JP3949641B2 - Trehalose powder and method for producing the same - Google Patents

Description

  The present invention relates to trehalose powder and a method for producing the same.

  As for the dehydration method using an anhydrous sugar, as disclosed in Patent Document 1, Patent Document 2, Patent Document 3 and the like, the present inventors previously captured an moisture-containing crystal by capturing moisture. This is a method of demonstrating dehydration power on the way to conversion. Unlike heat drying and the like, this method does not require harsh conditions, and thus has a characteristic of converting a hydrated product into a dehydrated article without deteriorating or deteriorating its quality.

  However, among these methods, in the case of using anhydrous aldohexose such as anhydrous glucose and anhydrous galactose disclosed in Patent Document 2, it is highly reactive because it is a reducing saccharide with a relatively large amount of dehydration, It was found that browning reactions with amino acids, peptides, etc. are likely to occur, and there is anxiety about the storage stability of dehydrated articles. It was also found that anhydrous aldohexose does not convert to water-containing crystals even at relatively high humidity, and has a poor dehydrating power. When anhydrous maltose disclosed in Patent Document 1 is used or anhydrous palatinose disclosed in Patent Document 1 is used, it is basically a reducing saccharide, although its reducing power is weak, and it is a long-term dehydrated article. It turns out that the stability is still anxious. In addition, the amount of water that can be captured is relatively small, about 5% of the saccharides in both cases, and it has also been found that there is a disadvantage that a large amount of anhydrous maltose or anhydrous palatinose is required as a dehydrating agent.

  On the other hand, non-reducible anhydrous glycosyl fructosides such as anhydrous raffinose, anhydrous erulose, and anhydrous meletitose disclosed in Patent Document 3 have no reducing power, so there is no browning reaction with amino acids, peptides, etc., and excellent long-term storage stability. It is thought that. However, since it has a fructoside bond with low acid resistance in its molecule, it is assumed that it is not necessarily suitable as a dehydrating agent for acidic water-containing products, and there remains concern about the stability of the resulting dehydrated article.

JP-A-62-136240 Japanese Patent Laid-Open No. 62-152536 Japanese Patent Laid-Open No. Sho 62-152537

  The present invention seeks to provide trehalose powder and a method for producing the same.

  The inventors of the present invention focused on natural non-reducing anhydrous carbohydrates for the purpose of eliminating the drawbacks of conventional dehydration methods using carbohydrates, and conducted intensive studies on the establishment and use of superior dehydrating agents. Has continued.

  As a result, among the non-reducing anhydrous carbohydrates, anhydrous trehalose (throughout this specification, α, α-trehalose is simply referred to as trehalose and α, β-trehalose is referred to as neotrehalose) is dehydrated from the hydrous material. It was found that both the amount and the dehydrating power are large, and the obtained dehydrated article is extremely stable, so that it can be applied in a wide range and is suitable as a dehydrating agent. In other words, anhydrous trehalose is contained in hydrated foods such as hydrated foods and hydrated pharmaceuticals and converted into hydrated crystals of trehalose, so that anhydrous trehalose captures a large amount of water and acts as a very powerful dehydrating agent. The present invention has been found to be applicable to a wide range of hydrated products including hydrated products, and confirmed that dehydrated articles such as high-quality dehydrated foods with good flavor and highly active and stable dehydrated medicines can be easily produced. Was completed.

  As is apparent from the above, the present invention provides a trehalose comprising one or more components selected from raw materials or processed intermediates of foods, pharmaceuticals, cosmetics, industrial chemicals, together with non-reducing trehalose. It is an invention relating to the use of the containing composition and trehalose. For example, anhydrous trehalose as trehalose reduces moisture contained in an atmosphere in a moisture-proof container enclosing, for example, dry food, and further, for example, food, pharmaceuticals, cosmetics, industrial chemicals, these raw materials, or It can be advantageously used for reducing the water content of various hydrates such as processing intermediates. In particular, the method of the present invention, in which anhydrous trehalose is converted to trehalose hydrated crystals and dehydrated to substantially reduce moisture, does not require severe conditions such as heat drying, and various hydrated substances such as flavors, A high-quality dehydrated article can be easily produced without degrading the quality of foods that tend to deteriorate aroma, degradation of active ingredients, and pharmaceuticals that are likely to have decreased activity. In addition, the obtained dehydrated article is prevented from being contaminated with microorganisms, is prevented from being deteriorated and deteriorated such as hydrolysis, rancidity, and browning, and the life of the product can be stably maintained over a long period of time.

  The present invention focuses on a dehydrating agent for non-reducing saccharides, and selects anhydrous trehalose that has not been attracted attention as a dehydrating agent. The anhydrous trehalose is added as a dehydrating agent to dehydrate a hydrated product. The method will be referred to as the arrow according to the present invention.

  The dehydration method of the hydrated product in the present invention is preferable as a dehydration method for those containing moisture, especially those containing free moisture different from bound moisture such as crystal water, for example, dried foods etc. When reducing the moisture contained in the atmosphere in the enclosed moisture-proof container, for example, when reducing the moisture of various hydrated substances such as food, pharmaceuticals, cosmetics, industrial chemicals, raw materials or processed intermediates thereof, etc. It can be advantageously applied.

  When anhydrous trehalose is added to these hydrates, the anhydrous trehalose has a water content of about 10 w / w% (hereinafter, unless otherwise specified, w / w% is simply abbreviated as%). It was found that this value (corresponding to twice the amount of anhydrous maltose) was strongly taken in from the hydrated product as the crystal water of the hydrated trehalose crystal, and the water content of the hydrated product was substantially reduced and dehydrated.

  For example, in a moisture-proof container filled with dried foods such as seasoned seaweed and cookies, anhydrous trehalose filled in a moisture-permeable sachet made of paper coexists to extremely reduce the relative humidity in the container and dry it It has been found that foods, powders, etc. can be maintained in high quality and stably for a long period of time.

  At this time, anhydrous trehalose is trapped in moisture and converted into water-containing crystals of trehalose, and after conversion, it does not stick or flow, and it is likely to contaminate dried food and moisture-proof containers. There is no. In addition, adhesion and consolidation of the powdery material can be prevented. Furthermore, trehalose itself is a non-toxic, harmless natural sweetener and has no danger.

