KR20040076150A - Composition of Container Comprising Biodegradable Starch and Manufacturing Method thereof - Google Patents

Abstract

PURPOSE: Provided is a composition for an environmental-friendly container, which is a complete substitute for conventional non-degradable disposable styrofoam containers in terms of functions and utilities, and has improved physical properties. CONSTITUTION: The composition for a biodegradable container comprises starch, a binder and a physical property reinforcing agent, and further comprises at least one component selected from the group consisting of a reactive agent, a filler, a foaming aid, a softening agent, a plasticizer, a binder/physical property reinforcing agent, a releasing agent, a moisturizing agent and a hydrophobicity imparting agent. In a method for manufacturing a biodegradable container, a reactive agent for donating at least hydrophobic functional groups or active functional groups, or a reactive agent for crosslinking starch molecules among themselves or for crosslinking between starch and side materials is mixed with starch as a base material, and the mixture is reacted while the container is formed.

Description

Composition of Container Comprising Biodegradable Starch and Manufacturing Method

The present invention relates to a biodegradable container composition containing starch as a main raw material and a method for producing the same. More specifically, the use and convenient functions are similar to the conventional non-degradable disposable plastic container containers using starch, which is a natural polymer, and / or their physicochemically modified starch, and their physical properties are similar, and their properties are improved. Starch-based disposable container composition that is easily biodegraded by microorganisms do not burden the environment at all, and a method for producing the same.

The increase in population, the development of various consumer products and fast food industries has caused the generation of large quantities of disposable plastic packaging waste, and the environmental pollution caused by the various waste plastics discarded after use is becoming more serious. Existing non-degradable disposable waste plastics that are left or landfilled are not decomposed by microorganisms present in nature, and remain intact, causing soil contamination and reducing the life of landfills. In addition, even if incinerated, it is known that air pollution due to toxic gas and its harmful effects to the human body are also serious. In particular, the non-degradable foam container used as a disposable food packaging container has a large volume per unit weight, which is easily visible and blown by the wind, causing further harm to environmental pollution and controversial social problems due to the controversy of environmental hormones. It caused a great deal.

Due to these problems, paper containers have been put to practical use as replacements for existing disposable plastic containers in terms of using pulp, which is a natural raw material. However, the paper container also imports all pulp, and as a result, the infinite procurement of raw materials reveals its limitations in terms of comprehensive environmental damage of air and water soils caused by forest damage. In addition, in terms of practical use, it is inferior in solidity, has low water and moisture resistance, and is environmentally friendly, but has a very slow biodegradation rate. It is known to have a number of disadvantages, including the loss of.

On the other hand, there have been attempts to reduce the burden of environmental pollution by replacing disposable packaging materials such as containers with biodegradable resins that are decomposed by microorganisms instead of non-degradable petrochemical plastic raw materials having a large environmental burden. However, the biodegradable resin as described above has the advantage that the existing plastic product manufacturing equipment can be used as it is, while replacing the disposable packaging material, the biodegradation of expensive and scarcity raw materials using polymerized monomers and complicated polymerization process Since the resin is produced, there is a problem that the price is too expensive as a raw material for disposable packaging materials.

In order to improve the above problems, various methods of manufacturing environmentally friendly containers using vegetable raw materials such as chaff, reed, corn stalk, grain flour and starch have been introduced. In particular, starch is abundant in resources and ease of supply as long as green plants exist on the earth, the most biodegradable as existing polymers, non-toxic as natural polymers and very inexpensive, and In terms of chemical structure, by having three hydroxy groups per glucose unit, the physical properties can be changed chemically and variously, and thus the interest of new plastic raw materials is increasing. The research is also active at home and abroad.

Until now, research on environmentally friendly containers using natural plant raw materials has been carried out using a method of manufacturing a composition consisting of a powder of a plant raw material consisting of chaff and a binder of a biodegradable material as a sheet member, and pressing and molding by heating and pressing. 2000-0057885), a method of compression molding by adding and mixing a blowing agent with pulp powder, cereal powder, sawdust powder, natural cotton, chaff powder, straw powder, rice straw powder, barley straw powder, and the like to polyvinylacetate (Korean patent) Application 94-8523), a method of preparing a container by mixing starch polyvinyl alcohol (Polyvinylalcohol) as a bubble adjusting agent, vegetable fats and oils as an auxiliary additive (Japanese Patent Publication No. Hei 8-157645), pulp, wood chips in starch A method of preparing a container by mixing a metal, glass, protein, shellac, and the like as a filler has also been introduced by US Patent 5376320.

