JP4919643B2 - Soluble film - Google Patents

Description

  When the soluble film is used as a coating / packaging material or carrier for food, medicine, cosmetics, etc., or as a film preparation for eating containing various functional ingredients, it is excellent in mouth solubility and / or water solubility. In addition, the present invention relates to a soluble film excellent in film properties such as drying resistance and blocking resistance.

  In recent years, soluble films have come to be used as packaging materials or carriers for foods, vitamins, pharmaceuticals, etc., or for the formulation of cosmetics and the like. For example, an edible soluble film is used as a flavor film holding a fragrance or the like for the purpose of mood change, prevention of bad breath, and the like. In addition, the idea of using a cosmetic film holding a moisturizer or the like as a pack, or dissolving it in water and using it as an emulsion has been presented. Furthermore, it has been studied to use an anti-inflammatory agent or the like as a poultice.

  Conventionally, wafers are known as soluble films. This is a potato starch that has been made alpha and then made into a thin film, which has been used as an auxiliary product for wrapping and drinking medicine. The idea of adding useful components can be proposed using the technique of wafers, but in the case of thin wafers, the amount of useful components added is limited due to the problem of film thickness. In addition, if the film thickness is increased, additive blending is possible, but since a highly viscous starch is used, it is necessary to reduce the starch concentration at the time of film preparation, and the resulting film becomes thin. is there.

  In order to expand the range of use as a soluble film, it is necessary to increase the film thickness. For this reason, gelatin, pullulan, modified starch, and starch-derived components are combined to form a film-forming material, which is combined with a gelling agent, a plasticizer, and the like to make a film. However, as the film thickness increases, the solubility of the film tends to deteriorate, and various devices have been made to improve the solubility.

  As an edible film for the purpose of disintegrating and dissolving the film, several examples based on starch are disclosed in Patent Publications. However, what is disclosed in the publication is not sufficient from the viewpoint of water solubility, is poor in water solubility, and when consumed as an edible film, the amount of saliva is insufficient when thirsty, etc. It is not satisfactory for film dissolution. In general, film dissolution is best achieved without creating so-called “dama”.

  In general, a soluble film is produced by dissolving a film-forming agent, a plasticizer, etc. in water, spreading it into a film, drying it, cutting it into an appropriate size, and putting it in a container. In general, a soluble film is required to dissolve in water or saliva without causing so-called “dama”. A supplement film containing ingredients such as vitamins can be considered as a supplement supply film. However, when the film melts poorly, a sense of incongruity occurs. In addition, this tendency is strong in people called dry mice who have a small amount of saliva secretion. Moreover, this tendency is stronger in elderly people, and it is desired to improve solubility in water and saliva. A definitive solution for water and saliva solubility and mouth melt is not yet known.

  In addition, when using a soluble film, it is required to have excellent mouth solubility and / or water solubility and excellent film properties such as drying resistance and blocking resistance. For example, a film made of gelatin is good for melting in the mouth, but under high-temperature and high-humidity conditions in summer, blocking occurs during storage, which is not satisfactory. Conventionally, various films have been disclosed for soluble films. However, no film satisfying the above-mentioned film characteristics required when using a soluble film has been proposed.

  For example, a film-like cosmetic is disclosed in which a raw material for external use is blended with a soluble film mainly composed of polysaccharides such as starch, mannan, locust bean gum, and carrageenan (Japanese Patent Laid-Open No. 2002-212027). However, since this film easily absorbs moisture, there is a problem that blocking is likely to occur. In addition, some kinds of polysaccharides such as carrageenan, pectin, pullulan, curdlan, thickening stabilizers such as xanthan gum and locust gum, plasticizers such as oligosaccharides and sorbit, flavorings, sweeteners, acidulants, extracts A food prepared as a film preparation that can be made into a film, dissolved in saliva with saliva, excellent in drought resistance, and capable of tasting aroma and refreshment is disclosed (Japanese Patent Laid-Open No. 5-23685). . However, this film has low moisture resistance, and blocking occurs under high humidity.