  In addition, for example, in the case of liquid, paste-like high moisture foods such as brandy, vinegar, royal jelly, fresh cream, mayonnaise, etc., by adding anhydrous trehalose and converting it to trehalose hydrated crystals, it is substantially High-quality dehydrated foods with reduced water content, for example, food products such as muskits and powders can be produced very easily.

  In this method, trehalose is a non-reducing saccharide and is stable, and does not require severe conditions such as heat drying, so it does not deteriorate or deteriorate a liquid or pasty high-moisture food, and has a good flavor. It has the characteristics that it can be easily converted into dehydrated foods with reduced moisture.

  Also, at this time, anhydrous trehalose was added in an amount more than the amount of water contained in food ingredients, etc., and anhydrous trehalose was partially converted into trehalose-containing water crystals, in other words, dehydrated food containing trehalose anhydrous crystals When this is sealed in a moisture-proof container, moisture in the container is trapped and dehydrated by anhydrous trehalose as water-containing crystals of trehalose, and the relative humidity is extremely reduced to keep the interior of the container highly dry. Turned out to be possible. As a result, the dehydrated food obtained according to the present invention is capable of preventing microbial contamination, preventing deterioration, degradation such as hydrolysis, rancidity, and browning, and maintaining a stable and high-quality product for a long period of time. There was found.

  In addition, in the case of pasty pharmaceuticals such as aqueous solutions of lymphokines and antibiotics, ginseng extract and suppon extract, anhydrous trehalose is added to these and converted to water containing trehalose, thereby substantially reducing water content. High quality dehydrated pharmaceuticals such as mass kits and powders can be produced very easily.

  This method does not require harsh conditions such as heat drying, and since anhydrous trehalose acts not only as a dehydrating agent but also as a stabilizer, a high-quality and stable dehydrated pharmaceutical can be produced. In addition, since there is no need to worry about energy waste for drying, such as a water-soluble polymer compound, a higher quality and more stable dehydrated medicine can be produced by using it as needed. This can also be advantageously carried out.

  In addition, for example, a certain amount of anhydrous trehalose is taken in a vial, and for this, for example, an aqueous solution containing a physiologically active substance such as lymphokine or hormone is required for the anhydrous trehalose to convert the anhydrous trehalose into trehalose-containing crystals. It is also possible to advantageously carry out production of a solid preparation or the like by adding only an amount smaller than the amount and sealing it.

  In this case, it was also found that anhydrous trehalose can dehydrate an aqueous solution containing a physiologically active substance, and can also moisture-dry the atmosphere in the vial.

  As a result, the dehydrated solid pharmaceutical product obtained by the present invention is not only easy to manufacture, but also can stably maintain its high quality for a long period of time, and further dissolves quickly in water during use. It was also found to have characteristics.

It is also possible to mix a predetermined amount of an aqueous solution containing a physiologically active substance with stirring a certain amount of anhydrous trehalose and enclose the resulting powder as it is in a container to make a high-quality and stable solid preparation. Further, the powder can be advantageously used after being molded into granules, tablets, etc. according to a conventional method. As described above, the dehydrating agent using the anhydrous trehalose of the present invention is a conventionally known silica gel, Unlike a dehydrating agent such as calcium oxide, it is not only a saccharide dehydrating agent that is edible and metabolized, but can also be advantageously used as a stabilizer for various physiologically active substances.

  Prior to the present invention, the present inventors studied a method for producing anhydrous trehalose, especially anhydrous trehalose powder.

  As anhydrous trehalose, for example, crystalline anhydrous trehalose, amorphous anhydrous trehalose and the like are suitable.

  For crystalline anhydrous trehalose, G. Birch reports a method of crystallization from pyridine in Journal of the Chemical Society, pages 3490-3490 (1965). is doing. This method uses a large amount of pyridine as a solvent and thus requires a production cost and is not preferable from the viewpoint of food hygiene.

  Therefore, the inventors first studied a method for producing crystalline anhydrous trehalose powder and established the method. That is, the method is, for example, an aqueous solution in which a commercially available trehalose hydrated crystal is dissolved, or an extract from yeast or the like described in Hayashibe et al. In Fermentation Association, Vol. 17, pages 106 to 115 (1959). The purified aqueous solution of trehalose is made into a high-concentration syrup having a water content of less than about 10%, desirably 2.0% or more and less than 9.5%, and this syrup is in the temperature range of 50 to 160 ° C. in the presence of seed crystals of anhydrous trehalose. The crystalline anhydrous trehalose may be crystallized and powdered while maintaining the above.

  As a pulverization method, for example, a known method such as a block pulverization method, an extrusion granulation method, a fluidized granulation method, or a spray drying method may be appropriately employed. In order to produce amorphous anhydrous trehalose powder, for example, commercially available trehalose hydrous crystals may be used as raw materials, or may be produced using a high-concentration solution of high-purity trehalose extracted and purified from yeast or the like. .

  In the case of using trehalose hydrous crystals, the crystals may be prepared by dissolving them in water and, for example, drying them at atmospheric pressure or vacuum at a temperature of about 100 to 160 ° C. and then pulverizing them. When a high-purity trehalose aqueous solution is used, for example, syrup having a concentration of about 70 to 90% is vacuum-dried or freeze-dried and then pulverized, or syrup having a concentration of about 60 to 85% is pressurized. It is also advantageous to produce the powder directly by spray drying methods such as the nozzle method or the rotating disk method.

  The anhydrous trehalose powder of the present invention thus produced is a non-reducing white powder having a refined low sweetness, its water content is low and substantially anhydrous, and is usually less than 3% by Karl Fischer method. Desirably, it is less than 2%, and its fluidity is substantially fluid, although it varies somewhat depending on the shape and size of the powder particles.

  Furthermore, the anhydrous trehalose referred to in the present invention may be substantially anhydrous trehalose which is converted into trehalose hydrated crystals and exhibits a strong dehydrating action. For example, the anhydrous trehalose promotes the conversion of anhydrous trehalose into trehalose hydrated crystals and serves as a dehydrating agent. In order to enhance the effect of the above, it is also possible to advantageously use a substantially amorphous anhydrous trehalose powder in which a trehalose-containing crystal as small as possible, usually less than 5%, desirably less than 1%, coexists as a seed crystal.

  When the anhydrous trehalose powder thus obtained is contained in, for example, a hydrated product such as food, pharmaceuticals, cosmetics, and industrial chemicals, the moisture contained therein is captured and fixed as crystallization water of trehalose hydrated crystals. It has been found that it acts as a powerful dehydrating agent on hydrated substances.