However, methods based on chaff, pulp powder, sawdust, and various types of straw are positively regarded as environmentally friendly container materials in that they use natural or plant-based raw materials. However, when discarded after use, microorganisms exist in nature. In terms of biodegradation rate or efficiency, which is decomposed into water and carbon dioxide or water and methane gas, and its efficiency, it is relatively late or lower than starch-based containers, and the color, weight, heat retention, and thermal barrier properties required for food containers. In terms of various functional aspects such as, there are still many points that are not enough for practical use. In addition, even in the case of a container containing the starch as a main component, the difference in biodegradation rate according to the starch content, a container having the starch which is hydrophilic as a main component, and a problem in imparting separate water resistance to the surface of the container and imparting water resistance It is known that there is a possibility that the appearance of the container during hot food packaging or hot water input may be deformed in the process of use due to the intrinsic content of starch, and the mechanical properties required for transportation or use during other distribution periods must also be supplemented. have.

It is an object of the present invention to provide a biodegradable starch-based container composition which is capable of completely replacing a non-degradable disposable styrofoam container in terms of functionality and practicality while improving all the problems of known environmentally friendly containers.

Another object of the present invention is to provide a method for producing a biodegradable container produced by changing the properties of the starch by mediating a chemical reaction by a pre-mixed reactant together with the molding process of the container to improve the physical properties of the container.

1 is a biodegradable disposable container picture according to the present invention

Figure 2 is a photograph of the microwave application result of the biodegradable disposable starch container

Figure 3 is a photograph of the landfill test results of the biodegradable disposable container according to the present invention

The present invention for achieving the above object comprises a starch, a binder and a physical reinforcing agent, wherein a reactive agent, a filler, a foaming aid, a collecting agent, a softening agent, a plasticizer, a binder and a physical reinforcing agent, a mold release agent, a moisturizing agent, a hydrophobic imparting agent It provides a biodegradable container composition comprising at least one component selected from.

In addition, the present invention is a biodegradable container which is prepared by mixing a reactant which provides at least a hydrophobic functional group or an active functional group, or a starch crosslinking agent or crosslinking agent between starch and subsidiary materials, with the starch as a predominant agent, and reacts with the molding process of the container. It provides a method of manufacturing.

Hereinafter, the content of the present invention will be described in detail.

Starch usable in the present invention includes at least one starch selected from above-mentioned starch, unmodified starch including underground starch, physically modified starch or chemically modified starch.

Starch is ground starch, potato starch, sweet potato starch, cassava starch and tapioca powder, such as wheat starch, corn starch, waxy corn starch, rice starch, glutinous rice starch, milo starch, wheat starch, etc. Underground starch such as sago starch, starch starch, etc. Physically or chemically treated modified starches, such as starch grafted with unsaturated monomer, are also various. These starches vary in viscosity, molecular structure, properties of starch particles, gelling properties, solution stability against water, aging, water retention, elasticity, etc., depending on the type or modification method of the source.

According to the present invention, the physical properties of the container required for each application can be variously changed by considering single or two or more kinds in consideration of the characteristics of each of the illustrated starch. For example, if the mechanical strength of the container is required, ground starch may be used alone or mixed with other starches, but modified starches such as acetyladipic acid crosslinked starch, phosphate crosslinked starch, alkylated starch, etc. may be used alone or in combination of two or more kinds. When the flexibility of the container is especially required, the underground starch may be used alone or in combination with other starches, but in order to increase the foaming efficiency, starch, acid treated starch, roasted starch, oxidized starch, ester starch, etc. When each is added alone or two or more kinds can be further improved the improvement effect according to the characteristics.

According to the present invention, it is possible to prepare a container for a specific use by controlling the content of amylose in the starch. For example, in the case of adjusting the total amount of amylose in the starch composition to 22% or less by combining various natural starch and modified starch as exemplified above, it can be used as a food container for a microwave oven, unlike a conventional environment-friendly container. Do.

The total amount of these starches in the starch container composition is preferably mixed by at least 70% by weight to 95% by weight in order to increase the efficiency and speed of biodegradability. Less than 70 weight% may be sufficient.

The chemical substitution of hydrophobic functional groups or active functional groups with the starch exemplified above, the introduction of chemical bonds between starch and starch or starch and subsidiary materials, is preferably carried out simultaneously with vessel shaping. Such chemical substitutions and / or chemical bonds formed between starch or starch prevent the deformation of the container due to the change of the moisture contained in the container during use of the container, and even when the hot product is packaged after imparting water resistance inside and outside the container. It prevents sinking due to moisture, and prevents damage due to loading load during product packaging and distribution and improves overall mechanical properties.

Chemical substitution of the hydrophobic functional group or active functional group, chemical bonding between the starch and starch or the starch supplementary material is carried out by a predetermined reactant added to the raw material mixing process.

