar or equivalent to those described herein may be used. Although any of the above methods may be used in the practice or testing of the present invention, preferred methods and The method and materials are explained.

[0026] As used herein, the term "biodegradable" or "biodegradable material" refers to a material that is biodegradable. Chemical decomposition processes convert it into decomposed biomass, CO2, and water within a maximum of 18 months. The biodegradable material according to the present invention refers to a compound or composition that can be converted into a biodegradable material, for example ( Biodegradation in specific environments, such as (but not limited to) industrial compost or marine environments Conforms to applicable ASTM (e.g. D6400) or ISO standards. Thermochemical processes are carried out at temperatures above ambient. The presence of bacteria, microorganisms, and / or aerobic conditions may be involved.

[0027] As a result of thermochemical decomposition, biodegradable materials generally have a biodegradability that can be quantified by standard tests. These types of biodegradable materials exhibit a loss of properties over time (limited may include (but are not limited to) polyhydroxyalkanoates Polyhydroxybutyrate and polylactic acid (including but not limited to), biomass, and polysaccharides Includes:

[0028] As used herein, the term "biomass" refers to organic residues derived from plants. refers to plant-based materials that contain a high percentage of lignocellulosic material, It may refer to a whole object or a part thereof, such as fiber from a plant or plant part.

[0029] Biodegradation is assessed by measuring accumulated CO2 compared to a baseline containing no test substance. CO2 accumulation can be monitored by the thermodynamic end product of the substance consumption. It is a direct measure and one of the most rigorous metrics for assessing complete biodegradation. Even if only the consumption of starting materials is monitored, it is not clear whether the starting materials are consumed but completely mineralized to CO2 (m The possibility that the mineralization has not occurred is not taken into account. Plot of percent mineralization vs. time was well fitted to a pseudo-first-order kinetic model (Equation 1 below, Figures 3 and 4).

number

[0030] First-order reaction rate constant (k obs ) to determine the reaction half-life and prediction of various materials. It is now possible to calculate the lifespan of the material (Table 1 below). As can be seen in Table 1, PVA is not biodegradable. However, alginate, pullulan, and carboxymethylcellulose (CMC) all It is biodegradable. [Table 1]

[0031] The terms "ionic polysaccharides" and "nonionic polysaccharides" refer to polysaccharides that differ in the number of charged units. The ionic polysaccharides of the present invention are those having at least 0.1 charged units per monomer. Ionic polysaccharides have less than 0.1 charged units per monomer. Examples of the hydrophilic polysaccharides include carboxymethylcellulose, alginate, xanthan gum, These include carboxymethyl starch, cationic starch, and chitosan. Examples of nonionic polysaccharides include pullulan, pullulan derivatives, inulin, etc. Polypropylene, Guar, Cellulose, Hydroxypropylmethylcellulose, Hydroxyethylcellulose Sucrose, hydroxypropyl guar, cellulose acetate, cellulose aldehyde, carboxymethyl starch, hydroxypropyl starch, hydroxyethyl starch, Examples include, but are not limited to, tert-butyl acetate, and starchaldehyde.

[0032] As used herein, the term "plasticizer" refers to an agent that increases flexibility and / or modifies the final composition. Plasticizers refer to materials that soften the product. It is a distinct and separate component from at least either of the two polysaccharides.

[0033] As used herein, the term "functional agent" refers to an agent that adds to the properties of the final composition product. Functional agents are materials that enhance or improve the properties of a material. Examples of functional agents include biocides, clays, These include, but are not limited to, metal oxides, dyes, pigments, fragrances, structural enhancers, and crosslinkers. Not determined.

[0034] The term "structure enhancer" refers to a compound added to a film-forming solution or dispersion to enhance the The term refers to a solid material that produces a film. Structure enhancers include crystals, nanocrystals, fibers, fibrils, and nanofibers, such structures The packaging composition may be made of any known material for biodegradable packaging. Ming utilizes only biodegradable structural enhancers.

