KR800000025B1 - Method of manufacturing a protein-starch binary molding compositon - Google Patents

Abstract

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Description

Method for preparing a protein-starch two-component molding composition

The present invention relates to a method for producing a protein-starch bicomponent molding composition. More specifically, the present invention relates to a protein-starch bicomponent molding composition and a method for producing a molded article obtained therefrom, the molding of which includes compression molding, transfer molding, extrusion molding, suction molding, inflation molding, injection molding, vacuum molding, Various conventional dry molding methods such as press molding can be used.

It is an object of the present invention to provide so-called water soluble, edible and thermoplastic molding compositions, all of which contain alkali or alkaline earth metal salts of edible proteins, starch, water, organic low molecular weight plasticizers and lubricants.

An object of the present invention is to provide a method for producing the molding composition, and another object is to provide a molded article obtained from the above-mentioned molding composition and this molded article and a method for producing the molded article.

The demand for edible sheet tubing and film materials has been increasing in order to increase the profitability of recognizing food packaging. To meet these demands, collagen products have a wide range of advantages. However, these products are expensive and limited in their use. Although cheap film materials made from starch (wafer sheets) are commercially available, they are used for limited applications because of their low strength.

In recent years, as the pollution problem caused by waste plastic products has increased, the development of plastic materials having a natural decay cycle has been longed for. Under these circumstances, the emergence of edible plastic products in terms of hygiene has been desired.

Examples of proteinaceous materials used as plastic materials include casein-based materials used in the form of films, molded articles, fiber adhesives and paints. In practical terms, however, these products have been limited because they must be molded only by the wet molding method, the molded parts are immersed in formalin for a long time, and the molded parts have insufficient physical properties.

For example, in films, films made from casein sodium with water and glycerol are rarely practical, although they retain high humidity retention, good heat fusion, clear and wet plasticizers that prevent them from breaking when dried. Even if it has some beneficial properties such as difficulty of bleed), it has low defects in blocking resistance, easy adhesion when wet, extremely low water resistance, and easy dissolution in water. As a result of the experiment, the present inventors found that various dry molding methods such as extrusion and injection molding can be easily applied to molding the casein composition described above (see Table 1).

In the past, starch sheets or films were generally made by a so-called film casting method, in which water was evaporated from an aqueous solution of starch to obtain a film or sheet. Although the sheet or film formed by this method has several characteristics, this wet casting method has its own fatal defects as described below, and in the case of the sheet or film in comparison with the phenomenal stretching of other plastics in production, Production is limited. That is, these drawbacks are as follows.

(1) A large amount of heat is required to evaporate and remove water from the aqueous solution of starch to obtain the final product. There is no suitable solvent other than water for starch.

(2) As known in the film casting method, it is difficult to obtain a starch sheet or a film having a large thickness, so that the product is practically limited.

(3) Molded products of complex design cannot be obtained.

(4) When obtaining a sheet or a film, especially a complicated technique and apparatus are needed.

(5) The obtained sheet and film are very susceptible to the influence of moisture in the atmosphere, and are broken in dry air, and the plasticizer compounded in wet air has a drawback in that bleeding phenomenon easily occurs.

In order to solve these drawbacks, it is proposed to use a conventional extrusion method using a conventional extruder as one of the dry methods, which provides a processability by chemically modifying the starch, various plasticizers and lubricants on the modified starch Is added to shape the resulting composition. This method has an important meaning in that it can be simplified compared with the film casting method.

However, chemical modifications of starch have the drawback of impairing the edibility, which is one of the original properties of starch. In addition, attempts have been made to improve the properties of starch moldings by using starch materials containing a large amount of, for example, 50% or more of a so-called amylose having a linear arrangement such as high amylose corn starch and fractional amylose as starch. However, starch containing a higher percentage of amylose tends to be rather difficult because it is difficult to dissolve in water and easy to crystallize. In other words, attempts to increase the processability of starch by chemical modifications involved the sacrifice of mechanical properties, moisture resistance and water resistance due to the strong hydrogen bonding of starch, and also the sacrifice of the preservation of starch that can only be obtained from unmodified starch. .

In order to improve the above method, untreated amylose is mixed with water and glycerol, ethylene glycol, propylene glycol, dimethylformamide, and the like, and a low molecular weight organic plasticizer having a vapor pressure of 100 mmHg or less at 100 ° C and high shear stress is applied to the mixture. A method of extruding the resulting hot homogeneous fluid through a mold has been proposed. However, the method of adding a low molecular weight plasticizer alone has the following fatal drawbacks.

(1) Due to the limited compatibility with starch, when a low molecular weight plasticizer is added in an amount exceeding 40% by weight with respect to 100% by weight of starch, it is soft and brittle during extrusion at high temperature, and a non-adhesive extrudate is obtained. The extrudate cannot withstand the tension of the winding retractor, making film formation extremely difficult under tension.

(2) As it is known, starch products are hard and brittle when dried. Starch products do not require a large amount of plasticizers. However, starch products tend to cause so-called bleeding under high humidity, especially when a large amount of this plasticizer is used. It will lower the quality of the product.

(3) The number of suitable low molecular weight plasticizers that are compatible with starch from the viewpoint of decorating is limited, such as water, glycerol, sorbitol, mannitol and maltitol. These plasticizers tend to lower the plasticizing effect at low humidity and cause bleeding at high humidity.

(4) In addition, a method of adding in combination with water-soluble polymer such as polyvinyl alcohol and water has not been proposed, but the bleeding phenomenon or insufficient elongation, elongation and strength are not sufficiently improved at high temperature, and pollution-free and decorative It's very falling from the point of view of sex.