The reactive agent for introducing a hydrophobic functional group into the starch is preferably a single or a mixture of two or more of alkenylsuccinic anhydrides having 10 to 32 carbon atoms (C _{10 to} C ₃₂ ), and active to starch. The reactant for introducing the functional group is preferably one or two or more selected from organic acids or anhydrides and derivatives thereof having at least 4 carbon atoms (> C ₄ ) and double bonds, and vinyl acetate, or having 1 to 10 carbon atoms. It is preferable to mix one or two or more selected from the organic acids of the dogs (C _{1 to} C ₁₀ ), anhydrides thereof, and glycine (Glycine).

Materials which induce crosslinking simultaneously between starch and starch or between starch and some subsidiary materials are preferably fumaric acid, maleic acid and its anhydrides, succinic acid, adipic acid and its anhydrides, sebacic acid, tartaric acid, malic acid, diglycolic acid, It is a dibasic acid or dihalide such as fumaryl chloride and the like, and for the crosslinking reaction, one or a mixture of two or more of each of the substances belonging to these groups may be added.

At the same time as forming the container, a method of inducing the substitution of hydrophobic functional groups or active functional groups in the starch structure and inducing chemical bonding between starch and starch or starch and subsidiary materials is as follows. In the whole composition which uses starch as a main raw material, single or at least 2 or more types of mixtures in the above-mentioned reactive agent are added preferably 0.1-15 weight% with respect to the total amount of the whole composition.

At this time, as a catalyst for inducing the reaction, when the reactant is a material having a double bond, at least one of benzoyl peroxide, ammonium persulfate, potassium permanganate, potassium persulfate, succinic acid peroxide, lauroyl peroxide, hydrogen peroxide Is added in an amount of 18% by weight or less relative to the amount of the reactive agent added. The catalyst used in the case of other reactants is preferably a basic aqueous solution. That is, the pH of the final mixture is preferably adjusted in the range of 7.5 to 12.5, more preferably 8.0 to 9.5 by adding an appropriate amount of basic aqueous solution in the process of mixing the composition and water.

The molding conditions of the container can be variously applied depending on the shape, height, thickness, size and use of the container, but in general, the mixture is injected into a heat-pressure foam molding machine preheated to 80 to 250 ° C and preferably 0 to 10 kg. At the pressure of / cm 2 for 5 to 720 seconds, the container molding and reaction proceed simultaneously.

Binders and physical reinforcing agents are added to increase the moldability and mechanical properties, for example, cellulose, ethyl cellulose, methyl cellulose, carboxymethyl cellulose, methyl hexapropyl cellulose, nitrocellulose, cellulose such as natural and recycled pulp, reed pulp Vegetables such as jute, jute, flax, hemp, hemp, sheep, sisal, cotton, gum, gum, guar gum, xanthan gum, gellan gum, cardamom gum, karaya gum, polyvinyl alcohol, polyvinyl acetate Or other carrageenan, algin, or lignosulfonate. Such binders and physical reinforcing agents are not particularly limited, but are preferably added in an amount of 0.5 to 50% by weight based on the total weight of the composition.

In addition, the container composition of the present invention, in addition to the starch, which is the main raw material, adds a lightweight filler, a foaming aid and a retaining agent for uniform foaming and weight reduction of the container, and a softening agent and a plasticizer for imparting flexibility of the container, and separating the container after forming the container. Release agent to facilitate the addition, moisturizer to increase the flexibility, hydrophobic imparting agent to prevent deformation of the container that may occur during high temperature product packaging after imparting water resistance to the inside and outside of the container, etc. Can be.

Filler is composed of talc, clay, igneous rock powder (preferably igneous rock powder heated at a high temperature of at least 500 ° C) and rice bran, rice husk, rice straw, reed, At least one of plant-based powders obtained by drying and pulverizing corn leaves and stems. These fillers may preferably be added in an amount of 0 to 25% by weight based on the total weight of the composition. At this time, the size of the filler does not require a special limitation, 50 ~ 350 mesh range is appropriate, especially considering the surface of the container, formability, mechanical strength, etc. Filler of less than 200 mesh is preferred.

Foaming aids used for uniform foaming are preferably ammonium bicarbonate, azide compounds, calcium bicarbonate, calcium carbonate, potassium carbonate, magnesium carbonate, sodium carbonate, calcium acetate, ethyl carbonate, azodicarbonamide, oxarylhydra At least one of gide and nitro urea. The foaming aid is preferably added 0 to 11.5% by weight relative to the total weight of the composition.

In particular, there are at least one kind of coagulant which helps to maintain the generated bubbles regardless of whether the foaming aid is added, such as sodium ethyl xanthate, potassium ethyl xanthate, sodium amyl xanthate, potassium amyl xanthate and the like. These collecting agents are preferably added in the range of 0 to 5.5% by weight with respect to the weight of the entire composition in order to obtain an even foaming effect, and more preferably, the addition effect of the collecting agent is further increased when used with the blowing aid.