  In addition, an edible film is disclosed that is formed from a compound material that does not contain pullulan and contains an aqueous colloid such as sodium alginate, maltodextrin, and a filler, and is used for oral ingestion of pharmaceuticals (US Patent No. 6). , 656,493). However, this film has low molecular weight maltodextrin added to improve the solubility in water. However, if the concentration is increased, moisture resistance decreases and blocking tends to occur. Is insufficient. Furthermore, an edible film excellent in flexibility and containing no gelatin is disclosed, in which a modified starch such as etherified starch or esterified starch is blended with a plasticizer of 50% by weight or more of the starch (US Patent). No. 6,528,088 patent). However, this film also has reduced blocking resistance due to a large amount of plasticizer.

  The main ingredients are starch modified with chemical modification such as cross-linking, acetylation and organic esterification, hydroxyethylation and hydroxypropylation, and starch modified by oxidation, enzymatic conversion, acid hydrolysis, etc. An edible film used as an oral film has been disclosed (Japanese Patent Laid-Open No. 2003-213038). However, this film uses substantially any one of the modified starches and has insufficient blocking resistance.

  On the other hand, polyglutamic acid such as γ-polyglutamic acid is a polymer produced by Bacillus natto and is known as a substance that is the main component of “stickiness” of natto. Polyglutamic acid has been used in cosmetics and the like because of its excellent moisturizing property in addition to thickening action (Japanese Patent Laid-Open No. 59-209635). In addition to the moisturizing effect, the effect of promoting salivary secretion is also disclosed (WO2005 / 049050A1). Furthermore, the use of γ-polyglutamic acid or a salt thereof in an edible capsule (WO2003 / 049771A1), and polyglutamic acid as a base material for a wound dressing (Japanese Patent Laid-Open No. 2003-38633) are also disclosed. Yes. In addition, it is disclosed that γ-polyglutamic acid having an average molecular weight of 2 million or more or a salt thereof is used as a cosmetic composition, and the cosmetic composition is also shown to be used in a dosage form such as a sheet. (Japanese Patent Laid-Open No. 2004-210699). However, these disclosures do not disclose a soluble film excellent in mouth solubility and / or water solubility.

  As described above, various soluble and edible films have been disclosed in the past, but as food / pharmaceutical coating / packaging materials or carriers, or as film preparations for eating with various functional ingredients. When used, a soluble film excellent in mouth solubility and / or water solubility and excellent in film properties such as drying resistance and blocking resistance is not disclosed.

JP 59-209635. Japanese Patent Laid-Open No. 5-236885. Unexamined-Japanese-Patent No. 2002-212027. JP2003-38633A. Japanese Patent Laid-Open No. 2003-213038. Japanese Patent Application Laid-Open No. 2004-210699. WO2005 / 049050A1. WO2003 / 049771A1. US 6528088. US Pat. No. 6,656,493.

  An object of the present invention is to dissolve a water-soluble film that does not cause lumps when a soluble film is used as a coating / packaging material or carrier for food, medicine or cosmetics, or as a film preparation for eating containing various functional ingredients. It is to provide a soluble film having excellent film characteristics such as drying resistance and blocking resistance, and having excellent solubility in the mouth.

The present inventors are diligently studying to solve the above-described problems, and include at least one selected from the group consisting of γ-polyglutamic acid and / or a salt thereof in a film formed from a water-soluble polymer. Thus, it has been found that a soluble film can be provided in which the solubility in the mouth and the solubility in water are greatly improved, and the moisture resistance and drying resistance are hardly lowered, and the present invention has been completed. In the soluble film of the present invention, a soluble film having further excellent film characteristics is obtained by forming a film by adding a gelling agent and / or a plasticizer together with a water-soluble polymer and γ-polyglutamic acid and / or a salt thereof. Can be provided.