As a result of intensive studies in consideration of the above-mentioned drawbacks, the inventors have found surprising mixing effects in alkali metal salts of protein materials or in two-component mixtures containing alkaline earth metal salts and starch-based products. This surprising effect is particularly pronounced in the case of binary mixtures containing salts and starches of unmodified proteins.

TABLE 1

In addition, by using the above two-component mixtures, it is possible to obtain a novel molding composition capable of addressing most of the shortcomings of molded articles such as conventional protein-based and starch-based sheets and films.

The inventors of the present invention have conducted extensive research on the purpose of using protein and starch as useful raw materials for plastics, and as a result, protein materials, especially alkali metal salts and alkaline earth metal salts thereof, are satisfactorily compatible with starch, and plasticizers and lubricants And found that it can be beneficially combined. Further research based on this finding found that by properly mixing salts, starch, water, plasticizers and lubricants of protein materials, it is possible to produce molded articles with good moldability and good properties. That is, a very practical edible molding composition could be obtained by selecting an edible composition containing a protein, starch, water, a low molecular weight organic plasticizer and a lubricant.

The present invention provides a water-soluble and edible thermoplastic molding composition containing starch, inorganic alkali salts of proteins, edible low molecular weight organic plasticizers and edible lubricants.

The water content in the molding composition is preferably adjusted to 10 to 40% by weight and the weight ratio of starch to protein is preferably 10:90 to 90:10.

The molding composition can be easily molded by compression molding, transfer molding, injection molding, extrusion molding, suction molding, inflation molding, vacuum molding or press molding, and is a molded article having excellent physical properties such as transparent or translucent. Sheets, films, tubs, bottles and other containers can be obtained. It is preferable to adjust the moisture content of the molded article to 5-30 weight%.

"Inorganic alkali salt" of a protein herein means a salt of a protein material with an alkali metal or an alkali metal.

Suitable protein substances for use in shaping such salts are those obtained by concentration or extraction from various animals, plants and microorganisms, such as casein (from milk, soybeans, etc.), albumin (from sap or eggs). Extract), collagen, gelatin, glue, gluutene and the like. These are each used alone or in mixtures.

Inorganic alkali salts of proteins are neutralized with inorganic alkaline substances such as hydroxides, carbonates or hydrogen carbonates or mixtures of these alkaline substances with protein substances and alkali metal or alkaline earth metals in water-soluble media to form salts and then to separate the resulting salts. It is prepared by drying.

Any compound of a protein substance with an alkali or alkaline earth metal may be used for the purposes of the present invention, but the sodium salt of casein is preferred. This is because the color is bright and excellent in water dispersibility, film-forming property and decorating property. It is desirable to increase the water resistance in order to replace part or all of the protein salt composition with alkaline earth metal salts, such as calcium salts, of the protein.

In preparing the present composition, it is not preferable to use a salt of a protein material prepared in advance, but the protein material and an aqueous solution of hydroxide, carbonate or hydrogen carbonate, or alkaline substance of alkali metal or alkaline earth metal may be combined with the composition alone. have. In this case, since the amount of the alkaline substance is preferably equivalent to the free carboxyl group of the protein substance to be used, the free alkali may not be contained in this composition.

It is not advisable to use only the protein itself in place of the alkali metal salt or alkaline earth metal salt in the composition, because the plasticity, water retention, and mechanical strength of the molded article are poor, although in other respects they have quite good properties. to be. Mixtures of protein components with their salts may also be used. A part of the protein component may be used by substituting a protein having a functional group modified by a conventional method to such an extent that it does not impair its decorability.

The protein component for use in the present composition may be used by substituting a part of protein powder such as skim flour or dry powder of edible microorganisms.

Suitable edible microorganisms include petroleum yeast (single-cell yeast) prepared using petroleum hydrocarbon gas, n-pyraffines, methanol or ethanol as carbon sources, toula yeast cultured in sulfite waste solution, and as a by-product of alcohol production. Excessive beer yeast produced, a fructose yeast using a fructose as a medium, a baker's yeast, and an edible microorganism using a food Busan as a medium can be mentioned. Dry powders of these microorganisms containing at least 30%, preferably at least 50%, protein in terms of dry matter are used in the composition. Among them, beer yeast and baker's yeast are particularly preferred. After extraction of the nucleic acid and other useful components, dry residues from the molasses yeast cells may be used. These dry edible microorganisms are highly hygroscopic and usually contain about 10% by weight of water. Since such hygroscopic moisture is contemplated in the preparation of the present composition, the composition prepared without adding moisture is often not satisfactory in achieving the object of the present invention.

The starch generally used in the present composition contains various common starches such as amylose obtained from grains, potatoes, edible roots and the like. Preferred to further improve the properties of the molded article include a special type of starch containing more than 50% amylose, for example a mixture of high-amylose starch and amylopectin and fractional amylose containing more than 50% by weight amylose. . Specific types of starch containing less than 10% amylose, such as waxy corn starch and adhesive rice starch, can be used in combination with high-amylose starch. In addition, so-called unmodified starch such as α-starch and dextrin may be used.

High-amylose starch contains more than 50% by weight of amylose and is a generally unique corn starch generally extracted from improved corn varieties. High-amylose starch is generally used in potato starch, such as potato starch, so-called amylose containing at least 90% by weight of amylose or high-amylose starch which can be replaced with a mixture of fractionated amylose and other ordinary starch. It is difficult to gelatinize because it has a higher gelatinization temperature compared to ordinary starch (including 15-30% amylose content). Cooled films made from high-amylose starch having an amorphous structure and sufficiently gelatinized are excellent in plasticity and abrasion. The properties of high-amylose starch are fully improved only in molded articles having an almost amorphous structure, and when the film is molded from insufficiently gelatinized high-amylose starch, the resulting film still contains a large amount of crystalline microparticles and is broken. It is easy and lacks in other physical properties and is worse than a film made from ordinary starch.