On the other hand, the flexibility of the container is also a very important factor in order to suppress the damage caused by the drop during the transportation and use of the container or the damage caused by the load during the loading process. It is also very important to control the moisture content of the container in order to give the flexibility of the container, but if it contains more than a certain percentage of water content, when the water resistance inside and outside of the container is imparted, the phenomenon of the container itself being collapsed due to the packaging of the hot product is concerned. If it contains 20% or more excess water, the risk of spoilage of the container itself due to propagation of microorganisms cannot be excluded. In the present invention, as the softening agent for imparting the flexibility, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid; Glycerine Fatty Acid Ester, Glycerine Acetic Acid-fatty Acid Ester, Glycerine Lactic Acid- Fatty Acid Ester, Glycerine Citric Acid- Fatty Acid Ester, Glycerine Succinic Acid Fatty Acid Ester, Polyglycerin Fatty Acid Ester, Sucrose Fatty Acid Ester, Sorbitan Fatty Acid Ester, Ethylene Glycol Fatty Acid Ester, Propylene Glycol Fatty Acid Ester Fatty acid esters such as these; Water-soluble or water-swellable polymers such as polyvinyl alcohol and polyvinylacetate; And water-soluble acrylic resins, polyoxyethylene, gelatin. These softeners are preferably added in an amount of 0 to 30% by weight based on the total weight of the composition.

In addition, when forming a complex container according to the use, there is a phenomenon in which the raw material is fixed to the mold of the heat-pressure molding machine, thereby degrading the formability of the container. To solve this problem, a release agent that facilitates the fixing of the raw material and the separation of the container Used. Examples of such release agents include beeswax, liquid paraffin, paraffin chloride, normal paraffin, paraffin and waxes such as paraffin wax, peanut oil, cottonseed oil, corn oil, rice bran oil, wheat germ oil, almond oil, avocado oil, poppy seed oil, There are vegetable oils such as olive oil, castor oil, sunflower oil, hazelnut oil, walnut oil, pumpkin seed oil, safflower seed oil, and the like. Such a release agent is preferably added so as to be 0 to 15% by weight relative to the total weight of the composition.

In particular, when vegetable oils are added as a release agent or fatty acids and fatty acid esters as described above as softeners, oleyl alcohol, cetyl alcohol and oleic acid may be used to increase the dispersibility or compatibility of the composition mixed with water and the oil component to be added. It is preferable to add at least one surfactant among amides, polysorbates, saponins. Such surfactant is preferably added in the range of 0.1 to 12% by weight based on the weight of the release agent or softener added.

Other containers The raw material composition of the container can be changed depending on the temperature of the product to be packaged.In order to improve the flexibility of the container as a product for low temperature product packaging, as a plasticizer and a moisturizer, monosaccharides such as sorbitol, glucose, maltose, lactose and dextrin and In polysaccharide, 0 to 9.5 weight% of single or 2 types or more can be added with respect to the weight of the whole composition.

In addition, when the high temperature product is packaged after imparting water resistance to both inside and outside of the container, it is preferable to add a hydrophobic imparting agent in order to prevent deformation of the container, deformation, and the like. Examples of the internal additive for imparting hydrophobicity include at least one of paraffin, wax, rosin, lecithin, glyoxal, inorganic water-based agent, and oily silicone resin. Such hydrophobic imparting agent is not particularly limited, but preferably 0.1 to 20% by weight relative to the total weight of the composition is added.

An example of a process of preparing a biodegradable foam container using a mixture containing the above essential ingredients and other additives as a raw material is as follows.

The mixture is again mixed with water at a ratio of 1: 0 to 1: 1.6 (w / w, mixture: water) by weight for 5 minutes to 60 minutes. In this case, when serving as a purpose of inducing the chemical reaction of the starch already mentioned, it is good to adjust the pH with a basic aqueous solution followed by mixing the raw materials. Then, a certain amount of the mixture is injected into a heated pressurized foam molding machine preheated to 80 to 250 ° C. and maintained at a pressure of 0 to 30 kg / cm 2 for 5 to 720 seconds to prepare a biodegradable disposable container.

The present invention can in particular produce a compression vessel or foam vessel as desired by adjusting the mixing ratio with water. More specifically, compression vessels are usually produced when the mixing ratio of water is less than 10% of the total weight of the composition, and foam containers are above that.

As described above, the final manufactured biodegradable disposable container requires a process of imparting water resistance depending on the use during the manufacturing process. The process of imparting water resistance may be carried out at high temperature by melting water-soluble inorganic coating agents such as fluorine and silicon, or polycaprolactone, polylactide, aliphatic polyester and aromatic / aliphatic polyester copolymer, which are known as biodegradable resins. The method includes coating and drying a solution dissolved in a solvent in a container by spraying or dipping to impart water resistance.

