JPH01165346A - Composition to be used in mouth - Google Patents

Abstract

PURPOSE:To provide the title composition such as sweetener, food, drink or medicine and composed mainly of essentially non-hygroscopic anhydrous crystalline maltitol or a honey-containing crystal containing the maltitol. CONSTITUTION:An essentially non-hygroscopic anhydrous crystalline maltitol can be easily crystallized by adding a high-purity anhydrous crystalline maltitol or a honey-containing crystal containing anhydrous crystalline maltitol having relatively low purity to a supersaturated solution of maltitol. The obtained anhydrous crystalline maltitol or a honey-containing crystal used as a raw material is optionally mixed with a diluent, excipient, binder, etc., and formed in the form of powder, granule, rod, sphere, tablet, plate, cube, etc. The product can be used as a food, drink, sweetener or other composition to be used in the mouth.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to uses of anhydrous crystalline maltitol and nectar-containing crystals containing the same, and in particular to oral use compositions containing anhydrous crystalline maltitol or nectar-containing crystals containing the same. Regarding.

Anhydrous crystalline maltitol and nectar-containing crystals containing the same in the present invention may be any crystalline maltitol that is substantially non-hygroscopic or hardly hygroscopic; It may also be a honey-containing crystal containing sugar alcohols such as sorbitol, maltotriitol, and maltotetriitol in addition to anhydrous crystalline maltitol.

Maltitol is a sugar alcohol produced by reducing maltose, and is a sugar alcohol produced by Masakazu Mitsuhashi et al.
As described in Publication No. 9, etc., its sweetness is elegantly sweet, close to that of sugar, and its sweetness level is about 75 times that of sugar. In addition, it is difficult to digest and absorb in the gastrointestinal tract and is difficult to ferment by oral bacteria, so it is used as a sweet source for low-calorie foods, diet foods, low-corrosion foods, health foods, etc. for people with diabetes, obesity, and adult diseases. It is used by people who are concerned about tooth decay.

However, conventional maltitol can only be handled in the form of an aqueous solution because its dry solid is highly hygroscopic and deliquescent and cannot be turned into powder, so its uses are extremely limited.

Furthermore, even if maltitol were to be boiled down to 180-190°C to obtain a virtually anhydrous amorphous candy, it would be so hygroscopic and deliquescent that it would have to be sealed in a moisture-proof container in the presence of a desiccant. , its handling is extremely difficult.

In this regard, M.G. Wolfrom (M.J.
Jolfro et al., ``Journal of the American Chemical Society''
the Avcerican Chemical 5
Society) J, Volume 62, Nos. 2553-255
5 (1940), ``Maltitol is amorphous,
It was obtained only in the form of a white, hygroscopic solid. ”, and also reported that J.E. Hodg.
e) etc. are “Cerial Science Today (Cer.
eal 5science Today)”, Volume 17,
No. 7, pp. 180-188 (1972), ``The authors have not yet obtained a non-hygroscopic solid form of maltitol.

Maltitol could be crystallized as a hygroscopic ethanol complex. ” is reported.

Thus, until now, maltitol was only known as a strongly hygroscopic solid.

In recent years, many attempts have been made to produce powdered maltitol by somehow alleviating this strong hygroscopicity.

For example, in JP-A No. 49-477 by Kuniriki Ueno et al. and JP-A-49-87619 by Shinsei Hidaka et al., a hydrophilic polymer compound such as an edible glue is added to an aqueous solution of maltitol, A method of making maltitol into powdered form by drying is disclosed, and also disclosed in Japanese Patent Application Laid-Open No. 50-5931 by Kazuaki Kuno et al.
In Publication No. 2, a small amount of one or more monosaccharides or monosaccharide alcohols is added to a maltitol-containing substance to form an anhydrous molten state, which is then cooled and sprayed and granulated in a moisture-proof tower to produce powdered malt. A method for making it tall is shown, and also disclosed in JP-A-49-110620 by Bushi Hiraiwa et al., JP-A-50-24206 by Bushi Hiraiwa et al., and JP-A-1988- by Takashi Oyamada et al.
25514, JP 51-32745 to Hiraiwa, JP 51-106766, JP 51-
113813, JP-A-51-128441, JP-A-52-47928, etc., solid maltitol is pulverized in a dry atmosphere, and an edible powder other than maltitol is deposited on the surface of the powder. In addition, in Japanese Patent Application Laid-Open No. 50-29510 by Jun Kanae et al., after wetting maltitol-containing powder with a solvent in which maltitol is poorly soluble, A method has been disclosed in which carbohydrates other than maltitol are adhered to and fixed on the particle surface of maltitol-containing powder by drying while mixing with fine powder of carbohydrates, thereby preventing caking of maltitol-containing powder.

However, all of these attempts not only require a large amount of other substances to be mixed with or adhered to maltitol, but also do not solve the drawback of maltitol's strong hygroscopicity.In fact, these methods The powder obtained in this process is only a powder in the air, but it still has strong hygroscopic properties, and after a short time in the air, it absorbs moisture, solidifies, and deliquesces. It cannot be used for practical use on the sole.In order to eliminate these drawbacks of maltitol, the present inventors have investigated the production method and physical and chemical properties of maltitol, and have developed a method that was previously believed to be impossible. He continued his intensive research in search of non-hygroscopic crystalline maltitol.