[0035] Other compounds may be added to the composition as long as they do not substantially interfere with the intended activity and efficacy of the composition. Whether a compound interferes with activity and / or efficacy can be determined, for example, as described below. This can be determined by the procedures used in

[0036] The amounts, percentages, and ranges disclosed herein are not intended to be limiting. Instead, the increments between stated amounts, percentages, and ranges are Specifically contemplated as part of the invention.

[0037] "Optional" or "optionally" means the following: means that an event or circumstance may or may not occur, and the statement includes This means that the situation may or may not occur. The phrase "comprising X" means that the composition may or may not contain X; This description is meant to encompass compositions that contain X and compositions that do not contain X.

[0038] The term "effective amount" of a compound or property provided herein refers to the amount of "Amount" means an amount capable of performing the function of the compound or property in which it is present. As noted above, the exact amount required will vary depending on the compound used and the process observed. It will vary from process to process depending on recognized variables such as process conditions. An "effective amount" cannot be specified; however, one skilled in the art would know using only routine experimentation. An appropriate effective amount can be determined.

[0039] The term "consisting essentially of" refers to a method (or additional methods (or processes) that substantially interfere with the intended activity of the composition process) and can be readily determined by one of ordinary skill in the art (e.g., from consideration of this specification or practice of the invention disclosed herein).

[0040] The inventions illustratively disclosed herein include any inventions not specifically disclosed herein. in the absence of an element (e.g., a method (or process) step or compositional component) It can be preferably implemented.

[0041] According to at least one exemplary embodiment, the present invention provides a biodegradable, water-soluble or The present invention relates to a packaging material composition that is either biodegradable or water-dispersible. In other embodiments, the composition may comprise a carboxylic polysaccharide, a biodegradable ionic polysaccharide, and a plasticizer. The packaging material may include pullulan or a pullulan derivative, a plasticizer, and a second polysaccharide.

[0042] Nonionic polysaccharides include pullulan, pullulan derivatives, inulin, guar, cellulose, Niacin, agar, agarose, curdlan, hydroxypropyl methylcellulose, hydro hydroxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxy Dipropyl guar, cellulose acetate, cellulose aldehyde, carboxymethyl cellulose Starch, Hydroxypropyl Starch, Hydroxyethyl Starch, Starch Acetate , starchaldehyde, and combinations thereof.

[0043] Ionic polysaccharides include carboxymethylcellulose, alginate, xanthan gum, and Gum labia, gum tragacanth, locust bean gum, tara gum, carboxymethyl Tart, cationic starch, chitosan, gelatin, gellan, pectin, carrageenan , and combinations thereof.

[0044] Plasticizers include sorbitol, glycerin, polyethylene glycol, and 1,2-propanediol. 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol ol, 1,3-pentanediol, C6-C10 diols, other polyhydric alcohols, maltodextrin Sugars, xylitol, maltitol, mannitol, erythritol, trehalose , isomalt, other alcohol derivatives, pectin, and dextran. It is possible.

[0045] Optionally, additional ingredients may be added to the packaging material for desired purposes. Biocides, clays, metal oxides (i.e. titanium dioxide and zinc oxide), modified nanoclays Fibers, dyes, pigments, fragrances, one or more cross-linking agents, other functional agents, and packaging material manufacturing processes Biocides may contain residual solvents from the process. Biocides act as preservatives, for example to prevent mold growth. It can function as an antifungal agent.

[0046] In the present invention, the "clay" contained in the film composition is a natural or synthetic clay. "Nanoclay" refers to a layered silicate, which may include any suitable colloidal layered silicate. It refers to clay that has nanoscale particles.

[0047] According to another exemplary embodiment, the present invention provides a biodegradable, water-soluble packaging material composition. The method comprises combining at least two different biodegradable polysaccharides and a plasticizer. and forming a film from the combination. The packaging material may be produced by any known or known method, including solution casting, lamination, or extrusion. can be made using conventional techniques.