  In the present invention, the amount of γ-polyglutamic acid and / or a salt thereof to be added is preferably 1 to 25% by weight per solid content. In the present invention, the water-soluble polymer used for forming the soluble film is preferably at least one selected from the group consisting of starches, modified starches, polysaccharides, proteins, peptides, cellulose derivatives, and synthetic polymers. An example is given. Furthermore, in the present invention, preferable examples of the water-soluble polymer used for forming the soluble film include a group consisting of etherified starch, esterified starch and / or low molecular weight product of etherified starch, and resistant dextrin. There may be mentioned at least one selected from the above.

  The soluble film of the present invention has water solubility that does not cause lumps when used as a coating / packaging material or carrier for food, medicine, cosmetics, etc., or as a film preparation for eating containing various functional ingredients. Disclosed is a soluble film having excellent mouth meltability and excellent film properties such as drying resistance and blocking resistance. In particular, the soluble film of the present invention is a edible film preparation prepared as an edible and soluble film containing a pharmacological component, a nutritional component, an oral aroma refreshing component for preventing bad breath or changing mood, or a favorite component. When used as, or when used as a cosmetic-containing film preparation formed as a soluble film containing a cosmetic ingredient, it has excellent mouth solubility and / or water solubility, and is resistant to drying and Provided is a soluble film having excellent film properties such as blocking resistance. In the edible film of the present invention, the thickness of the film differs depending on the application, but it can be used in the range of 20 μm to 200 μm.

Specifically, the present invention specifically relates to (1) a water-soluble polymer formed from a water-soluble polymer that is at least one selected from the group consisting of starches, modified starches, polysaccharides, proteins, peptides, and cellulose derivatives. A soluble film excellent in mouth solubility, water solubility, drying resistance and blocking resistance, characterized in that γ-polyglutamic acid and / or a salt thereof is contained in the film in an amount of 5 to 20% per solid content , (2) The water-soluble film formed from the water-soluble polymer is a film formed by adding a gelling agent and / or a plasticizer to the water-soluble polymer. soluble Phil nothing Ranaru.

In the present invention, ( 3) at least the water-soluble polymer is selected from the group consisting of etherified starch, esterified starch, low molecular weight product of etherified starch, pullulan, casein, hydroxycelluloses, and indigestible dextrin. wherein characterized in that it is a type (1) or (2) soluble films and described, (4) the thickness of the soluble film, which is a 20μm~200μm (1) ~ (3) It consists of the soluble film of any one of these.

According to the present invention, a soluble film having the following excellent film properties is provided as an edible and soluble film to be taken orally, and as a soluble film carrying other active ingredients such as pharmaceuticals and cosmetics. Can do.
(1) According to the soluble film of the present invention, it is possible to provide a soluble film having water solubility without causing so-called “dama”. That is, in the present invention, based on the mixing ratio of the water-soluble polymer, γ-polyglutamic acid and / or salt thereof, and the plasticizer, the water dissolution rate is variously adjusted according to the intended use of the film. It is possible to dissolve in water without causing “dama” in the end.
(2) The soluble film of the present invention hardly breaks or curls due to drying. Therefore, it is excellent in drying resistance.

(3) The soluble film of the present invention exhibits excellent solubility and film characteristics as a packaging material for foods, pharmaceuticals and the like, and as a carrier for holding active ingredients such as foods and pharmaceuticals, and is suitably used for these applications. be able to. Moreover, the film which hold | maintained the active ingredient as cosmetics can be used suitably as a cosmetic film preparation. In the case of these uses, the film can be used by being affixed using a liquid containing water as a main component, or dissolved and applied in the liquid. Moreover, the soap film which hold | maintained the soap component is a utilization form of this invention which can be carried around easily and can be utilized suitably.
(4) Furthermore, since the soluble film of the present invention is excellent in melting in the mouth, it can be suitably used as a flavor film having a cooling effect, a cooling film in the mouth, or a supplement film holding vitamins and the like. Furthermore, these films can be easily carried in a compact plastic container or the like.