From the above facts, it is considered that a suitable modification of high-amylose starch exerts an effect similar to that when converted to α-form. However, the form and extent of deformation used in terms of edibility are quite limited. Thus, in the case of molding compositions for use in the manufacture of edible shaped articles, as in the case of the present invention, it is not desirable to depend on the deformation of the starch material because the tolerance of deformation is small.

In order to increase the performance properties of high-amylose starch according to the present invention, gelatinization is carried out using heat and pressure in the presence of moisture in the preparation of the molding composition as well as the molded article. It is suitable to use starch previously modified to α-form. α-type high-amylose starch is obtained by treating high-amylose starch in a neutral or weakly alkaline aqueous solution using heat and pressure to perform gelatinization, followed by dehydration and rapid drying. α-starch has an increased compatibility with neutral inorganic alkali salts of proteins and improves the moldability and processability of the molding composition. Molded articles obtained from such moldings have improved transparency, plasticity and water solubility. Although good effects are clearly found in the transformation to α-form compared to ordinary starch, these effects are more pronounced compared to high-amylose starch.

According to the present invention, the mixture of the starch material and the neutral inorganic alkali salt of the protein component is not a simple mixture, and these two materials in the amorphous form are uniformly dispersed, but some bond is formed between the two materials by chemical reaction, It seems to contribute to improvement. The chemical reaction between the two materials is not only necessary in the preparation step of the composition, but also in the molding step of the composition.

The occurrence of a chemical reaction between the starch material and the neutral inorganic alkali salt of the protein material, with the passage of time during the heating of the mixture of these two components, decreases the dissolution rate of the mixture in cold water and results in pale yellow discoloration of the mixture. Proved by the fact that It is advantageous to transform the starch material into α-form before mixing the composition, because it enhances both the usability of the protein component with neutral inorganic alkali salts and the reaction between them.

Examples of edible modified starches that can be used in the compositions of the present invention include carboxymethyl starch, hydroxyethyl starch, hydroxypropyl starch, methyl starch, ethyl starch, methylhydroxyethyl starch, ethyl hydroxy Propyl starch, starch phosphate, and the like. By using such edible modified starch, the moldability and processability of the composition can be increased, and the physical properties of the sheet and the film can also be increased. To be edible, the modified starch should have as little strain as possible, mixed with a large amount of unmodified starch, and should have as little strain as possible in the molded article, mixed with a large amount of unmodified starch. It should be used and the preferred amount of modified starch in the molded product should be less than 10% by weight.

The weight ratio between the starch and the alkali salt of the protein may be in a wide range, but the preferred ratio is the starch 90 to 10 weight ratio relative to the 10 to 90 weight ratio of the inorganic alkali salt of the protein component. If the amount of starch is less than 10% by weight, the water resistance and blocking resistance of the molded article is reduced, and if it exceeds 90% by weight, the water retention characteristics are lost. The weight ratio of the alkali salt of the protein to the starch of the protein is more preferably in the range of 30/70 to 70/30.

Another important thing in this molding composition is the addition of an edible hydrophilic plasticizer capable of giving plasticity or swelling to a two-component mixture of an alkali metal salt or alkaline earth metal salt of a protein component and a starch component.

When an edible hydrophilic plasticizer capable of plasticizing the aforementioned two-component mixture is used, the plasticizing effect is somewhat changed depending on the form of the neutral inorganic alkali salt of the protein component, the form of the starch, and the combination of these components. It is effective to combine water, an edible low molecular weight organic plasticizer and optionally an edible polymeric plasticizer. Examples of edible low molecular weight organic plasticizers suitable for use are polyhydric compounds such as glycerol, sorbitol, sorbitan, mannitol, maltitol, ethylene glycol, propylene glycol, diethyl glycol, dipropylene glycol, hydrogenated starch syrup, sucrose and maltose. Alcohol can be mentioned.

Examples of edible polymeric plasticizers used with edible low molecular weight organic plasticizers include natural polymers such as sodium celluloseglycolate, cellulose methyl ether, sodium alginate, mannan, pullulan, agar, pectin and gum. And derivatives thereof.

Edible lubricants for use in the present molding compositions or molded articles should have the following properties. It must be compatible with inorganic alkali salts of starch and starch, be harmless to human or nutritious to humans, and have proper compatibility with binary mixture of neutral inorganic alkali salts and starch of protein. And have a lubricating effect on molding.

Examples of such lubricants include edible polyhydric alcohols such as glycerol, sorbitol, sorbitan, mannitol, maltitol, ethylene glycol, dienylene glycol, propylene glycol, dipropylene glycol, hydrogenated starch syrup and sucrose, stearic acid, Mono-, di- and triesters with edible higher fatty acids having 10 or more carbon atoms such as oleic acid, linoleic acid, linolenic acid, talmic acid and lauric acid: phospholipids such as lecithin (soybean phospholipid) and the aforementioned acids And phosphoric acid derivatives. Among these lubricants, lecithin is particularly suitable as a lubricant for use in the present composition because it has a favorable affinity and a suitable HBL value for both protein and starch, and an appropriate amount of lecithin added is 1 weight based on the total weight of the composition. Less than or equal to If necessary, more than 10% by weight of lecithin may be added. Compositions containing about 10% by weight lecithin have good glassy properties and films made from such compositions can be used for release paper for bread or buns.