[0048] For example, cast films are prepared by evaporation of water over a range of temperatures and times. For example, at room temperature (25°C), It may take several days to form a film, but at temperatures above 100°C, it may take on the order of minutes or seconds. It may be possible to form a film with [Example]

[0049] Example 1: Films and their mechanical properties Film manufacturing

[0050] Glycerin was obtained from ADM. Acticide® MBS was obtained from Thor. Sorbitol Maltodextrin 70% and sorbitol 100% powders were obtained from Ingredion. Aqualon® CMC7LT is a carboxymethylcellulose copolymer with a degree of substitution of 0.7. The alginate Protanal 6650 was obtained from DuPont. Orchids were purchased from NutriScience Innovations. All materials were purified to a standard of 100% purity. It was used without any problems.

[0051] Several different compositions of packaging film were prepared and the films were cast using a solution casting method. The compositions of each film are shown in Tables 2a and 2b below. Table 2a shows the composition of the casting film. Table 2b shows the composition of the coating solution and Table 2b shows the composition of the final film on a dry weight basis. [Table 2-1] [Table 2-2]

[0052] For each film preparation, the liquid and aqueous components were added to DI water and heated to approximately 50-60°C. The remaining ingredients were placed in a homogenizer (Silverson L5M-A) or mixed in other ways. The components were dry mixed together separately from the aqueous solution and then the dry mixture was added to the aqueous solution. The resulting suspension was then heated to just above 50°C. The solution was stirred for 1 hour while maintaining the temperature. The resulting solution was then cast in a silicon mold. The mixture was then dried at 40°C overnight.

[0053] Film characterization

[0054] The tensile properties of the films were tested and compared to commercially available PVA (Solublon), see Table 3 below. [Table 3]

[0055] As can be seen in Table 3, based on the specific composition of ingredients used, the film properties and The film composition can be adjusted (see Tables 2a and 2b). The composition can be further adjusted with additional additives as desired.

[0056] Example 2: Mechanical properties influenced by additives Clay, metal oxide, cellulose fiber, cellulose aldehyde fiber, crosslinking agent, and The effect of adding plasticizers to the films was examined. In all cases, the PVA film was used as a control. and modifying the base film composition to include the indicated additives in the indicated amounts. The effect of additives was investigated by preparing test films. The hydroxybenzoates were added beforehand to ensure uniform distribution within the film, so all of the ingredients listed in the tables below The weight (wt) % given represents the weight % in solution. That information can be used to calculate the dry weight percent. Cut.

[0057] Clay Two types of Laponite® (colloidal layered silicate) and Hectorite The effect of clay powder was investigated and the results are shown in Table 4 below. [Table 4]

[0058] As can be seen in Table 4, when added to the base formulation (171-2), Laponite (registered trademark) The addition of α-methyltrimethylsilane generally increases elongation with a corresponding decrease in modulus and tensile strength. The addition of hectorite increased the modulus and maintained elongation, but had no effect on tensile strength. Without being limited by theory, Laponite® is Due to its ability to disperse within a polymer matrix and generate a gel-like structure when It is possible that it may have such an effect.

[0059] metal oxides By adding titanium dioxide and zinc oxide, the metal oxides contribute to the mechanical properties of the film. The effects of acetaminophen on the hydroxybenzoates were determined and the results are shown in Table 5 below. [Table 5]

[0060] As can be seen in Table 5, the addition of ZnO or TiO2 significantly improved the tensile properties from the base formulation. There was no significant change. At 1 wt% ZnO, the modulus increased slightly.

[0061] cellulose fiber Hemp and eucalyptus nanofibers (cellulose nanofibers, CNF) were prepared and used. , one commercially available source of cellulose nanocrystals (obtained from the University of Maine) and cellulose nanocrystals. Two commercially available sources of fiber (Cellulon L93, CP Kelco; and Exilva, Borregaard) The Exilva fiber was compared to commercially available materials containing microfibrillated cellulose fiber (MFC). ) and may be called as such.