  The dehydrating agent of the present invention can be advantageously applied when the atmosphere in the moisture-proof container is dehumidified and dried, and further, a hydrated product that is easily altered or deteriorated in a process such as heat drying or vacuum drying, or a hydrated product that is difficult to dry. In some cases, high-quality dehydrated articles such as mass kits and powders are manufactured from products.

  In the case of dehumidification and drying, for example, not only can it be used for preventing moisture absorption of seasoned seaweed, cookies, etc., but also, powdery materials that are easily absorbed and consolidated, such as pudding mix powder, hot cake mix powder, etc. Premixed powder, salt, sugar, powdered soy sauce, powdered miso, powdered sushi vinegar, powdered dashi nori, powdered compound seasoning, powdered paprika, powdered garlic, powdered cinnamon, powdered nutmeg, powdered pepper, powdered sage and other powdered spices Powdered yeast extract, powdered milk, powdered yogurt, powdered cheese, powdered juice, powdered herb, powdered vitamin, granule soup, granule bouillon, fish powder, blood powder, bone meal, powdered lactic acid bacteria, powdered enzyme preparation, granule digestive, etc. By blending the product with anhydrous trehalose and enclosing it in a package, the relative humidity in the packaging container is reduced, and adhesion and solidification of the powdered product are reduced. Since can be prevented, it can be utilized for purposes such as maintaining fluidity good quality immediately after production long term.

  In addition, when dehydrating a hydrate, for example, it is advantageous when dehydrating various hydrates such as animals, plants, microorganism-derived organs, tissues, cells, ground products, extracts, components, or preparations thereof. Available to:

  For example, in the case of food, its raw materials or processed intermediates, raw fruits, juices, vegetable extracts, soy milk, sesame paste, nut paste, raw bean paste, gelatinized starch paste, wheat flour and other agricultural products, sea urchin paste, oyster extract, Marine products such as sardine paste, raw eggs, lecithin, milk, whey, fresh cream, yogurt, butter, cheese, livestock products such as maple syrup, honey, miso, soy sauce, mayonnaise, dressing, bonito extract, meat extract, Kelp extract, chicken extract, beef extract, yeast extract, mushroom extract, licorice extract, stevia extract, hydrous seasonings such as these enzyme-treated products and pickled seasonings, alcoholic beverages such as sake, wine, brandy, whiskey, medicinal liquor , Green tea, tea, coffee, etc., mint, wasabi, garlic, mustard, sun Water-containing spices extracted from leopard, cinnamon, sage, laurel, pepper, citrus, etc., water-containing colorants extracted from Acacia, redwood, turmeric, paprika, red beet, safflower, gardenia, saffron, red yeast, etc. It is possible to easily produce a dehydrated food having a stable and good taste from a liquid or paste-like material such as a hydrous emulsifier prepared from sugar fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, etc. it can.

  Dehydrated foods obtained in this manner, such as powdered agricultural and aquatic products, powdered fats and oils, powdered fragrances, powdered colorants, powdered emulsifiers, powdered preservatives, seasonings such as mayonnaise, soup bases, hard candy, cakes Can be advantageously used as processing materials for various foods and drinks such as confectionery, hot cake mix, instant juice, etc., for example, natural bulk flavors with good flavor.

  In the case of pharmaceuticals, raw materials or processed intermediates, interferon-α, -β, -γ, Tsumore necrosis factor-α, -β, macrophage migration inhibitory factor, colony stimulating factor, transfer factor, interleukin Lymphokine-containing liquids such as II, insulin, growth hormone, prolactin, erythropoietin, hormone-containing liquids such as egg cell stimulating hormone, BCG vaccine, Japanese encephalitis vaccine, measles vaccine, polio vaccine, seedling, tetanus toxoid, hub antitoxin, human immunity Biologic-containing liquids such as globulins, penicillin, erythromycin, chloramphenicol, tetracycline, streptomycin, kanamycin sulfate and other antibiotic-containing liquids, thiamine, riboflavin, L-ascorbic acid, liver oil, carotene Vitamins containing liquids such as id, ergosterol, tocopherol, lipases, elastase, urokinase, protease, β-amylase, isoamylase, glucanase, lactase and other enzyme containing liquids, ginseng extract, suppon extract, chlorella extract, aloe extract, propolis Extracts such as extracts, viable pastes such as viruses, lactic acid bacteria and yeast, and liquid or pasty products such as royal jelly can also be used as stable, high-quality dehydrated medicines and dehydrated health foods without losing their active ingredients. Easy to manufacture.

  In the case of cosmetics, raw materials or processed intermediates, as in the case of the foods and pharmaceuticals, raw eggs, lecithin, fresh cream, honey, licorice extract, fragrances, coloring agents, enzymes, etc. can be dehydrated. High quality dehydrated cosmetics can be easily obtained.

  This cosmetic can be advantageously used as a skin beautifying agent, hair beautifying agent, hair restoring agent and the like. Further, when the dehydrated article is an enzyme, it can be advantageously used as a catalyst for processing foods, pharmaceuticals, industrial raw materials and the like, as a therapeutic agent, a digestive agent and the like, and further as an enzyme detergent.

  As a method of adding anhydrous trehalose to the hydrated material, known methods such as mixing, kneading, dissolution, infiltration, spraying, coating, spraying, pouring, etc. are appropriately used until the desired dehydrated article is completed. To be elected.

  The amount of anhydrous trehalose to be added to the hydrated product also varies depending on the amount of water contained in the hydrated product and the properties of the target dehydrated article. If necessary, the hydrated product is partially dehydrated or concentrated by other known methods. After that, anhydrous trehalose may be added, and is usually 0.01 to 200 parts by weight, preferably 0.01 to 50 parts by weight with respect to 1 part by weight of the hydrated product. At this time, it is also advantageous to use appropriate flavorings, coloring agents, flavoring agents, stabilizers, extenders, etc. in combination in order to further improve the quality of the dehydrated articles obtained, such as foods, pharmaceuticals, and cosmetics. Can be implemented.

  In particular, for the stabilizer, since the present invention is a powerful dehydration method using anhydrous trehalose, it is not necessary to limit to a low molecular compound such as an antioxidant, and a water-soluble polymer compound that has been conventionally difficult to dry, For example, soluble starch, dextrin, pullulan, erucinan, dextran, xanthan gum, gum arabic, locust bean gum, guar gum, tragacanth gum, tamarind gum, carboxymethylcellulose, hydroxyethylcellulose, pectin, agar, gelatin, albumin, casein Can be used as advantageous.