When the molding composition does not contain any lubricant, it is difficult to continuously produce a uniform molded article at the time of molding. The need for lubrication has been neglected in the past, since the conventional starch-based moldings by the wet method were extruded or injected in a relatively viscous solution form, containing relatively large amounts of water, and the lubricating effect of the composition was almost undetectable. Could not.

The composition is prepared by uniformly mixing the components. This mixing can be achieved by simply mixing at room temperature using a variety of methods, such as stirring mixers and on the other hand by grinding to 40-50 ° C., or by grinding at Henschel mixers, roll mills, pressure mixers, or extruders at high temperatures. It is performed using the same heat grinder. It is preferable for the pulverized mixed molding composition, because the above-mentioned composition can be more uniformly supplied to the extruder or the injection machine through a hopper, can be regrind under milder conditions in the extruder or the injection machine, and extruded This is because a more uniform molded article can be produced by injection molding.

The molded article obtained from the present molding composition is completely edible because the components used as the composition are all selected from foods suitable for the Japanese food hygiene law or its food participation, and an important reaction that impairs edibleness during the manufacture of the molding composition or molded article Because this does not happen at all. Powdered, granular or pelletized compositions obtained by milling, cooling and grinding or granulating should be adjusted to have a predetermined amount of moisture content by drying or squeezing before molding by extrusion, injection or other molding techniques. Such adjustment of the moisture content can be made during the grinding of the components to produce the molding composition. This method is one of the advantages of the grinding method in preparing this molding composition.

By controlling the water content in the molding composition, it is possible to avoid the formation of pinholes caused by the evaporation of excess moisture as is common in extrusion molding, or the formation of bubbles caused by the release of gas. Since the present molding composition is characterized by a reduced water content compared with the conventional composition, it can be molded by the dry wet method.

The present molding composition is suitably stored in a cool dark place to prevent the growth of fungi and bacteria. In some cases, fungal remedies or fungicides may be added, or the composition may be sterilized by exposure to microwaves or ultraviolet light. In this respect, a low moisture content is advantageous. Moreover, it is preferable to store the molded article manufactured from the molding composition in a sealed and frozen container.

The molding composition thus prepared is a thermoplastic molding material which is uniformly dispersed and can be processed in the same way as conventional thermoplastic molding materials by compression molding, transfer molding, extrusion molding, injection molding, blow molding and inflation molding and economically. Water-soluble or hydrolyzable edible and pollution-free molded articles can be produced. Molded articles provide an excellent barrier to the delivery of oxygen gas and are advantageously used in food packaging, either on their own or together with other plastics.

Molded articles obtained by extrusion or injection molding are almost transparent or translucent because the inorganic alkali salts and starch materials of the protein component are uniformly dispersed and distributed. The edible molded article obtained from the composition has a much better advantage than the conventional one in terms of the balance between performance characteristics and production cost.

Molded articles of a predetermined form may be fed through the present molding composition to an extruder or injector at 100 ° C., or by heating the composition therein at a high temperature and injecting the molten composition into a mold maintained at a temperature of 90 ° C. or lower, or 100 Obtained by extrusion through a mold maintained at a temperature of not more than ℃. Since the two-component mixture of the inorganic alkali salt and the starch of the protein used in the composition exhibits good melt fluidity and plasticity in spite of the reduced water content, the composition is advantageously extruded through a mold or injected into a mold cavity. The extruded film can be calendered to increase the commercial value of the product.

The composition is extruded under the following conditions.

Extruder: L / D = 20-30

(Branch type is suitable)

Screw: Compression Ratio = 1.5-4.5

(Dulmadge is suitable)

Barrel: Water-cooled at the supply point.

Barrel Temperature, 90 ~ 200 ℃, 100 ~ 170 ℃

Suitable, withstand pressure, 10-150kg / ㎠

Mold: 70 ~ 120 ℃, 70 ~ 100 ℃ suitable

The atmosphere in the room should be controlled to maintain relative humidity between 20% and 80%. Extremely dry air is undesirable.

The composition is injection molded under the following conditions. The temperature inside the barrel should be in the range of 100-200 ° C., because below 100 ° C. the molding compositions do not have sufficient melt fluidity for molding and above 200 ° C. they are markedly discolored due to the decomposition of amylose. The injection pressure should be 10 kg / cm 2 or more, because below this limit, bubbles are formed inside the molded product, resulting in an incomplete product. The molding misuse should be 90 ° C. or lower, because at 90 ° C. or higher, the molded article is too soft and the molded article is not constantly discharged by the mold release pin, making continuous molding operation difficult. The composition has good moisture resistance when injected under suitable conditions as described above, and a transparent or translucent molded article is obtained in high yield. Accordingly, the present invention provides a novel method that can be industrially carried out to continuously produce a molded article of a predetermined form from a two-component mixture of an inorganic alkali salt of a protein component and a starch.

Other molding methods can also be applied to the present compositions under conditions somewhat similar to those described above.

Water-soluble and edible shaped articles according to the invention, in particular extruded films, are useful in the field of food packaging. However, in the case of using a film for packaging high functional foods, the film lacks water resistance. One way to increase the water resistance is to perform ultraviolet radiation treatment. As described above, an important feature of the present invention is that the compatibility between the neutral inorganic alkali salt of the protein component and the starch is sufficient to form a uniform mixture, and loose crosslinking is formed between the two component systems by chemical reaction. This crosslinking phenomenon is strongly promoted by heating or by ultraviolet radiation. When the molded article obtained by the usual method is exposed to ultraviolet radiation for a suitable time depending on the thickness of the molded article, the water resistance is increased to a predetermined value, and the molded article is obtained that it is soluble in moderately warm water even though it is insoluble in cold water.