[0062] To prepare hemp and eucalyptus fibers in a dispersed state, the fibers / fibrils must be separated. To facilitate mechanical separation, the fibers were first oxidized to remove anions. This resulted in electrostatic repulsion events between the positively charged cellulose microfibrils. may also remove residual lignin in the pulp.

[0063] To oxidize the fibers, uncut raw hemp and eucalyptus pulp fibers were added to water and mixed. The mixture was stirred to initiate dispersion. The fibers were then treated with 0.08 g of TEMPO(2,2, 6,6-Tetramethylpiperidine-1-oxyl radical catalyst) and 0.5 g of N dissolved in 10 mL of water The two solutions of αBr were added and mixed well. The dispersion was diluted with 6% B12 while maintaining the pH between 9.5 and 11. The amount of bleach solution to be added was 10 mmO per gram of fiber pulp. It was determined that the pH was 1 when NaClO was present. After all the bleach was added, the reaction The pH was maintained at 10 during the reaction process by adding the H solution dropwise. The reaction was continued for 3 hours after the addition of 50 mL of 100% ethanol to stop the oxidation. The pH of the reaction was lowered to 7 by adding HCl solution dropwise to the mixture. Wash with deionized water on a 0.05 µm sieve and resuspend the solid in deionized water in a glass bottle. Ta.

[0064] The oxidized fibers were then separated using mechanical fibrillation. First, the suspended fiber sample was fibrillated at a solids concentration of 0.5% using a homogenizer. and place the container on ice to prevent overheating of the suspension during the high shear mixing process. The suspension was mixed at 8000 rpm for 40 minutes and, upon completion, was added to the mixture for later use as an additive in the film. To add the fibers to the film-forming mixture, the fibers were stored in suspension. A calculated amount of fiber suspension in g / L was added to achieve the desired final concentration in the film. .

[0065] The results of adding various cellulose sources to the films are shown in Table 6 below. [Table 6]

[0066] As can be seen in Table 6, hemp and eucalyptus fibers were used in the base formulation and the commercial cell However, the nanofiber concentration The elongation rate also decreased significantly with increasing densities. This trade-off was not observed in Cellulon L93. This is evident in Exilva. In particular, the addition of 6 wt% eucalyptus CNF changed the modulus by an order of magnitude. This more than doubled the tensile strength.

[0067] Cellulose aldehyde fiber Cellulose fibers are made by oxidizing the C2-C3 carbon atoms of the cellulose ring with NaIO4 (sodium periodate). It can be chemically modified by cleaving the bond to give two aldehyde units. These aldehyde groups can be the basis for various functionalizations of cellulose.

[0068] To prepare cellulose aldehyde fibers, chemically and mechanically separate the fibers as described above. The hemp fibers were suspended in water at a concentration of about 0.33% by weight. 385 mL of the suspension was heated to about 70°C. The solution was heated, then the pH was lowered to 4 using sulfuric acid solution, and finally 1.98 g of NaIO4 (sodium periodate) was added. The reaction beaker was covered with aluminum foil to prevent decomposition of NaIO4. The mixture was completely covered with a lid and mixed with a magnetic stir bar at 260 rpm for 4.5 hours while maintaining the heat at approximately 70°C. After 5 hours, the reaction mixture was washed with deionized water over a 125 μm sieve and then resuspended in deionized water. UV-VIS spectroscopy was used to monitor the concentration of NaIO4 remaining in the reaction mixture. The response completion rate was calculated to be approximately 50%.

[0069] The results of adding cellulose aldehyde fibers to the film are shown in Figures 5A-5C. At ~3 wt%, there is a relatively rapid increase in Young's modulus (modulus) from 20 MPa to about 45 MPa. However, at higher concentrations, especially 8 wt%, this effect appears to plateau. The modulus remains relatively constant. On the other hand, the elongation remains constant at low concentrations, increasing to 8 wt.%. Unlike the cellulose nanofibrils from which they were derived, The aldehyde nanofibers exhibit enhanced modularity without sacrificing elongation properties. Without being limited by theory, this benefit is due to the Between alcohol and acid functional groups and aldehyde groups of cellulose aldehyde nanofibers This may be due to cross-linking.