  When these water-soluble polymer compounds are used, for example, the water-soluble polymer compound is uniformly dissolved in advance in a liquid or pasty hydrated product, and then mixed with anhydrous trehalose and uniformly mixed by a method such as kneading. By containing, a dehydrated article in which fine trehalose hydrous crystals are precipitated can be obtained.

  In this product, aroma components derived from hydrated substances, active ingredients, etc. are coated with a film of a polymer compound, or are encapsulated with fine trehalose hydrated crystals in microcapsules surrounded by the film. Since quality deterioration is prevented, it is extremely excellent in the stable retention of aroma components derived from hydrated substances and active ingredients. At this time, if necessary, a cyclodextrin that forms an inclusion compound with an aroma component or the like can be advantageously used as a water-soluble polymer.

  The cyclodextrin is not necessarily limited to a high-purity product, but is a low-purity cyclodextrin that is difficult to dry and pulverize, for example, a starchy starch hydrolyzate containing various cyclodextrins together with a large amount of maltodextrin Etc. can also be used advantageously.

  In the dehydrated article of the present invention, various methods can be employed for producing a powdered article. For example, anhydrous trehalose is uniformly contained in a moisture content containing relatively high moisture such as foods, pharmaceuticals, cosmetics, raw materials or processed intermediates thereof so that the moisture content is about 40% or less, preferably 10 to 30%. After that, it is left in a bat for about 0.1 to 5 days at about 10 to 50 ° C., for example, room temperature, converted to a trehalose hydrated crystal, and solidified into a block shape, for example, by cutting, pulverizing or the like. What is necessary is just to manufacture. If necessary, a drying step, a classification step, and the like can be added after the powdering step such as cutting and pulverization. In addition, a powder product can be directly produced by a spraying method or the like.

  For example, while an anhydrous trehalose powder is fluidized, a predetermined amount of liquid or pasty hydrated product is sprayed on the powder and brought into contact with it, and granulated. Then, if necessary, about 0.1 to about 0.1 to about 30 to 60 ° C. After aging for 10 hours, convert to trehalose hydrated crystals, or after mixing anhydrous trehalose with liquid or pasty hydrated product, knead, etc., immediately or start conversion to trehalose hydrated crystals. The method of aging a powder product obtained by spraying in the same manner as necessary and converting it into a water-containing trehalose crystal is suitable as a method for mass production of a powdered dehydrated article.

  In the case of this spraying method, in order to promote the conversion of anhydrous trehalose into water containing trehalose, it is possible to reduce or eliminate the ripening period by coexisting with water as little as possible trehalose water-containing crystals as seed crystals. Can be advantageously implemented. The powdered dehydrated article thus obtained is used as it is or in combination with a bulking agent, an excipient, a binder, a stabilizer, etc., as necessary, and further, granules, tablets, capsules, It can be freely used after being molded into an appropriate shape such as a rod, plate or cube.

  In addition, foods such as peanuts, almonds and candies, and pharmaceutical intermediates such as granules and uncoated tablets are used as a core, and a binder of about 60 to 90% aqueous solution of anhydrous trehalose, preferably a water-soluble polymer. It is also possible to advantageously carry out the production of sugar coating by coating an aqueous solution in which an appropriate amount is coexisted, and then converting it into trehalose-containing crystals and allowing it to crystallize.

  In general, starch requires a large amount of water for swelling and gelatinization. Therefore, gelatinized starch is extremely susceptible to microbial contamination. Anhydrous trehalose can also be effectively used as a dehydrating agent for such gelatinized starch. For example, gelatinized starch such as fertilizers can contain anhydrous trehalose and be converted to water containing trehalose to substantially reduce moisture and prevent microbial contamination.

  Also, anhydrous trehalose is easily and uniformly mixed with gelatinized starch and acts as an anti-aging agent, so that the product life of various processed foods containing gelatinized starch can be greatly extended.

  In addition, anhydrous trehalose is a high moisture content food that is susceptible to microbial contamination on the surface, such as peeled bananas, oranges, sliced steamed rice cakes, open rice cakes, sword fish, raw noodles, boiled noodles, rice cake confectionery, etc. The surface is coated with crystalline anhydrous trehalose powder to convert it into water containing trehalose, substantially reducing the moisture on the surface, improving the shelf life of these foods, improving the quality of the food, It can be advantageously used as a stabilizer or a quality improver. At this time, if necessary, for example, lactic acid, citric acid, ethanol, etc. can be used in combination, or vacuum packaging, gas filling packaging, refrigeration, etc. can further extend the product life.

  Anhydrous trehalose shows a high affinity for alcohol. From this property, it can be advantageously used as a dehydrating agent for water contained in alcohols such as methanol, ethanol, butanol, propylene glycol, glycerin and polyethylene glycol or alcohol-soluble materials.

  For example, dehydrated liquors such as sake, shochu, wine, brandy, whiskey, and vodka are dehydrated with anhydrous trehalose, and the resulting trehalose hydrated crystals are useful in dehydrated liquors such as maskits and powders that retain their active ingredients, aroma, etc. Can be manufactured. The powdered liquor thus produced can be used for confectionery, premixes, etc., and can be reconstituted with water for drinking.

  In this case, anhydrous trehalose can exhibit not only an effect as a dehydrating agent and a stabilizer, but also an effect as an elegant sweetness, body, appropriate viscosity imparting agent, and the like.

  In addition, an alcohol solution such as iodine is mixed with anhydrous trehalose, added to an aqueous solution containing a water-soluble polymer, etc., and then converted into a trehalose hydrous crystal, thereby stably holding an active ingredient such as iodine, and It is also advantageous to manufacture a mass kit-like salve having a suitable viscosity, elongation and adhesion.

  Also, anhydrous trehalose is impregnated and mixed with water-containing oil-soluble substances, emulsions, latex, etc. to convert anhydrous trehalose into trehalose water-containing crystals, powdered oils, spices, fragrances, colorings, foods, cosmetics, powders It is also advantageous to produce pharmaceuticals such as vitamins and hormones.