Another way to increase water resistance is to add an edible protein coagulant as a component of the molding composition. Suitable coagulants are edible inorganic salts such as chlorides, carbonates, phosphates of tartium, potassium and calcium, lactic acid, nitric acid, citric acid, tartaric acid, acetic acid, butyric acid, maleic acid, fumaric acid and succinic acid, edible low molecular weight, organic acids, tactical It is selected from the group consisting of neutral or acid salts with one organic acid and sodium, potassium or calcium. These coagulants are used alone or in combination.

The protein coagulant is added in an appropriate amount to the usual blending amount of the present composition consisting of starch, neutral inorganic alkali salt of protein, water, edible plasticizer and lubricant. The resulting mixture is ground in the manner described above to form a water soluble, edible thermoplastic molding composition containing protein coagulant. The composition was molded in the same manner as described above to produce a water-soluble and edible thermoplastic molded article containing a protein coagulant. The molded article thus obtained has a cold water solubility which is somewhat reduced according to the amount of the coagulant added as compared with the molded article which does not contain the coagulant, and has almost the same solubility in hot water. Therefore, according to the present invention, the balance between the water resistance and the water solubility of the molded article can be controlled by varying the solubility in cold water within a wide range by controlling the amount of ultraviolet radiation or the amount of the coagulant.

The water-soluble and edible thermoplastic molded articles according to the present invention are more difficult to dissolve in aqueous solutions containing soluble inorganic salts such as common salts than in ordinary water, slightly soluble in acidic water but readily soluble in alkaline water. Thus, enteric capsules can be produced using this molded article. This is one of the important features of the present invention.

According to the present invention, a fully extinguishing molded article and a fully edible molded article can be easily obtained. This is another feature of the present invention.

Water-soluble, edible moldings containing a bicomponent mixture of starch-proteins can be used in subdivided packaging in the food, feed and pharmaceutical industries. The main use is water-soluble and edible pre-processed cooked food, pre-processed feed, fishing rice and edible It can be used for the packaging of additives. This is a seasoning (eg dehydrated soup stock, dehydrated soup stock, dehydrated "smile" soup stock, common salts, sugars, sodium salts of amino acids, sodium inosinate): dehydrated grains, vegetables, fruits, meats, eggs Etc .: Seasonings and condiments: Dry granules or powders such as nutritional vitamins, minerals, essential amino acids, and medicines are suitable for subdivision packaging by a few people. Such subpackages are convenient to use because they can be placed in cold or hot water without unpacking, and can be used representatively for the packaging of seasonings for instant noodles.

The film or sheet may also contain foods that contain an appropriate amount of water, such as mayonnaise, jam, margarine, shortening, "smile" (soybean paste), cappuccino, concentrated soup stock, broth stock, curry stew Cured stew storck: Suitable for food packaging such as salted fish, vegetables, fruits, fish, meat fishing rice and pet food. When these foods packaged with the film are placed in cold or hot water, the film easily collapses. When used in the packaging of foods containing common salt, vinegar, lactic acid, alcohol, etc., the film or sheet increases the water resistance and also has an antibacterial and antiseptic effect.

In the baking industry, this film or sheet packs a certain amount of bakery additives such as yeast food, margarine, sooting, common salt, sugar, yeast, eggs, cheese, seasonings, condiments, and milk powders. Can be used. Such packaging eliminates weighing errors and contributes to the hygiene and rationalization of the bakery. Similar uses for films and sheets can be found in the confectionery industry. In the case of using butter or margarine as the weighing sheet frond (eg for so-called roll-in margarine), the partition film or paper is advantageously used as the water-soluble and edible film or sheet of the present invention. It can be substituted. The film or sheet can be used as a release paper in the baking and confectionery industry and does not need to be removed after use because it is edible and can be incorporated into the product.

Fishing bait can be packaged with this film or sheet and stored for a long time or can be conveniently transported. In use, the package gradually collapses in water, giving the advantage of a durable fishing bait. The film or sheet also swells in water and the packaging is significantly improved in length, formation and ideal fishing.

This water-soluble and edible film or sheet made from a two-component mixture of starch-proteins is resistant to low temperatures and will not break and will not break other plastics for packaging high-functional frozen foods (eg fish, vegetables, fruits and meats). It is much more suitable than film and has the advantage of being non-tacky on ice.

Foods such as chocolate, curry loux and the like can be thermally deformed by heat contacting the mold, or cast into a packaging case made by injection molding to use the molding composition as a casting case. . The molded article is also suitable as a capsule for pharmaceutical packaging.

As described above, the edible sheets, films and shaped articles obtained from the water-soluble and edible molding compositions according to the present invention can be used in various fields, and the advantages for the industrial field are also remarkable.

The present invention will be described in more detail with reference to the following examples. In these examples, weight ratios and percentages are indicated unless otherwise stated.

Example 1

ratio

High Amyloscoon Starch (60% Amylose Content) 70

Casein-Sodium (Food Additives) 30

Glycerol (Food Additives) 60

The mixture was ground in a two-roll mill at a surface temperature of 120 ° C., on the one hand continued to add an appropriate amount of water, and on the other hand at the same time water was evaporated to form a uniform sheet. The resulting sheet was ground with an impact mill and mixed with a ratio of lecithin (food additive) 2 and then left at room temperature and high humidity until the water content of this material reached 25% to obtain granular, water soluble, edible and thermoplastic molding compositions. The granular molding compositions thus obtained had good keg-feedability and also showed good moldability when tested by various molding methods such as extrusion, injection, inflation and flow molding. The molding composition was stored in a cold dark below 10 ° C. After 6 months no change was seen.