In another process, especially in the case of a foam container with relatively free air permeation, a 100% biodegradable film having a thickness of 50 to 300 μm, a partially degradable biodegradable film and a conventional non-degradable film may be used at 60 to 200 ° C. Laminating process of vacuum suction through the mold from the outside of the container to the surface of the container while heated to

The evaluation method of the biodegradable disposable container of this invention is as follows.

Mechanical Properties: Flexural Strength and Flexural Modulus

After cutting the specimen of the prepared container into the size of 3cm × 10㎝, the maximum stress (strength) and the degree of warpage (elasticity) of bending when applying force to the specimen at 500kg Load cell, 10mm / min speed using Instron The measurement was performed 10 times in total and the average value was taken.

Biodegradability

1) Culture method

The American standard test method (ASTNI, G21-70 & D1924-70) was modified and measured. In other words, aspergillus niger, Aspergillus oryzae, and penicillium funiculosum, which are commonly found in soil, are placed in solid agar media. ) And inoculated mixed spores such as Pulularia pulluans and incubated at 32 ℃ (± 2 ℃) for 15 days to record the extent of the fungus covered on the sample to evaluate the biodegradability.

Growth rate (%) 0 1-9 10-29 30-59 60 or more Score 0 One 2 3 4

2) Landfill Act

After filling a certain amount of container samples per 50 cm depth of the formulation of the composition, landfill containers were taken for each period and the degree of degradation according to the landfill period was visually observed.

Water supply

Fill the container with water at 95 ° C, close the lid, check the container for deformation or leakage, and measure the time required for deformation or leakage.

Oil resistance

After castor oil, toluene, and N-heptane, 16-grade test solutions were prepared as follows, and the prepared test solutions were carefully dropped onto the container specimens by grade. The deformation of the dropped test solution after a certain time (10 minutes) was rejected. As shown in Table 1 below, the test solution was carried out step by step, and the oil resistance of the test piece was determined as the average value of three times using the highest grade of oil resistance and the lowest grade of 1 as 1.

<Table 1> Composition of test standard solution and evaluation table of oil resistance

Oil resistance Castor Oil toluene N-heptane Oil resistance Castor Oil toluene N-heptane One 100 0 0 9 20 40 40 2 90 5 5 10 10 45 45 3 80 10 10 11 0 50 50 4 70 15 15 12 0 45 55 5 60 20 20 13 0 35 65 6 50 25 25 14 0 25 75 7 40 30 30 15 0 15 85 8 30 35 35 16 0 0 100

Sealing of Lid

Lid coated with polyethylene (PE) and polyethylene glycol (PEG) was sealed on the surface of the container for 2 seconds at a temperature of 100 to 190 ° C and a pressure of 1 to 3 kgf / cm ² , and then removed after 24 hours. At this time, desorption / adhesion state, desorption / adhesion strength, and peeling phenomenon of the surface were examined.

Microwave range applicability (high frequency adequacy test)

The test vessel was placed in a microwave oven, heated at a rated high frequency output for 2-3 minutes, taken out, and left to cool until the vessel reached 23.5 ° C. The same operation was repeated twice. Sparks at the time of heating and abnormality of the container after the test were visually observed and evaluated.

Hereinafter, various biodegradable disposable containers manufactured according to the present invention are attached to FIG. 1. In addition, the following examples and comparative examples can be more clearly the technical spirit of the present invention, the scope of the present invention is not limited thereto.

<Comparative Example 1>

For comparison with the biodegradable container prepared in the following example, a non-degradable styrofoam container of similar shape and same thickness was purchased and used as a control.

<Comparative Example 2>

For comparison with the biodegradable container produced by the following example, a similar type of uncoated paper container currently in circulation was purchased and used as a control.

<Comparative Example 3>

For comparison with the biodegradable container produced by the following example, a similar type of PE coated paper container currently in circulation was purchased and used as a control.

<Example 1>

In a V-type mixer, 1 kg of corn starch with 12.3% moisture, 15 g of oleic acid, 25 g of polyvinyl alcohol copolymer, 5 g of polyoxyethylene, 30 g of methylcellulose, 1.5 g of cardi gum, 1.5 g of lignosulfonate, 18 g of corn oil and 245 g of dextrin Charged and mixed for 30 minutes. The mixture was then transferred to a kneader and mixed again for 15 minutes with the addition of 1.5 kg of water, and then a predetermined amount was taken into a mold of a heated press molding machine with an internal temperature of 160 ° C. for 2 minutes and 30 seconds at a pressure of 0.5 kgf / cm ² . Molding to prepare a foam container. In addition, a plurality of the same container was manufactured in an iterative operation and used as an evaluation sample.