  In the present invention, a film formed from a water-soluble polymer contains at least one selected from the group consisting of γ-polyglutamic acid and / or a salt thereof, and is used as a coating / packaging material for food, medicine, cosmetics, etc. When used as a carrier or as a film preparation containing various functional ingredients, it has water solubility that does not cause lumps and excellent mouth solubility, and has film properties such as drying resistance and blocking resistance. It consists of an excellent soluble film. In the soluble film of the present invention, a soluble film having further excellent film characteristics can be obtained by adding a gelling agent and / or a plasticizer to the water-soluble polymer.

The soluble film of the present invention is prepared from the following components.
(Γ-polyglutamic acid):
The γ-polyglutamic acid of the present invention is a product in which glutamic acid is bound by a γ bond, has a molecular weight of about several tens of thousands to two million, and is produced by a fermentation method. Examples of the microorganism to be used include microorganisms belonging to the genus Bacillus having the ability to produce γ-polyglutamic acid, and examples thereof include Bacillus subtilis, Bacillus anthracis, Bacillus licheniformis, and the like. The component glutamic acid is generally a mixture of D-form and L-form. It is also possible to use γ-polyglutamic acid mainly composed of D form. γ-polyglutamate can be produced by reacting γ-polyglutamic acid with a basic compound. Although there is no restriction | limiting in particular as this basic compound, Organic basic compounds, such as alkali metals, alkaline-earth metal hydroxides, such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide, or ammonia, amines, etc. Can be used. Further, in order to form a cross-linked product of γ-polyglutamic acid, a bivalent or higher metal capable of reacting with a plurality of carboxyl groups of γ-polyglutamic acid is used. Preferably, calcium, iron, aluminum, chromium, or the like can be used.

(Soluble film):
The soluble film of the present invention is a film containing a water-soluble polymer and, if necessary, a plasticizer. When used as a soluble film preparation, as an optional component, for example, a fragrance, a vitamin, an herbal extract, an inorganic substance, a cosmetic Ingredients such as soap and soap are processed into a film or sheet. Water-soluble polymers that can be used in the present invention include gelatin, carrageenan, microfibrous cellulose, locust bean gum, modified starch, dextrin, indigestible dextrin, hydroxypropylated starch, hydroxyethylated starch, pullulan, hydroxypropylmethylcellulose , Hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl pyrrolidone, carboxymethyl cellulose, polyvinyl alcohol, polyethylene glycol, xanthan gum, gum tragacanth, guar gum, gum acacia, gum arabic, sodium polyacrylate, alginic acid and its salts, agar, methyl methacrylate copolymer, carboxy Vinyl polymer, high amylo starch, hydroxypropylated high amylose starch, dextst Emissions can pectin, chitin, chitosan, levan, elsinan, collagen, zein, gluten, soy protein, whey protein, be selected from casein and the group consisting of mixtures thereof. Preferred water-soluble polymers are hydroxypropylated high amylose corn starch, low molecular weight products obtained by oxidative bleaching of hydroxypropylated starch, indigestible dextrin, dextrin, celluloses, and the like.

(Plasticizer):
The plasticizer in the present invention has a function of softening the film, and for example, one or more of glycerin, sugar alcohol, monosaccharide, oligosaccharide and the like can be used. The blending ratio of the plasticizer is preferably about 3 to 40 parts by weight with respect to 100 parts by weight of the water-soluble polymer. If the plasticizer is less than this range, the drying resistance tends to decrease, while if it exceeds this range, the blocking resistance tends to decrease, such being undesirable. The blending ratio of the plasticizer is more preferably about 7 to 35 parts by weight.