The molding composition described above was continuously fed through a barrel to a barrel of a commercial extruder for a thermoplastic resin having a full fight screw (L / D = 20: compression ratio = 1.4) and ground under the following conditions. Barrel internal temperature = 120 ~ 160 ℃, screw rotation 30 ~ 100r.pm, barrel internal pressure = 40 ~ 70kg / cm ² , pulverizing the suspended mold (surface temperature = 100 ℃, opening gap 0.1mm at mold lip) It is continuously extruded through and wound into a cold winding roller, while the winding speed is adjusted to maintain the film thickness within the range of 60 to 100 mu. The extrudate was dried to a water content of 15 to 20% and wound up by a winder. The water soluble, edible thermoplastics thus obtained were extruded, pale yellow, plastic, at 20% RH, and had bleeding and blocking resistance at 80% RH. The film showed no change when stored in a closed polyethylene bag for 6 hours at temperatures below 10 ° C.

In a similar manner to the above, an extruded sheet having a thickness of 1.0 mm was obtained.

Inflation films, tubs, appearances and suction-molded articles were satisfactorily obtained from the molding compositions obtained above.

Various molded articles were satisfactorily produced from the extrudate by various techniques for thermoplastic resins, for example, heat fusion, vacuum molding, press molding and thermal welding.

The molded articles produced have been found to be useful for food, animal and fish food, and edible packages for fishing (crushed fishing rice).

The performance characteristics of the extruded film are shown in the second table.

TABLE 2

The molding composition obtained as described above was automatically supplied to the barrel of a commercial injection molding machine for thermoplastic resin and calcined under the following conditions. Barrel inner temperature: the bottom temperature of the barrel 30~50 ℃ (water-cooled), a middle portion temperature of 120~160 ℃ tube, from the bottom part of the bottle in the temperature 160~200 ℃ melt injection pressure of 20~100kg / cm ² to the barrel Injection into a mold cavity at 60 to 90 ° C yielded a water-soluble, edible and thermoplastic injection molded article. This molded article was translucent, pale yellow, static free, oil resistant, heat fused and difficult to pass oxygen. The moldings have been found to be useful in containers for cooking oil and butter and capsules for pharmaceutical packaging.

Translucent blow molded articles can be produced by injection suction molding.

EXAMPLES 2-4

TABLE 3

Water-soluble and edible thermoplastic molding compositions were prepared in the same manner as in Example 1 by the blending ratios shown in Table 3.

The molding compositions of Examples 2-4 produced molded articles having good moldability and excellent properties for various molding methods, such as extrusion, injection inflation and suction molding, for thermoplastic resins. The water contents of the compositions obtained in Examples 2, 3 and 4 were 25, 28 and 30%, respectively.

The molding compositions obtained in Examples 2 to 4 were extrusion molded under the same conditions as in Example 1. The obtained molded article was almost the same as that obtained in Example 1 in appearance and physical properties. The 100 μm-thick extruded films, obtained from the molding compositions of Examples 2, 3 and 4, exhibited an elongation of 18 to 23% at a tensile strength of 1.3 to 1.6 kg / cm ² and a 20 R.H.

Example 5

ratio

High-amylose coon starch (amylose content, 20%: water content, 10%) 40

Casein-sodium (food additive: water content, 10%) 40

Glycerol (Food Additives) 60

Gelatin-Sodium 20

Lecithin 5

The above components were mixed in a Henschel mixer (800-1,200 rpm) at 40-70 ° C., while water was continuously added to adjust the water content to 20% to obtain water-soluble and edible thermoplastic molding compositions in particulate form. The resulting particulate molding composition had good flowability and good moldability in various molding methods. Sodium gelatin in the above formulations may be substituted with salts of protein concentrates extracted from soy casein, milglutene, corm zein, or yeast, and neutralized to pH 6-8 with alkali to form salts. .

Through the molding composition obtained above, the barrel of a branched extruder having a dulmadge-typescrew (L / D = 30: compression ratio = 1.8) was continuously filled and plasticized and applied under the following conditions. . Bottom temperature of barrel 30 ~ 50 ℃ (water cooling), middle temperature of cylinder 100 ~ 140 ℃, front temperature of cylinder 70 ~ 110 ℃: Screw rotation speed, 60 ~ 200rpm, Barrel pressure 60 ~ 120kg / cm ² , the melt is extruded into a fish-shaped mold (internal temperature, 70-90 ° C.:0.05 mm opening gap in the mold lip), stretched through a water-cooled roller, and wound up to maintain the film thickness within the range of 40-60 μm. The speed was adjusted. The compact was dried to obtain a water content of 8-15% and wound with a winder to obtain a water-soluble and edible thermoplastic extruded film with a thickness of 60 μ, which had a tensile strength of 1.5 kg / cm ² and at 10% RH. Elongation was 15%.

Using the molding composition obtained above, a translucent container having a wall thickness of 0.5 mm was molded using an injection suction molding technique under conditions similar to those described in Example 1. While the vessel quickly collapsed in water, it could withstand a freezing temperature of -20 ° C when used as a container for cooking oil or margarine.

Example 6

ratio

High amylose scotch starch (amylose content, 50%) 40

Casein-sodium 30

Glycerol 50

Dry Yeast 30

Lecithin 5

In the same manner as in Example 5, the mixture was blended according to the above-described compounding amount to obtain a water-soluble and edible thermoplastic molding composition containing 40% of water content. This had good formability. Dry yeast in the formulation is edible and has a particle size of 80 mesh or less, for example baking yeast, beer yeast, torula yeast and so-called "petroleum yeast" incubated in a medium such as ethanol, methanol, n-paraffin or methane gas. (SCP). Molded articles obtained from molding compositions containing these yeasts had almost the same performance characteristics.