  In this case, anhydrous trehalose is converted not only as a dehydrating agent but also into trehalose hydrated crystals and acts as a stabilizer, a holding agent, an excipient, a carrier and the like.

  Also, anhydrous trehalose is advantageously used in the case of foods containing oily substances that dislike moisture such as chocolate and sand cream. In this case, it is used not only as a dehydrating agent but also for improving processability, melting in the mouth, flavor and the like. Furthermore, the product obtained has the characteristic that it can be stably maintained for a long time with its high quality.

  As described above, the present invention is achieved by finding that anhydrous trehalose, which is a non-reducing saccharide, strongly dehydrates the water of various hydrates, and that the resulting dehydrated article is extremely stable. By using the anhydrous trehalose as a dehydrating agent, it is possible to produce high-quality foods with reduced water content without degrading or evaporating the flavor and aroma from liquid or pasty water-containing substances, It is possible to advantageously produce cosmetics and high-quality pharmaceuticals and cosmetics with reduced moisture without degrading and reducing the active ingredients and activities thereof.

  Anhydrous trehalose is not only a special case as described above, but also a natural sweetener. It is digested and absorbed in the human body without any concerns such as induction of caries or blood cholesterol, and is almost the same as maltooligosaccharides. Demonstrate the degree of nutrition. Furthermore, since it has properties such as elegant sweetness, body addition, shine, viscosity, and water retention, it can be advantageously used in the production of foods, pharmaceuticals, cosmetics and the like. Next, other usage examples will be described.

  Anhydrous trehalose can be used as a seasoning having a strong dehydrating action. If necessary, for example, powdered rice cake, glucose, isomerized sugar, sugar, maltose, honey, maple sugar, sorbitol, maltitol, dihydrochalcone, steoside, α-glycosyl stevioside, rakanka sweet, glycyrrhizin, thaumatin, L-aspara It can also be used in admixture with other sweeteners such as tilphenylalanine methyl ester, saccharin, glycine, alanine and the like, and with bulking agents such as dextrin, starch, lactose and the like.

  Anhydrous trehalose is a non-reducing saccharide and has an elegant sweetness inherent in trehalose, well harmonized with various substances having other tastes such as acidity, salt to taste, astringency, umami, bitterness, Since it has high acid resistance and heat resistance, it can be advantageously used not only as a dehydrating agent for general foods but also for sweetening, taste improvement and quality improvement.

  For example, soy sauce, powdered soy sauce, miso, powdered miso, moromi, horsetail, flicker, mayonnaise, dressing, vinegar, three cups of vinegar, powdered sushi vinegar, Chinese food, tentsuyu, noodle soup, sauce, ketchup, grilled meat sauce, curry roux, stew As a dehydrating agent for various seasonings such as Nomoto, soup, dashi, composite seasoning, mirin, new mirin, table sugar, coffee sugar, sweetener, taste improver, quality improver, etc. Can also be advantageously implemented. Also, for example, Japanese rice cakes such as rice crackers, hail, rice cakes, fertilizers, potatoes, manju, sea bream, bean pastes, sheepskin, water sheepskin, brocade, jelly, castella, candy balls, bread, biscuits, crackers, cookies , Pie, pudding, butter cream, custard cream, cream puff, waffle, sponge cake, donut, chocolate, chewing gum, caramel, nougat, candy, and other Western confectionery, ice cream, sorbet and other ice confections, fruit syrup pickles, ice honey Syrups such as, pastes such as flower paste, peanut paste, fruit paste, fruits such as jam, marmalade, syrup pickles, sugar cane, processed foods of vegetables, pickles such as pickled Fukujin pickles, bedara pickles, thousand pieces pickled, oyster pickles, Takuan pickles, Chinese cabbage pickles Pickled vegetables such as ham, sausage and other meat products, fish meat ham, fish meat sausage, fish products such as sea urchin, chikuwa, tempura, sea urchin, squid salted salt, vinegared kombu, suki-meme, dried puffer fish, cod , Thai and shrimp and other delicacies such as rice fields, seaweed, wild vegetables, sea cucumbers, small fish, shellfish, etc., boiled beans, potato salad, side dish foods such as kombu rolls, dairy products, fish meat, livestock meat Bottles of fruit, vegetables, canned foods, alcoholic beverages such as synthetic liquor, brewed sake, fruit liquor, liquor, soft drinks such as strawberries, cocoa, juice, carbonated beverages, lactic acid beverages, lactic acid bacteria beverages, pudding mix, hot cake mix To be used as a dehydrating agent for various foods such as instant juices, instant coffee, instant suruko, instant soup and other instant beverages, as well as sweeteners, taste improvers, quality improvers, etc. It can be advantageously carried out.

  Hereinafter, the present invention will be described in detail using experiments.

<Experiment 1>
<Comparison of the amount of dehydration with various non-reducing carbohydrates and the stability of dehydrated articles>
Non-reducing saccharides used in the experiment were sugar, crystalline anhydrous trehalose, amorphous anhydrous trehalose, trehalose hydrated crystal, amorphous anhydrous neotrehalose, neotrehalose hydrated crystal, amorphous anhydrous erulose, erulose hydrated crystal, Amorphous anhydrous raffinose, raffinose hydrated crystals, amorphous anhydrous melethitose and meletitol hydrated crystals. Commercially available reagents were used for sugar, trehalose hydrated crystals, erulose hydrated crystals, raffinose hydrated crystals, and melecitose hydrated crystals. Crystalline anhydrous trehalose and amorphous anhydrous trehalose were prepared by the methods of Reference Example 1 and Reference Example 3, respectively. Neotrehalose hydrous crystals were prepared by the method disclosed in Experiment 2 of JP-A-4-179490. Amorphous anhydrous neotrehalose, amorphous anhydrous erulose, amorphous anhydrous raffinose, and amorphous anhydrous meletitol were prepared by dissolving hydrated crystals in water and then vacuum drying at room temperature.

  First, the dehydration amount of each non-reducing carbohydrate was examined. A mixture obtained by mixing 8 parts by weight of each saccharide with 2 parts by weight of plain yogurt was placed in a vat and allowed to stand overnight at 25 ° C., and then the state change of the mixture was observed. The determination of the amount of dehydration was large for completely solidified, small for incompletely solidified, and nothing without change.