<Example 2>

1.2 kg of corn starch with water 12.3%, polyglycerol fatty acid ester 15g, polyvinyl alcohol copolymer 35g, reed pulp powder 30g, cardi gum 1.5g, lignosulfonate 1.5g, corn oil 18g, dextrin 245g and 40 g of adipic acid as a reactant was added and mixed for 30 minutes. The mixture was then transferred to a kneader and 1.6 kg of water were added and mixed again for 15 minutes. However, the pH of the mixture was adjusted to 10.2 while adding an appropriate amount of 1N-NaOH aqueous solution as a reaction catalyst during the mixing process, and a predetermined amount was taken into a mold of a heat press molding machine preheated to 210 ° C. to a pressure of 1.2 kgf / cm ² . Reaction and foaming vessel molding were performed simultaneously for 1 minute 40 seconds. In addition, a plurality of the same container was manufactured in an iterative operation and used as an evaluation sample.

Example 3

Instead of corn starch, 13.2% moisture potato starch was used and prepared in the same manner as in Example 1, and used as an evaluation sample.

Example 4

Mixed starch mixed with corn starch and potato starch in a weight ratio of 6: 4 was prepared in the same manner as in Example 1 using instead of the corn starch of Example 1 and used as an evaluation sample.

Example 5

2g of oleyl alcohol was further mixed as a surfactant of corn oil used as a releasing agent in Example 1, which was prepared in the same manner as in Example 1 and used as an evaluation sample.

Example 6

In a V-type mixer, 1 kg of corn starch of 12.3% moisture, 25 g of glycerin lactic acid-fatty acid ester, 18 g of natural pulp mill, 1.5 g of cardiac gum, 1.5 g of lignosulfonate, 25 g of beeswax powder, and 30 g of vinyl acetate as a reaction catalyst 1.5 g of potassium persulfate was added and mixed for 30 minutes. Then, the mixture was transferred to a kneader, mixed again for 15 minutes by adding 1.2 kg of water, and then a predetermined amount was taken into a mold of a heat press molding machine with an internal temperature of 185 ° C., and molded at a pressure of 1.5 kgf / cm ² for 2 minutes. Foam containers were prepared. In addition, a plurality of the same container was manufactured in an iterative operation and used as an evaluation sample.

Example 7

In Example 6, 24 g of calcium acetate was further mixed as a foaming aid, which was prepared in the same manner as in Example 6 and used as an evaluation sample.

Example 8

In Example 7, 12 g of potassium ethyl xanthate and 8 g of potassium amyl xanthate were further mixed as a coagulant for maintaining the bubbles, and manufactured in the same manner as in Example 7 below and used as an evaluation sample.

Example 9

500g of acetyladipic acid crosslinked corn starch with water 12.5%, 300g of corn starch with water 12.3%, potato starch with 200g water with 5.6% moisture, 15g with oleic acid, 25g with polyvinyl alcohol copolymer, 5g with polyoxyethylene, methylcellulose 30 g, cardigan gum 1.5 g, lignosulfonate 1.5 g, corn oil 18 g and dextrin 245 g were added and mixed for 30 minutes. The mixture was then transferred to the kneader and mixed again for 15 minutes with the addition of 1.5 kg of water, and then a predetermined amount was taken into a mold of a heated press molding machine with an internal temperature of 160 ° C. for 2 minutes and 30 seconds at a pressure of 0.5 kgf / cm ² . Molding produced a foam container. In addition, a plurality of the same container was manufactured in an iterative operation and used as an evaluation sample.

Example 10

800g of water 12.3% corn starch, 200g of water treated corn starch 200g, 15g oleic acid, 15g polyvinyl alpolymer, 5g polyoxyethylene, 30g methyl cellulose, 1.5g cardigan gum, lignosulfonate 1.5 g, corn oil 18g and dextrin 245g were added and mixed for 30 minutes. The mixture was then transferred to the kneader and mixed again for 15 minutes with the addition of 1.5 kg of water, and then a predetermined amount was taken into a mold of a heat press molding machine with an internal temperature of 160 ° C. for 2 minutes and 30 seconds at a pressure of 0.5 kgf / cm ² . Molded. In addition, a plurality of the same container was manufactured in an iterative operation and used as an evaluation sample.

Example 11

Corn starch, corn phosphate cross-linked starch and sweet potato starch are mixed in a V-type mixer to adjust the total amylose content to 22% or less 1kg of mixed starch, glycerin acetic acid-fatty acid ester 30g, polyvinylacetate 15g, guar gum 1.5g, 25 g of beeswax powder and 45 g of glycine were added as a reactant and mixed for 30 minutes. Subsequently, the mixture was transferred to a kneader, 1.2 kg of water was added, and mixed again for 15 minutes. Stage mixing the reaction catalyst with 1N-KOH aqueous solution of an appropriate amount was added while the mixture of the pH was adjusted to 9.5, taking the temperature inside a heat and pressure molding machine of a mold of 2.5 kgf / cm ² pressure were charged into a pre-heated to 160 ℃ a certain amount during the It was molded for 2 minutes 30 seconds. In addition, a plurality of the same container was manufactured in an iterative operation and used as an evaluation sample.