The obtained molding composition was extruded under the same conditions as described in Example 5 to obtain an inexpensive pale brown film having a water content of 20 to 25%. As water soluble and biodegradable, this film is suitable for making "seed tape" and "seed map". Low cost, water soluble and edible injection molded articles can also be obtained by molding the molding compositions described above under similar conditions as in Example 1.

EXAMPLES 7-9

TABLE 4

The components described in Table 4 were mixed in a mixer at room temperature to form fine particles having a water content of 25%. Using the conventional extruder (full flight screw (L / D = 22, extrusion ratio = 1.5)) used for the thermoplastic resin, the above-mentioned fine particles were extruded into a rod having a diameter of 3 mm under the following conditions. In-cylinder temperature, rotation speed of a screw of 120 to 160 ° C.-100 rpm: Mold temperature of 80 to 110 ° C. The rod was cut into pellets to obtain a water-soluble and edible thermoplastic molding composition having good moldability.

Each of the molding compositions thus obtained was extruded through a rotating tubing mold under substantially the same conditions as in Example 1 and expanded with compressed air to form an inflation film having a thickness of 40 to 80 µm, which contained 15% water and was carried out. It had almost the same appearance and properties as the film obtained in Example 1. The resulting film was particularly good in heat sealability and bags were automatically produced from the aforementioned films at periodic time intervals between 0.5 and several seconds by means of a commercial heat bonder between 110 and 150 ° C.

Water-soluble and edible injection-molded articles having excellent appearance and performance characteristics were obtained from the respective molding compositions under almost the same conditions as in Example 1.

[Examples 10 to 13]

TABLE 5

A method similar to that described in Example 5 was used to obtain a water soluble and edible thermoplastic composition adjusted to a moisture content of 15% with good moldability from the components listed in Table 5.

Each molding composition can be molded by the method used in Example 1 and the resulting molded article had almost the same performance characteristics as Example 1. In particular, the compressed film and the sheet containing 15% of moisture had excellent blocking resistance at a relative humidity of 80% or more.

[Examples 14-17]

TABLE 6

A method similar to that described in Example 7 was used to obtain a 25% water-soluble and edible thermoplastic composition having good molding from the components listed in Table 6. Each composition was extruded under similar conditions as those described in Example 5 to obtain films and sheets of 15-20% moisture content having performance characteristics comparable to those obtained in Example 1. These compressed films have excellent transparency and sheeting is suitable for thermoforming. Injection molding was carried out under similar conditions as those described in Example 1 to obtain an injection molded article having excellent transparency.

Example 18-19

TABLE 7

In the same manner as described in Example 5, water-soluble and edible thermoplastic molding compositions having a water content of 35% were obtained from the components listed in Table 7. The compositions were molded under the molding conditions used in Example 1 to obtain a variety of molded articles having only good appearance performance compared to those obtained in Example 1, with the exception of Examples 18 and 19, compared to the compositions of Example 1 The composition of was slightly poor in moldability, which hindered the continuous molding operation slightly, especially during the high speed extrusion process, and often caused agitation resulting in fluctuations in the thickness of the extrudate.

[Examples 20-23]

TABLE 8

In the same manner as described in Example 1, a water-soluble and edible thermoplastic molding composition having a water content of 25% having good moldability was obtained from the components described in Table 8. These compositions were molded under the molding conditions described in Examples 1 and 5 to obtain various molded articles having excellent transparency. The moisture content was adjusted to 12%, and the properties of the extruded film having a thickness of 60 mu are shown in Table 9.

Table 9

Performance characteristics of the compressed film obtained in Example 20 (thickness 60 µ, relative humidity 45%)

The compressed films obtained in Examples 21-23 were also excellent in transparency, solubility in cold water and plasticity.

[Examples 24 to 25]

TABLE 10

In the same manner as described in Example 1, a water-soluble and edible thermoplastic molding composition having a water content of 40% having good moldability was obtained from the components listed in Table 10. These compositions were molded under the molding conditions described in Examples 1 and 5 to obtain various molded articles having performance characteristics comparable to those obtained in Example 20.

[Examples 26-28]

TABLE 11

In a manner similar to that described in Example 7, water-soluble and edible thermoplastic molding compositions having a water content of 23% having good moldability were obtained. These molding compositions were molded under the conditions described in Examples 1 and 5 to obtain various molded articles having appearance and performance characteristics comparable to those obtained in Example 1.

Example 29

By the method of Example 1, a water-soluble and edible thermoplastic molding composition having a water content of 28% was obtained from a mixture of the ingredients blended in the same manner as in Example 2 except for various ratios of 40 casein powder and 20% aqueous sodium hydroxide solution. Was used instead of a casein-sodium powder 40 ratio. The molding composition thus obtained had characteristics comparable to those of the molding composition obtained in Example 2. When similar formulation changes were applied to the formulations of Examples 3 and 4, the properties of the resulting molding compositions did not differ significantly from those of the original formulation compositions.

Example 30

A water-soluble and edible thermoplastic molding composition having a water content of 15% was obtained in the same manner as in Example 5, except here the casein 40 ratio, the gelatin 20 ratio, and the sodium hydroxide instead of the casein-sodium 40 ratio and the gelatin-sodium 20 ratio. A 10% 20% aqueous solution and 5% calcium hydroxide 20% dispersed aqueous solution were used.