  Next, the stability of the obtained dehydrated article was examined using the completely solidified product. That is, the completely solidified material is pulverized by a cutting method, made into a particle size of about 100 to 150 μm, taken in a plastic petri dish with a diameter of 10 cm, and left in an atmosphere of 37 ° C. adjusted to a relative humidity of 70% for 2 weeks. The degree of coloring was compared. The degree of coloring was defined as the difference between the absorbance at 420 nm and the absorbance at 720 nm in a 10 cm cell using the supernatant of a 30 w / v% suspension. In the determination of stability, the degree of coloring was excellent when it was less than 0.1, normal when it was 0.1 or more and 0.2, and poor when 0.2 or more.

  The results are shown in Table 1.

  As is apparent from the results in Table 1, it was found that crystalline anhydrous trehalose and amorphous anhydrous trehalose have a large amount of dehydration and are excellent in the stability of dehydrated articles and are suitable as a dehydrating agent.

<Experiment 2>
<Dehydration by anhydrous trehalose>
Using crystalline anhydrous trehalose and amorphous anhydrous trehalose as anhydrous trehalose, the dehydrating action, that is, the strength of the dehydrating power and the amount of dehydrated were examined in detail. As a control, water containing trehalose was used. In the experiment, each trehalose prepared by the method described in Experiment 1 was made into a powder product having a particle diameter of about 100 to 150 μm, and 1 g was taken on each plastic petri dish with a diameter of 5 cm, and the atmosphere at 25 ° C. adjusted to a relative humidity of 70%. The water (%) was measured over time. The results are shown in Table 2.

  As is apparent from the results in Table 2, anhydrous trehalose has a strong dehydration power, and it has been found that the moisture in the atmosphere is strongly captured, and about 10% of its weight is captured. Further, when examined over time with a powder X-ray diffraction pattern, it was found that anhydrous trehalose captures moisture and converts it into trehalose-containing crystals, reaches equilibrium at about 10% moisture, and stabilizes. The powder X-ray diffraction pattern of the trehalose hydrate crystal is shown in FIG.

  Similarly, when the moisture (%) was measured over time in an atmosphere of 25 ° C. adjusted to a relative humidity of about 90%, anhydrous trehalose was converted into trehalose-containing crystals as before. Equilibrium was reached at about 10% moisture. At this time, the powder state was maintained, and no sticky or flowing phenomenon was observed.

  From this property, it has been found that anhydrous trehalose can be advantageously used as a powerful dehydrating agent for foods, pharmaceuticals, cosmetics, hydrates such as these raw materials or processed intermediates.

<Experiment 3>
<Comparison between anhydrous trehalose and trehalose-containing crystals for gelatinized starch>
Dissolve 4 parts by weight of glutinous powder in 6 parts by weight of water, pour it into a wooden frame covered with a wet cloth and steam it at 105 ° C for 10 minutes to obtain gelatinized starch. To this, 7 parts by weight of crystallized anhydrous trehalose prepared by the method of Reference Example 1 or trehalose hydrated crystal was mixed with a mixer. When uniform, 2 parts by weight of water syrup was further added and kneaded sufficiently, and further molded at 40 ° C. The fertilizer was obtained by lightly drying with warm air for 2 hours.

  When this product was left open at room temperature of 25 ° C. and left to stand, water using trehalose-containing crystals showed the occurrence of black mold colonies after 15 days, but those using crystalline anhydrous trehalose were also used after 30 days. There was no microbial contamination.

  Moreover, when the thing after 30 days was cut | disconnected and the cross section was observed, although the surface layer part hardened | cured a little and the crystal | crystallization precipitated, the inside is the same as immediately after manufacture. It was translucent and had an appropriate gloss and viscosity. The crystal in the surface layer portion was found to be obtained by converting crystalline anhydrous trehalose into a water-containing trehalose crystal from an X-ray diffraction pattern.

  As a result, it was found that anhydrous trehalose acts as a dehydrating agent for gelatinized starch, prevents microbial contamination, and further prevents aging of gelatinized starch. This property can be advantageously used for various products using gelatinized starch such as fertilizer and flour paste.

  Hereinafter, a method for producing anhydrous trehalose powder will be described with reference examples.

<Reference Example 1>
Trehalose hydrous crystals were dissolved by heating with a small amount of water, and this was taken in an evaporation kettle and boiled under reduced pressure to give syrup having a moisture content of 5.0%. Next, it was transferred to an auxiliary crystal machine, to which 1% of crystalline anhydrous trehalose was added as a seed crystal per syrup solid, stirred at 120 ° C. for 5 minutes, then taken out into an aluminum vat and crystallized at 100 ° C. for 6 hours. A block was prepared by aging.

  Next, this block was pulverized with a cutting machine and fluidized to obtain crystalline anhydrous trehalose powder having a moisture content of 0.32% with a yield of about 87% based on the raw trehalose-containing crystals. A powder X-ray diffraction pattern of the obtained crystalline anhydrous trehalose is shown in FIG.

  This product can be advantageously used not only as a dehydrating agent for water-containing products such as foods, pharmaceuticals, cosmetics, raw materials thereof, or processed intermediates, but also as a white powder sweetener with elegant sweetness.

<Reference Example 2>
A high-purity trehalose aqueous solution is taken in an evaporating kettle and boiled under reduced pressure to obtain a syrup having a moisture content of 4.0%. To this, 5% of crystalline anhydrous trehalose is added as a seed crystal per syrup solid and stirred at 95 ° C. Granulation with an extrusion granulator, aging and drying, and pulverization with a pulverizer gave a crystalline anhydrous trehalose powder with a moisture content of 0.53% in a yield of about 95% based on the raw material.

  Similar to the crystalline anhydrous trehalose powder obtained by the method of Reference Example 1, this product can be advantageously used not only as a dehydrating agent for various hydrates but also as a sweetener.

<Reference Example 3>
The trehalose hydrous crystals are completely dissolved in water at room temperature and then vacuum dried at 60 ° C. for 24 hours. The obtained dried product was pulverized by a pulverizer to obtain an amorphous anhydrous trehalose powder having a water content of 0.83% in a yield of about 89% based on the raw material trehalose-containing crystals. The powder X-ray diffraction pattern of the obtained amorphous trehalose is shown in FIG.

  Similar to the crystalline anhydrous trehalose powder obtained by the method of Reference Example 1, this product can be advantageously used not only as a dehydrating agent for various hydrates but also as a sweetener.

  Examples of the present invention and excellent effects will be described below.