<Example 12>

Potato starch, corn phosphate cross-linked starch, sweet potato starch, glutinous rice starch were mixed in a V-type mixer to adjust the total amylose content to 22% or less, and prepared in the same manner as in Example 11 below and used as an evaluation sample.

Example 13

Into the V-type mixer, 1 kg of corn starch with 12.3% moisture, 250 g of rice bran and clay powder, 15 g of oleic acid, 25 g of polyvinyl alcohol copolymer, 1.5 g of cardigan gum, 1.5 g of lignosulfonate, 18 g of corn oil and 245 g of dextrin were added. Mix for 30 minutes. The mixture was then transferred to a kneader and mixed again for 15 minutes with the addition of 1.5 kg of water, and then a predetermined amount was taken into a mold of a heated press molding machine with an internal temperature of 160 ° C. for 2 minutes and 30 seconds at a pressure of 0.5 kgf / cm ² . Molded. In addition, a plurality of the same foam container was manufactured by repeated operation and used as an evaluation sample.

Example 14

1.2 kg of corn starch with water 12.3%, polyglycerol fatty acid ester 15g, polyvinyl alcohol copolymer 35g, reed pulp powder 30g, cardi gum 1.5g, lignosulfonate 1.5g, 25g of rosin and hydrophobic additive 15 g of glyoxal and 20 g of octenylsuccinic anhydride as a reactant were added and mixed for 30 minutes. Subsequently, the mixture was transferred to a kneader, 1.2 kg of water was added, and mixed again for 15 minutes. However, the pH of the mixture was adjusted to 11.5 while adding an appropriate amount of 1N-NaOH aqueous solution as a reaction catalyst during the mixing process, and a predetermined amount was taken into a mold of a heat press molding machine preheated to 160 ° C to give a pressure of 2.5 kgf / cm ² . Reaction and foam container molding were simultaneously performed for 2 minutes. In addition, a plurality of the same container was manufactured in an iterative operation and used as an evaluation sample.

.

<Examples 15 to 18>

Take two of each container sample prepared in Examples 1, 12, 13, and 14 and use a silicon compound-based aqueous coating agent and a spray gun diluted to 25% solids, and evenly coat the inner surface of the container and Was evaluated.

<Examples 19 to 22>

Polycaprolactone, a biodegradable resin (melting point 60 ° C, for injection) was used as a coating agent, and injected into a sprayer equipped with a heating device, and prepared according to Examples 1, 12, 13, and 14 at a temperature of 120 ° C and a spray pressure of 3.5 bar. The inner surfaces of each of the two container samples were melt coated and used as evaluation samples after drying.

<Examples 23 to 26>

After cutting the biodegradable blown film having a thickness of 150 μm made of biodegradable aliphatic polyester into a suitable size for a container, the vacuum suction coating device with the same mold as the shape of the container was used at 200 ° C. and a vacuum pressure of 15 psi. The inner surfaces of the container samples prepared in Examples 1, 12, 13, and 14 were laminated to impart water resistance, and then used as evaluation samples.

<Examples 27 to 31>

Prepared in the same composition and ratio as in Examples 1, 3, 4, 13, and 14, respectively, but the amount of water added is 98 g, the preheating temperature of the heating press molding machine is 90 ° C., and the pressing force 6 kgf / cm ² In addition, the molding time was adjusted to 1 minute and 20 seconds to prepare compression containers, and the same container was manufactured in the repetitive operation and used as an evaluation sample.

<Example 32>

Container samples prepared from Examples 1, 11, 12, and 13 were taken and cut into appropriate sizes, respectively, and the applicability of the microwave was confirmed by the above-described test method, and the results are attached to FIG. 2.

<Example 33>

One of the container samples prepared in Example 15 was directly buried according to the above-described landfill test method, and biodegradability was compared over time, and the results are attached to FIG. 3.

The results of evaluating the mechanical properties, biodegradability, water and oil resistance, Lid sealing property, microwave oven applicability, etc. of each biodegradable disposable container prepared in Example and Comparative Example are shown in the following tables.