[0070] Crosslinkers and Plasticizers Polyethylene glycol (PEG) is used as a plasticizer and borax as a cross-linking agent. The effects of these types of additives were investigated, and the results are shown in Table 7 below. [Table 7]

[0071] Notably, the addition of PEG to 171-2 doubled the overall elongation and increased the strength and The modulus either decreased (2.5 wt%) or remained the same (6 wt%), while the 12-1 fill Additives to rubber typically provide higher modulus and Borax at 2.5 or 3 wt.% resulted in either greater tensile strength or greater elongation. In both base solutions, the concentration was in excess compared to the alginate concentration, which The increase in tensile properties is due to the fact that the cross-linking occurs within the polymer matrix. It may be the result of cross-linking (e.g., borax and CMC).

[0072] Looking at the individual mechanical properties, plastic bags, films, bottles, etc. In applications where flexibility is desired, elongation is important. High modulus and tensile strength is required for a more rigid tear- and puncture-resistant structure. and formulations will be beneficial in specific applications depending on their inherent strengths. .

[0073] Example 3: Optical properties of the film One important factor for a soluble film is its transparency. 171-2) is transparent, and the increase in load due to cellulosic fibers is not visible by visual observation. However, both clay additives tested did not have a significant effect on film transparency. The addition of metal oxides gave the resulting film a brownish color. It became clear.

[0074] Example 3: Moisture barrier and uptake Water vapor permeability (WVP) tests were performed in PVC tube cells with a depth of 2.5 cm and an average radius of 1.5 cm. g of anhydrous MgSO4 was used to maintain 0% relative humidity in the permeation cell. All measurements were performed in duplicate. Weight gain was recorded twice daily for 5 days and plotted against time. , the initial slope (g / hr) is obtained, from which it is divided by the area of ​​the exposed film as follows: The water vapor transmission rate (WVTR) was calculated by

number

[0075] Next, WVP was calculated from WVTR as follows:

number

[0076] where:

number

[0077] As can be seen in the table above, clays (bentonite, hectorite, and laponite ( )) provides an improved moisture barrier (lower WVP) compared to the base formulation and Fiber and borax also had similar effects. However, commercially available cellulose fiber and cellulose The aldehyde fibers increased WVP and weakened the moisture barrier.

[0078] A 4.5 cm diameter circular film was cut out and placed in a desiccator at 50% RH. The water uptake of the films was also tested. The water uptake was measured immediately after being placed in a 40°C oven overnight and after the weight After 5 days of constant weight, the weight was recorded. Water uptake was calculated by comparing the final weight and the initial weight (W f and W i ) was calculated as follows:

number

[0079] The results are shown in Table 9 below. [Table 9]

[0080] What is particularly noteworthy about the above data is that the relative moisture uptake trend does not necessarily correspond to the water vapor For example, hectorite had a significant effect, but The addition of Laponite® had no significant effect on uptake.

[0081] Example 4: Film solubility and degradation Tests were conducted to determine the solubility of films according to the present invention compared to commercially available PVA. The test was performed by placing a 30 g sample (thickness ranging from 0.2 to 0.4 mm) in DI water at room temperature. Film composition 12-1 was used as the base film for this test. Various additives to the composition were studied to determine their effect, if any, on solubility. Tests were performed in triplicate and the results were averaged, as shown in Table 10 below. The PVA had a thickness of 0.1 mm. [Table 10]

[0082] As can be seen from Table 10, different additives can significantly affect solubility. In particular, citric acid The formulation containing required treatment with sodium carbonate to dissolve the film in water.

[0083] Additionally, testing was conducted on the ability of the 171-2 formulation to degrade in a marine environment (data available). (Not shown). Tests were performed on the film formulation alone and on the film formulation in a water-soluble paper. As a result, the half-life of the film itself was about 4 days. It was shown that the half-life of the film coated on paper was about one month. This is significantly faster compared to the previous example (shown in Table 1).