(Gelling agent):
The gelling agent in the film of the present invention has a property of gelling upon cooling, and for example, one or more of carrageenan, gelatin, gellan gum, agar, alginate and the like can be used. Examples of the alginate include an alkali metal alginate such as sodium alginate; an alkaline earth metal alginate such as calcium alginate. The blending ratio of the gelling agent is usually preferably about 12 to 50 parts by weight with respect to 100 parts by weight of the water-soluble polymer. If the gelling agent is less than this range, the resulting film tends to curl easily, while if it exceeds this range, the meltability tends to decrease, which is not preferable. The blending ratio of the gelling agent is more preferably about 15 to 30 parts by weight.

(Optional component):
In addition to the water-soluble polymer and plasticizer, which are essential components, the soluble film of the present invention is a nutrient, various plant extracts, herbal ingredients, vitamins, minerals, antibacterial agents, anti-inflammatory agents, depending on the purpose of the film. , Antidepressant, bad breath prevention agent, saliva secretion promoter, antiallergic agent, antitussive agent, motion sickness agent, nitroglycerin, catechin, polyphenol, enzymes, organic acid, fragrance, dye, emulsifier, soap ingredient, flavoring agent, Fragrances, coloring agents, oils and fats, ultraviolet absorbers, and the like can be blended in time.

The soluble film of the present invention is prepared as follows.
(Preparation of film):
The film of the present invention comprises a water-soluble polymer and a plasticizer, if necessary, containing other optional components, and is prepared into a film shape by a conventional method. For example, it can be easily prepared by the steps of (1) preparation of stock solution, (2) coating, (3) drying, (4) aging, and (5) cutting. The following describes these steps:

(1) Preparation of stock solution: γ-polyglutamic acid and a water-soluble polymer are dispersed in about 1.5 to 4.5 times the amount of water at room temperature, and then heated as necessary to form a water-soluble polymer. Dissolve and suspend. While maintaining the liquid temperature at about 60 ° C., a plasticizer is added and dissolved and mixed. Furthermore, the said arbitrary component is melt | dissolved or disperse | distributed as needed, and a stock solution is obtained.
(2) Coating: After adjusting the solid content concentration so that the viscosity becomes about 2,000 to 5,000 mPa.s while maintaining the temperature of the above stock solution at 50 to 55 ° C. (usually 20 to 30% by weight) About), use an applicator to adjust the film thickness on the synthetic resin sheet. As the synthetic resin sheet, for example, a polyester resin sheet or the like can be used.

(3) Drying: Dry with hot air of about 80 to 110 ° C. to obtain a dry film. The thickness of the dried film is usually about 20 μm to 200 μm in view of drying resistance, touch feeling, water solubility and the like. The water content of the film is usually about 5 to 15% by weight from the viewpoints of touch and storage.
(4) Aging: The obtained film is allowed to stand in a humidity-controlled room at a temperature of 25 ° C. and a relative humidity of 45% for 24 hours to stabilize the moisture content and the like of the film.
(5) Cut: The aged film is peeled off from the synthetic resin sheet, cut appropriately, and commercialized.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.

(Materials and evaluation)
Material: The film in each example prepared the film of 3.3 cm length, 2.3 cm width, and 45-60 micrometers in thickness according to the said preparation method. Moreover, each performance test of the film piercing of the obtained film, water solubility, drying resistance, and blocking resistance was performed by the following method.

Film formability: Ease of film formation in the coating process and cut film (mouth): Relative in the test group how smoothly the film melts on the tongue. evaluated. The higher the score, the better.
(Water solubility): A film was taken on the palm of the hand, 1 ml of distilled water was added thereto, and when the film was melted with a fingertip, a relative evaluation was made as to how much it was dissolved without causing “dama”. The higher the score, the better.
(Moist feeling): “Moistness” of each film was relatively evaluated. The higher the score, the better.

(Drying resistance): Stored in a desiccator adjusted to “RH 20%, 25 ° C.” for one week, and the appearance of “crack” and “curl” was relatively evaluated and scored. The higher the score, the better.
(Blocking resistance): The film was adjusted in a desiccator adjusted to “relative humidity (RH) 45%, temperature 50 ° C.” (high temperature condition) for 24 hours or “RH 81%, 25 ° C.” (high humidity condition). It was stored in a desiccator for 1 week, and the expression state of blocking was relatively evaluated. The higher the score, the better.