<Table 2> Evaluation results of mechanical properties and biodegradability

division Flexural Strength (kg / cm ² ) Flexural Modulus (kg / cm ² ) Biodegradability (culture method) Comparative Example 1 18 837 0 Comparative Example 2 Not measurable Not measurable One Comparative Example 3 Not measurable Not measurable 0 Example 1 41 3,765 4 Example 2 46 3,654 4 Example 3 32 4,126 4 Example 4 37 3,921 4 Example 5 43 3,897 4 Example 6 49 3,916 4 Example 7 48 3,954 4 Example 8 51 4,093 4 Example 9 44 3,782 4 Example 10 38 4,039 4 Example 11 43 4,125 4 Example 12 42 4,263 4 Example 13 42 4,299 4 Example 14 39 3,876 4 Example 15 46 3,784 3 Example 19 47 4,253 4 Example 23 51 4,376 4 Example 27 121 4,197 3 Example 28 105 4,327 3 Example 29 116 4,216 3 Example 30 139 4,083 3 Example 31 122 4,204 3

<Table 3> Measurement results of water resistance and oil resistance

division Water supply Oil resistance Comparative Example 1 No deformation, no leak 4 Comparative Example 2 Less than 1 minute deformation, leakage 2 Comparative Example 3 No deformation, no leak 10 Example 1 Deformation after 2 minutes, leak General purpose 3 Example 13 Deformation after 2 minutes, leak General purpose 6 Example 14 Deformation after 6 minutes, leak Humid Product Packaging 4 Example 15 No deformation, no leak Low temperature / high temperature liquid packaging 16 Example 19 No deformation, no leak Low temperature / high temperature liquid packaging 10 Example 23 No deformation, no leak Low temperature / high temperature liquid packaging 10

<Table 4> Lid suture measurement results

division Sutureability Remarks Comparative Example 1 Good sealing Comparative Example 2 Lid suture is impossible Comparative Example 3 Good sealing Example 1 Good sealing 100 ~ 190 ℃ 1-3kgf / cm ² Example 13 Example 14 Example 15 Example 19

<Table 5> Evaluation result of microwave oven applicability

division Suitability Comparative Example 1 can not be used Comparative Example 2 Unavailable (very severe carbonization after one test operation) Comparative Example 3 Example 1 Carbonization after one test operation Example 11 Carbonization after one test operation Example 12 Microwave available Example 13 Microwave available Example 16 Microwave available Example 20 Microwave Applicable

According to the present invention, biodegradation is easy, deformation of the container due to the change of the moisture contained in the container is prevented during use, and the impurity of the moisture contained in the container can be prevented even when packaging a high temperature product after imparting internal and external water resistance of the container. In addition, it is possible to prevent damage due to the loading load during the packaging and distribution of the product and to improve the overall mechanical properties.

In particular, by controlling the content of amylose in the starch, it is also possible to mold into a container having a specific use.

Claims (16)

A starch, a binder, and a physical reinforcing agent, including a reactive agent, a filler, a foaming aid, a preservative, a softening agent, a plasticizer, a binder and at least one component selected from a physical reinforcing agent, a mold release agent, a humectant, and a hydrophobic imparting agent. Biodegradable Container Composition The method of claim 1, Starch is a biodegradable container composition, which is a single or mixed starch selected from natural starch or modified starch. The method of claim 1, Biodegradable container composition containing 70 to 95% by weight of total starch The method of claim 1, Biodegradable container composition containing less than 70% by weight starch The method of claim 1, Biodegradable container composition with less than 22% total amylose in starch The method of claim 1, The reactive agent provides a hydrophobic functional group to the starch and is a biodegradable container composition, alone or in combination, from substances belonging to the group of alkenylsuccinic anhydrides of C _{10 to} C ₃₂ . The method of claim 1, The reactive agent provides an active functional group to the starch, and the active functional group is C ₄ or more, an organic acid or anhydride and derivative thereof having a double bond in the structure, or two or more selected from vinyl acetate, or an organic acid of C _{1 to} C ₁₀ . And anhydrous, glycine alone or two or more biodegradable container composition The method of claim 1, The reactive agent provides crosslinking between starch or between starch and subsidiary materials and is a biodegradable container composition, alone or in combination, selected from dibasic acids, dihalides or anhydrides thereof. The method of claim 1, Biodegradable container composition further comprising a surfactant when a softener of a fatty acid or fatty acid ester is included The method of claim 1, Biodegradable container composition further comprising a surfactant when a release agent of vegetable oils is included A method for producing a biodegradable container prepared by mixing at least a hydrophobic functional group or a reactive agent that provides an active functional group or a reactive agent which crosslinks each other or between starch and subsidiary materials with starch as a predominant agent and reacts with the molding process of the container. The method of claim 11, Starch is a production method is a single or mixed starch selected from natural starch or modified starch The method of claim 11, When the reactant is a compound having a double bond, the catalyst used in the reaction is at least one selected from benzoyl peroxide, ammonium persulfate, succinic acid peroxide, lauroyl peroxide, and hydrogen peroxide. The method of claim 11, When the reactant is other than a compound having a double bond, the catalyst used in the reaction is a basic aqueous solution, and the pH of the final product is 7.5-12.5. The method of claim 11, The method further includes coating and drying the water-soluble inorganic coating agent or the biodegradable polymer resin alone or two or more mixed melts or solutions after the molding of the container. The method of claim 11, Laminating the biodegradable film, biodegradable film or non-degradable film in the container after the molding of the container further comprising the manufacturing method