[0084] Example 5: Effect of humidity The above experiments were conducted at the same humidity. To test the solubility of the solubility-in-water mixture, 12-1 was used as the base formulation at 40%, 50%, and 90% humidity. Mechanical and water vapor permeability tests were performed on the various formulations (different additions to the base formulation). (Several additives were tested.) The results are shown in Tables 11 and 12 below. [Table 11] [Table 12]

[0085] As can be seen in the table above, there is no consistent overall effect between 40% and 50% humidity, but the relative At 90% humidity, the WVP tends to be higher and the mechanical properties tend to be weaker. However, the percent elongation at break indicates that the material retains its structural integrity even when weakened. It is noted that these films do not deteriorate rapidly, as shown.

[0086] Example 5: Stickiness and Brittleness The film must be balanced between flexibility and brittleness. If it is too flexible, its strength will be compromised. The minimum tends to be high in elongation, while the opposite is true for brittleness. Another important property to consider is its stickiness. If it is too sticky, it will be difficult to handle and stretch. It has a tendency to become distorted, lose strength, and stick to surrounding objects (including the film itself). To address the stickiness of the film, several options were tried.

[0087] Using formulation 58-1 as a base, the amount of maltodextrin and glycerin in it In other studies, the maltodextrin and / or sorbitol were used to modify the Higher levels of these ingredients generally result in higher softening properties. This provides softness and flexibility, but also results in a more adhesive film.

[0088] To compare carboxymethylcellulose (CMC) with alginate, Product 58-1 was used as a base. In general, increasing the level of alginate improved adhesiveness and This resulted in a decrease in modulus and elongation, accompanied by a slight increase in modulus and strength.

[0089] The foregoing description and accompanying drawings illustrate the principles, preferred embodiments and modes of operation of the invention. However, the present invention should not be construed as being limited to the specific embodiments discussed above. Further variations of the above-discussed embodiments will be apparent to those skilled in the art. It will be understood.

[0090] Accordingly, the above-described embodiments should be considered illustrative rather than limiting. Therefore, it is within the skill of the art to make modifications without departing from the scope of the invention as defined by the claims. It should be understood that modifications to these embodiments may be made by those skilled in the art.

Claims

1. Biodegradable nonionic polysaccharides, biodegradable ionic polysaccharides, and plasticizer A packaged composition comprising:

2. The nonionic polysaccharide is pullulan, pullulan derivatives, inulin, guar, cellulose , Konjac, agar, agarose, curdlan, hydroxypropyl methylcellulose, Hydroxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxy Hydroxypropyl guar, cellulose acetate, cellulose aldehyde, carboxymethyl stannous acid starch, hydroxypropyl starch, hydroxyethyl starch, starch acetate, and starchaldehyde. 。

3. The ionic polysaccharide is carboxymethyl cellulose, alginate, xanthan gum , gum arabic, gum tragacanth, locust bean gum, tara gum, carboxymethicone starch, cationic starch, chitosan, gelatin, gellan, pectin, and 10. The packaging composition of claim 1, wherein the at least one of the following is lageenan:

4. The plasticizer is sorbitol, glycerin, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-penta Diol, 1,3-pentanediol, C6-C10 diol, maltodextrin, xylitol Toluitol, maltitol, mannitol, erythritol, trehalose, isomalt, 10. The packaging composition of claim 1, wherein the composition is at least one of cutin and dextran. thing.

5. The composition further comprises a functional agent, wherein the functional agent is selected from the group consisting of biocides, clays, nanoclays, metal oxides, structural The packaging composition of claim 1 , wherein the at least one of the following is a structural enhancer and a cross-linking agent.

6. The functional agent is a biocide, and the biocide is an isothiazolinone, sorbic acid, sol Potassium benzoate, benzoic acid, sodium benzoate, caprylhydroxamic acid, thymol, Kavacrol, 4-isopropyl-3-methylphenol, gallic acid ester, caprylyl At least one of glycerol, ethyl lauroyl arginate, and guanylhydrazone The packaging composition of claim 5 .