<Dehydrating agent>
Using the crystalline anhydrous trehalose powder obtained by the method of Reference Example 1, 20 g each was filled into a paper moisture-permeable sachet to produce a dehydrating agent. This product can be advantageously used as a dehydrating agent in a moisture-proof container atmosphere in which dried foods such as seasoned seaweed and cookies are enclosed. In addition, it is also possible to advantageously carry out stable storage of various foods such as dried foods and oil-based foods by using an oxygen scavenger together with the dehydrating agent.

<Soro fertilizer>
Dissolve 4 parts by weight of starch in 6 parts by weight of water, pour it into a wooden frame covered with wet cloth, steam it at 100 ° C for 20 minutes, and then obtain crystalline anhydrous trehalose obtained by the method of Reference Example 1. Add 7 parts by weight of powder and 1 part by weight of sugar, then add 2 parts by weight of starch syrup, knead thoroughly, and mold, and leave it in the room for 16 hours to add anhydrous trehalose to the surface layer of this product. It was converted to water-containing crystals, and this was lightly rolled to crack the surface, and a fertilizing foliage was obtained. This product has good flavor, is less susceptible to microbial contamination, and maintains high quality over a long period of time.

<Potato sweets>
Sliced sweet potato to a thickness of about 1 cm, steamed and allowed to cool, then coated with crystalline anhydrous trehalose powder obtained by the method of Reference Example 1 to convert it to water containing trehalose, dehydrated, and water-containing trehalose on the surface A confectionery to which crystals were attached was produced. This product is a confectionery with good flavor and stability.

<Powder brandy>
Ten parts by weight of pullulan is dissolved in 2 parts by weight of brandy, and 8 parts by weight of crystalline anhydrous trehalose powder obtained by the method of Reference Example 2 is mixed with this, then transferred to a vat and left to stand for 2 days to convert into trehalose-containing water crystals. Blocks were prepared. The block was pulverized by a cutting machine and classified to obtain a powdery brandy with good flavor. If this product is included in the mouth, it has a moderate sweetness and is a sufficient powdery flavor of brandy. This product can be advantageously used as a fragrance for black tea or as a confectionery material such as premix and candy. Further, the present powder can be advantageously formed as a granule or a tablet by molding it with a granulating machine or a tableting machine.

<Powder miso>
Mix 2 parts by weight of red miso with 5 parts by weight of crystalline anhydrous trehalose powder obtained by the method of Reference Example 2 and pour it into a metal plate provided with a number of hemispherical recesses, and let it stand at room temperature overnight to solidify. Then, the mold was released to obtain about 4 g of solid miso per piece, which was pulverized to obtain a powder miso. This product can be advantageously used as a seasoning for instant ramen and instant soup. The solid miso can be used not only as a solid seasoning but also as a miso confectionery.

<Powdered soy sauce>
While flowing 4 parts by weight of amorphous anhydrous trehalose powder obtained by the method of Reference Example 3 and 0.02 part by weight of commercially available trehalose hydrated crystals on a conveyor, the ratio of thin soy sauce is 1 part by weight. And then transferred to an aging tower and allowed to stand at 30 ° C. overnight to convert anhydrous trehalose into trehalose hydrated crystals to obtain powdered soy sauce. This product can be advantageously used as a seasoning for instant ramen and instant soup.

<Powdered egg yolk>
Egg yolk prepared from raw eggs is sterilized with a plate-type heat sterilizer at 60 to 64 ° C., and 4 parts by weight of crystalline anhydrous trehalose powder obtained by the method of Reference Example 1 is obtained per 1 part by weight of the liquid egg yolk obtained. After mixing at a ratio, the mixture was blocked and powdered in the same manner as in Example 4 to obtain powdered egg yolk. This product can be advantageously used not only as a confectionery material such as premix, frozen confectionery, and emulsifier, but also as a baby food such as oral liquid food and tube liquid food, and a therapeutic nutrient. It can also be used effectively as a skin beautifying agent or hair restorer.

<Powdered yogurt>
After mixing 8 parts by weight of crystalline anhydrous trehalose powder obtained by the method of Reference Example 1 with 2 parts by weight of plain yogurt, it was blocked and powdered in the same manner as in Example 4 to obtain powdered yogurt. This product not only has a good flavor, but also can stabilize lactic acid bacteria for a long period of time. In addition to confectionery materials such as premixes, frozen desserts, emulsifiers, weaning foods such as oral liquid foods and tube liquid foods, therapeutic nutrients, etc., for example, margar margarine, whipped cream, spread, cheese It can be advantageously used to make a yogurt-flavored product that is contained in cakes, jellies and the like. Furthermore, the powder can be molded with a granulating machine, a tableting machine or the like to obtain a lactic acid bacterium preparation, which can be advantageously used as an intestinal regulating agent.

  Mixing 200 parts by weight of wheat flour with 60 parts by weight of powdered egg yolk obtained by the method of Example 7, 25 parts by weight of butter, 10 parts by weight of sugar, 12 parts by weight of baking powder and 0.5 parts by weight of sodium chloride to prepare a hot cake mix Obtained. This product can be easily prepared with a good-tasting hot cake by melting it in water, milk or the like and baking it.

<Powdered ginseng extract>
After mixing 1.5 parts by weight of crystalline anhydrous trehalose powder obtained by the method of Reference Example 2 with 0.5 parts by weight of medicinal carrot extract, it was blocked and powdered in the same manner as in Example 4 to obtain powdered ginseng extract. It was. This product was applied to a granule molding machine together with appropriate amounts of vitamin B1 and vitamin B2 powder to obtain a vitamin-containing granular ginseng extract. This product can be advantageously used as a fatigue recovery agent, tonic, toughening agent and the like. It can also be used as a hair restorer.

<Solid formulation for liquid food>
500 parts by weight of crystalline anhydrous trehalose powder obtained by the method of Reference Example 2, 270 parts by weight of powdered egg yolk obtained by the method of Example 7, 209 parts by weight of skim milk powder, 4.4 parts by weight of sodium chloride, 1. A formulation comprising 85 parts by weight, thiamine 0.01 parts by weight, sodium L-ascorbate 0.1 parts by weight, vitamin E acetate 0.6 parts by weight and nicotinamide 0.04 parts by weight was prepared. Each 25 g was filled into a moisture-proof laminated sachet and heat sealed to produce a liquid food solid preparation.