Example 1
Γ-polyglutamic acid Na (Mitani Enterprise Co., Ltd .: molecular weight: about 2 million) was added to a soluble film mainly composed of modified starch, and a mouth-cooling film was prepared, which was evaluated for dissolution in the mouth and water solubility. . As shown in Table 1, γ-polyglutamate Na was added to the film (water content: 10%) formulation and evaluated. As reference examples, a dextrin (DE: 16) and a sodium alginate were prepared and compared.

  Hydroxypropylated high amylose corn starch (DS 0.12, amylose content 65 wt%, 20 wt% aqueous solution viscosity (50 ° C., B-type viscometer 10 rpm) 248,000 mPa · s), hydroxypropylated tapioca starch oxide (Viscosity of 20 wt% aqueous solution (50 ° C., B-type viscometer 10 rpm) 500 mPa · s), κ-carrageenan (manufactured by CP Kelco) and glycerin are mixed and used in the composition shown in Table 1 below, and the final moisture content Six types of films of 10% by weight and a thickness of 60 μm were prepared and subjected to a performance test. Table 1 shows the composition and performance test results of the cool film in the mouth. The numerical value in a table | surface shows a weight part.

  As shown in Table 1, with regard to mouth opening, no. All the effects were observed with 2 to 8 films. Reference examples No. 2 and No. 2 Compared with the film No. 3, the film No. 7 was excellent in the mouth opening, water solubility, moist feeling, drying resistance and blocking resistance. No. No. 1 film and No. 1 film. In the film comparison of No. 4, the mouthfeel was improved by adding γ-polyglutamic acid Na. No. As shown in film No. 8, when γ-polyglutamic acid Na was 30%, the drying resistance and blocking resistance tended to decrease.

(Example 2)
A pullulan was used as a water-soluble polymer, and a supplement film comprising γ-polyglutamic acid Na (manufactured by Ajitan Enterprises Co., Ltd .: molecular weight of about 2 million) and glycerin was prepared and evaluated. Table 2 shows the composition of the supplement film and the performance test results. The numerical value in a table | surface shows a weight part. The resulting supplement film melted well and it was easy to eat the supplement.

(Example 3)
Γ-polyglutamic acid Na (manufactured by Ajitan Enterprise Co., Ltd .: molecular weight of about 2 million) was added to a film mainly composed of a cellulose-based material, and a soap component was further added to evaluate water solubility. γ-Polyglutamic acid Na was added to the following film (water content: 10%) formulation so that the final concentration was 8.1% and evaluated. Table 3 shows the composition of the soap film. The numerical value in a table | surface shows a weight part. The resulting soap film melted smoothly and was able to be whipped without creating lumps.

Example 4
Casein was used as the water-soluble polymer, and a cosmetic film was prepared in combination with γ-polyglutamic acid Na. Table 4 shows the composition of the cosmetic film. The resulting film dissolved smoothly with water and could be melted and applied to the face, or water could be applied and applied to the face.

Claims (4)

Γ-polyglutamic acid and / or a salt thereof in a water-soluble film formed from a water-soluble polymer that is at least one selected from the group consisting of starches, modified starches, polysaccharides, proteins, peptides, and cellulose derivatives Is a soluble film excellent in mouth solubility, water solubility, drying resistance and blocking resistance, characterized by containing 5 to 20% per solid content . The water-soluble film formed from a water-soluble polymer is a film formed by adding a gelling agent and / or a plasticizer to a water-soluble polymer. The water-soluble polymer is at least one selected from the group consisting of etherified starch, esterified starch and low molecular weight product of etherified starch, pullulan, casein, hydroxycellulose, and indigestible dextrin. The soluble film according to claim 1 or 2 . The soluble film according to claim 1 , wherein the soluble film has a thickness of 20 μm to 200 μm.