7. The functional agent is a clay or nanoclay, and the functional agent is laponite and hectorite.

6. The packaging composition of claim 5, wherein the composition is at least one of the following:

8. The functional agent is a metal oxide, and the metal oxide is selected from the group consisting of titanium dioxide and zinc oxide. The packaging composition of claim 5, wherein the composition is at least one of:

9. The functional agent is a structure enhancing agent, and the structure enhancing agent is cellulose nanofiber, cellulose 5. The method according to claim 4, wherein the cellulose nanocrystals are at least one of cellulose fibers. The packaged composition described.

10. 6. The packaging composition of claim 5, wherein the functional agent is a cross-linking agent, and the cross-linking agent is borax. 。

11. The nonionic polysaccharide is present in an amount of about 20 to 70% by weight on a dry basis, and the ionic polysaccharide is present in an amount of about 20 to 70% by weight on a dry basis. and the plasticizer is present in an amount of about 15 to 30% by weight on a dry basis.

2. The packaging composition of claim 1.

12. The packaging composition of claim 1 , wherein the packaging composition is in a solid state.

13. 13. The packaging composition of claim 12, wherein the packaging composition is biodegradable in at least one environment. packaging composition.

14. The packaging composition of claim 1 , wherein the packaging composition is attached to a substrate.

15. 15. The method of claim 14, wherein the substrate is at least one of water-soluble and water-dispersible. Packaging composition.

16. All of the nonionic polysaccharides, ionic polysaccharides, and plasticizers are food grade.

10. The packaging composition of claim 1, wherein

17. The first polysaccharide, a second polysaccharide, and plasticizer wherein the first polysaccharide is any one of pullulan and pullulan derivatives. packaging composition.

18. The second polysaccharide is selected from the group consisting of inulin, guar, cellulose, hydroxypropyl methylcellulose, and the like. cellulose, hydroxyethyl cellulose, hydroxypropyl guar, cellulose acetate, Lubricating oil, carboxymethyl starch, hydroxypropyl starch, hydrolyzed Dihydroxyethyl starch, starch acetate, starch aldehyde, carboxymethylcellulose Rose, alginate, xanthan gum, carboxymethyl starch, cationic starch 18. The packaging composition of claim 17, wherein the cellulose is at least one of chitosan and chiral cellulose.

19. The plasticizer is sorbitol, glycerin, polyethylene glycol, 1,2-propanediol, ol, 1,3-propanediol, maltodextrin, xylitol, maltitol, Some of the following: thritol, trehalose, isomalt, pectin, and dextran 18. The packaging composition of claim 17, wherein the composition comprises at least one of:

20. The composition further comprises a functional agent, wherein the functional agent is selected from the group consisting of biocides, clays, nanoclays, metal oxides, structural 18. The packaging composition of claim 17, wherein the additive is at least one of a structural enhancer and a cross-linking agent. 。

21. The first polysaccharide is present at about 20-70% by weight on a dry basis, and the second polysaccharide is present at about 20-70% by weight on a dry basis.

18. The composition of claim 17, wherein the composition is present at about 1 to 15% by weight on a dry basis and the plasticizer is present at about 15 to 30% by weight on a dry basis. The packaging composition according to claim 1.

22. (i) A biodegradable nonionic polysaccharide, a biodegradable ionic polysaccharide, and a plasticizer are dissolved in an aqueous solution. Combining it inside, (ii) forming a film from the aqueous solution produced in (i); A method for producing a packaging composition film, comprising:

23. (i) combining a first polysaccharide, a second polysaccharide, and a plasticizer in an aqueous solution; (ii) forming a film from the aqueous solution produced in (i); wherein the first polysaccharide is any one of pullulan and pullulan derivatives. A method for producing a packaging composition film.

24. Forming the film from the aqueous solution can include solvent casting, lamination, and extrusion.

24. The packaging composition filler of claim 22 or 23, wherein the filler is prepared using any of the following methods: Manufacturing method of .

25. A packaged composition produced using the method of claim 22 or the method of claim 23. film.

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