  This solid preparation reduces moisture in the sachet atmosphere, does not require low-temperature storage, and is stable for a long time at room temperature. Moreover, the dispersion and dissolution in water are good. This solid preparation is dissolved in about 150 to 300 ml of water to make a liquid food, and is used orally or by tube administration to the nasal cavity, stomach, intestine and the like.

<Solid pharmaceutical preparation>
A newborn hamster was injected with an antiserum prepared from rabbits by a known method to attenuate the immune reaction of the hamster, and then BALL-1 cells were transplanted subcutaneously, and then bred for 3 weeks in the usual manner. The tumor mass produced under the skin was excised and shredded, dispersed in physiological saline and loosened. The obtained cells were washed with a serum-free RPMI 1640 medium (pH 7.2), suspended in the same medium at about 2 × 10 ⁶ cells / ml, and kept at 35 ° C.

To this was added partially purified human interferon-α at a rate of 200 IU / ml and kept for about 2 hours, and then Sendai virus was added at a rate of about 300 hemagglutination / ml and kept for 20 hours to maintain human interferon- α was induced. This is centrifuged at about 1000 ° C. at about 4 ° C. to remove the precipitate, the resulting supernatant is further microfiltered, and the filtrate is immobilized with anti-interferon-α antibody according to a known method. After removing the non-adsorbed fraction by applying to a column, the adsorbed fraction was eluted and concentrated in a membrane to obtain a concentrated solution of about 0.01 w / v% concentration and specific activity of about 2 × 10 ⁸ IU / mg protein. A yield of about 4 ml per animal was obtained.

6 g each of pyrogen-free crystalline anhydrous trehalose obtained by the method of Reference Example 1 was put in a 100 ml moisture-proof plastic bottle, and 0.2 ml (about 4 × 10 ⁶ IU) of the interferon-α concentrate obtained previously was added thereto. ) And aseptically sealed with a rubber stopper and cap to obtain a solid pharmaceutical preparation. In this production method, since the interferon-α-containing liquid is dehydrated simply by adding it to anhydrous trehalose powder, it does not require treatment, equipment, energy, etc. for freeze-drying, but also stabilizes interferon-α. It is effective.

  Since this product is readily soluble in water, it can be used as an anti-sensitive disease agent such as antiviral agent, antitumor agent, anti-rheumatic agent, anti-immune disease agent, etc. It can be advantageously used for injection. In addition, this product can be advantageously used as an internal preparation, an oral preparation and the like. It can also be advantageously used as a test drug for testing.

<Solid pharmaceutical preparation>
Human-derived lymphoblastic cell BALL-1 cells were inoculated into Eagle's minimal basic medium (pH 7.4) supplemented with 20% fetal calf serum, and suspended in vitro at 37 ° C. according to a conventional method. . The obtained cells were washed with Eagle's minimum basic medium without addition of serum (pH 7.4) and suspended in the same medium at about 1 × 10 ⁷ cells / ml. To this suspension, Sendai virus was added at about 1,000 hemagglutination per ml, and kept at 38 ° C. for 1 day to induce and produce Tsumore necrosis factor-α. This was centrifuged at 4 ° C. and about 1,000 g, and the resulting supernatant was dialyzed with physiological saline containing pH 7.2, 0.01 M phosphate buffer for 15 hours, and further subjected to microfiltration. The filtrate was passed through an anti-interferon antibody column according to a conventional method, and the non-adsorbed fraction was purified by affinity chromatography using an anti-Thumor necrosis factor-α monoclonal antibody gel column, concentrated, and concentrated. A concentrated solution of 0.01 w / v% specific activity about 2 × 10 ⁶ JRU / mg protein was obtained. The active yield was about 5 × 10 ⁴ JRU per liter of suspension during induction.

10 g each of pyrogen-free crystalline anhydrous trehalose obtained by the method of Reference Example 1 is put into a 100 ml glass bottle, and 0.5 ml (about 1 × 10 ⁵ JRU) of Tsumer Necrosis Factor-α concentrate is added thereto. ) And aseptically sealed with a rubber stopper and cap to obtain a solid pharmaceutical preparation. This production method is effective not only for freeze-drying treatment but also for stabilization of tmore necrosis factor α because the tmoire necrosis factor-α containing liquid is dehydrated to anhydrous trehalose powder. It is.

  Since this product is easily soluble in water, it can be used as an antitumor agent, antiviral agent, anti-ascites agent, anti-immune disease agent, etc., as an antitumor agent, as an anti-tumor agent, for intramuscular use. It can be advantageously used for injections such as. In addition, this product can be advantageously used as an internal preparation, an oral preparation and the like. It can also be advantageously used as a test drug for testing.

<Treatment for trauma>
3 parts by weight of iodine was dissolved in 450 parts by weight of crystalline anhydrous trehalose obtained by the method of Reference Example 2, 50 parts by weight of methanol was added and mixed, and then 200 parts by weight of 10% pullulan aqueous solution and 50 parts by weight of maltose hydrous crystals were added. The mixture was allowed to stand overnight at room temperature to convert it into trehalose hydrated crystals, thereby obtaining a trauma-treating salve having moderate elongation and adhesion.

  This product can be used to treat wounds such as cuts, abrasions, burns, and pickles by athlete's foot by applying it to the wound surface or applying it to gauze or oil paper. In addition, this product acts not only as a bactericidal action by iodine but also as a nutritional supplement to cells by trehalose, so the treatment period is shortened and the wound surface is repaired neatly.

The powder X-ray diffraction pattern of a trehalose hydrate crystal is shown. 1 shows a powder X-ray diffraction pattern of crystalline anhydrous trehalose. 1 shows a powder X-ray diffraction pattern of amorphous anhydrous trehalose.

Claims (3)

Anhydrous trehalose having a moisture content of less than 3% by Karl Fischer method, obtained by spray-drying syrup containing trehalose at a concentration of 60 to 85% while maintaining a temperature range of 50 to 160 ° C. in the presence of seed crystals of anhydrous trehalose Powder. Anhydrous anhydrous with a water content of less than 3% by Karl Fischer method , characterized by spray drying the syrup containing trehalose at a concentration of 60 to 85% in the presence of seed crystals of anhydrous trehalose while maintaining the temperature range of 50 to 160 ° C. A method for producing trehalose powder. The method for producing anhydrous trehalose powder according to claim 2 , wherein the spray drying is performed by a high-pressure nozzle or a rotating disk method.

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