The molding composition thus obtained had properties comparable to those of the molding compositions obtained in Example 5. The properties of the resulting molding composition when similar formulation changes were applied to the formulations of Examples 19 and 22 did not differ significantly from those of the original formulation composition.

Example 31

A water-soluble and edible thermoplastic molding composition (water content 28%) was obtained in the same manner as in Example 7, except here the casein-65 ratio and 20% mixture with potassium hydroxide and potassium carbonate instead of the casein-sodium 70 ratio ( The ratio of 27 aqueous solution containing the weight ratio 1: 1) was used. The molding composition thus obtained exhibited comparable properties to those of the molding composition obtained in Example 7. When similar formulation changes were applied to the formulations of Examples 8 and 9, the properties of the resulting molding compositions did not differ significantly from those of the original formulation compositions.

Example 32

A water-soluble and edible thermoplastic molding composition (moisture content) was obtained in the same manner as in Example 20 except that a casein 49 ratio and a sodium carbonate 20% aqueous solution 15 ratio were used instead of the casein-sodium 50 ratio. The molding composition thus obtained had properties comparable to those of the molding composition obtained in Example 20. The properties of the resulting molding compositions when similar formulation changes were applied to the formulations of Example 23 did not differ significantly from those of the original formulation compositions.

Example 33

A water-soluble and edible thermoplastic molding composition (moisture content 35%) was obtained in the same manner as in Example 24 except that the gelatin 80 ratio and the sodium hydroxide 20% aqueous solution 10 ratio were used instead of the gelatin-sodium 80 ratio. The molding composition thus obtained had properties comparable to those of the composition obtained in Example 24. The properties of the resulting molding composition when similar formulation changes were applied to the formulations of Example 25 did not differ significantly from those of the original formulation composition.

Example 34

A water-soluble and edible thermoplastic molding composition (water content 23%) was obtained in the same manner as in Example 26 except for the casein 77% ratio and the sodium hydroxide 20% 15% aqueous solution instead of the casein-sodium 77 ratio. The molding composition thus obtained had properties comparable to those of the composition obtained in Example 26.

Example 35

The compressed film obtained in Example 1 was exposed to ultraviolet radiation for 3 minutes at room temperature. The exposed film was tested to find a phenomena of the divergence of odor and a marked decrease in water solubility (see Table 12).

Table 12 Changes in water solubility

These phenomena are a common phenomenon although there is a difference in degree with respect to the voltage-extracting films of Examples 1 to 34. The above-mentioned advantageous phenomenon can be used to increase the water resistance of the water-soluble extruded film to some extent. Ultraviolet radiation does not change the cohesiveness in heat sealability and other physical properties, and an extruded film that is not dissolved by such treatment is useful for the packaging of hydrated foods such as margarine, "smile" (miso) and the like.

Example 36

A water-soluble edible thermoplastic molding composition (moisture content 20%) was obtained in the same manner as in Example 5, except that a proportion of 10 salts was added to the mixture. The resulting composition did not have a significant change in the formability, appearance and physical properties of the molded article, but exceptionally low water solubility at low temperatures as shown in Table 13.

[Table 13] Change in Water Solubility

This trend was found to be common for all formulations described in Examples 1-28. This phenomenon was found to be nearly identical when salts were replaced with potassium chloride, potassium phosphate, potassium carbonate, sodium phosphate, sodium carbonate, calcium hydroxide and calcium chloride.

Example 37

A water-soluble and edible thermoplastic molding composition (water content 22%) was obtained in the same manner as in Example 7, except for the addition of 5 ratios of lactic acid. The resulting composition showed no change in moldability, appearance and physical properties of the molded article, except that the water solubility at low temperature was markedly reduced as shown in Table 14.

Table 14 Changes in Water Solubility

This phenomenon was a general trend for all the formulations described in Examples 1 to 34. This phenomenon was observed to be substantially the same when lactic acid was replaced with nitrate, citric acid, tartaric acid, acetic acid and butyric acid.

Example 38

According to the method described in Example 7, granular water-soluble and edible thermoplastic molding compositions (water content of 20%) were obtained from a mixture of the same ingredients as in Example 20, except that the blend contained sodium phosphate 3 ratio and One ratio of citric acid was further added. The resulting composition showed no change in moldability, appearance and physical properties of the molded article, with the exception that the molded article was insoluble although swelled at cooling below 10 ° C.

Claims (1)

At least one edible unmodified starch, at least one edible natural concentrated protein, at least one inorganic alkaline aqueous dispersion selected from hydroxides, carbonates and bicarbonates of sodium, potassium and calcium to form salts of this protein, glycerol, ethylene One or more edible organic low molecular weight plasticizers selected from glycols, sorbitol, sorbitan, mannitol, maltitol, hydrogenated starch syrup and sucrose, and edible polyhydric alcohols in these plasticizers and mono- or higher edible fatty acids having 10 or more carbon atoms. A mixture of di- and tri-esters, phosphoric acid derivatives of these esters and at least one lubricant selected from lecithin is heated and heated at a temperature above 50 ° C. so that the amylose content of the starch is at least 50% by weight, the starch to the protein salt of The weight ratio is 30/70 to 70/30, and the organic low molecular weight plasticizer The amount of the agent is 20 to 60 parts by weight and 1 to 11 parts by weight, respectively, per 100 parts by weight of the starch and protein salt, and the amount of the aqueous dispersion of the at least one inorganic alkali is sufficient to substantially neutralize the protein. The method for producing a water-soluble and edible thermosetting granular molding composition characterized by obtaining and adding water thereto little by little, and then granulating the mixture and adjusting its water content to 10 to 40% by weight. .