As a result, isoamylase (EC3, 2, 1, 68) and β-amylase (EC 3, 2, 1, 2) were applied to a starch liquefied solution obtained by liquefying starch to a low DE to create a maltose-rich saccharified solution. The high-purity maltose obtained by crystallizing and separating maltose (indicated by weight % based on solid matter; hereinafter simply referred to as purity) of 99z is purified under a Raney nickel catalyst. Hydrogenated and purified to purity 9
8.5% high purity maltitol was obtained and an aqueous solution concentrated to a concentration (expressed in weight %, hereinafter simply referred to as concentration) of 75z was placed in a soft glass bottle and kept at 30-5°C for about 6 months. Crystals were deposited on the inner wall. These crystals are added as seed crystals to the above-mentioned high-purity maltitol aqueous solution with a concentration of 80%, and are allowed to crystallize while being slowly stirred. The crystals were dissolved in water, treated in the same manner, and recrystallized to obtain higher purity crystals, and the physical and chemical properties of these crystals were investigated. They discovered that it is anhydrous crystalline maltitol, and completed the present invention.

Below, various properties of the anhydrous crystalline maltitol of the present invention will be described.

(1) Elemental analysis measurement value C=41.9X)l=7.1X0
=51. OK theoretical value C=41.86X H=7.0
3X 0=51.11! (Molecular formula: Cl2H240
(2) Molecular weight 344.3 (3) Melting point 146.5-147.0°C (4) Specific optical rotation [α] δ0◆106.5° (0.1 g in 1 cc of water) ( 5) Ultraviolet absorption When measured as an aqueous solution, no characteristic absorption is shown.

(6) Infrared absorption spectrum (a) Infrared absorption spectrum of anhydrous crystalline maltitol 5 mg of anhydrous crystalline maltitol powder and dry KBr22
Stir and mix 0.0 g to form a transparent tablet (thickness approx. 0.0 g).
6 mm) was prepared and its infrared absorption spectrum was measured.

The results are shown in Figure 1.

(b) Infrared absorption spectrum of anhydrous amorphous maltitol Anhydrous crystalline maltitol 3B and 220 mg of KBr were completely dissolved in hot water, and then heated and dried to form an amorphous anhydride. About 0.81a) was prepared and its infrared absorption spectrum was measured. The results are shown in Figure 2.

(7) Solubility: Anhydrous crystalline maltitol is 1% per 100g of water at 25°C.
Holds 65g.

(8) 190 ola of water at a heat of dissolution of 15°C, anhydrous crystalline maltitol 1
(2) When ale is dissolved, it exhibits an endotherm of 5.5 Kcal.

(9) Physical Properties: It is a colorless and transparent crystal of the substance. The microcrystals are white powder-like with a sweet taste and no depth. It is non-hygroscopic and does not deliquesce. Also, 13
When the loss on drying is measured at 0° C. for 2 hours, it is 0.5z or less.

Examples of crystals being crystallized from an aqueous maltitol solution are shown in FIGS. 3 and 4 as microscopic photographs. Note that the aqueous solution is neutral or slightly acidic.

(10) Solubility for drugs Water, 0. Easily soluble in IH-HaOH, 0,1N-HCl.

Slightly soluble in methanol and ethanol.

Insoluble in chloroform and ethyl acetate.

(11) Color reaction It appears green due to the anthrone-sulfuric acid reaction.

Fehling pressure fluid reduction reaction was negative. Iodine reaction was negative.

(12) Constituent sugar (a) When the sugar obtained by hydrolysis with IN-sulfuric acid is analyzed by vapor chromatography or gas chromatography, it consists of equimolar amounts of D-glucose and D-sorbitol.

(b) After complete methylation, when the sugar obtained by hydrolysis is analyzed by gas chromatography, the results are 2.3, 4.6
-tetra-0-methyl-〇-glucose and 1.2.3.
and 5.8-penta-0-methyl-〇-sorbitol in equimolar amounts.

(c) The specific rotation is as high as 106.5 degrees, and the infrared absorption spectrum is 840 am.
``Since it exhibits absorption near the area, it is α-bonded.

(d) When this crystal is analyzed by vapor chromatography, gas chromatography, or high performance liquid chromatography using a currently commercially available maltitol aqueous solution (special grade reagent) as a standard, it shows a single spot and a single peak, and It is detected in the same location as maltitol.

(13) X-ray analysis Maltitol supersaturated aqueous solution at 40°C (a1 degree 75
X-ray analysis of the single crystal crystallized from z) revealed that the crystal was orthorhombic with a space group of P2+2+21 and a lattice constant of a; 8.166A1b=12.721ASc"13
．． It was 629A.

A schematic diagram of the three-dimensional structure of the molecules in this crystal is shown in FIG.

From the above facts, the crystal of the present invention is a water-containing crystal, unlike the β-maltose monohydrate crystal.
It is also determined that it is a non-hygroscopic anhydrous crystalline maltitol, which has not been previously reported and is not an ethanol complex.

Hereinafter, the method for producing anhydrous crystalline maltitol of the present invention and honey-containing crystals containing the same will be described.

The maltitol solution for crystallization used in the present invention may be a supersaturated solution of maltitol in which anhydrous crystalline maltitol is precipitated, and any method for producing maltitol may be used. Normally, the degree of supersaturation is about 1.05 to 1.5, and to be more specific, maltitol with a purity of 65 or more is desirably made into an aqueous solution with a concentration of about 65 to 95. Further, it is desirable that the temperature is in the range of 0 to 95° C., where there is relatively little heat loss in the manufacturing process. In order to adjust the degree of supersaturation and viscosity of the solution, for example, methanol, ethanol, acetone, etc. can be freely added. In addition, the crystallization method is such that a supersaturated maltitol solution at a relatively high temperature of usually 40 to 95°C is placed in an auxiliary crystal can, and seed crystals are added to this, preferably 0.1 to 20°C.
% coexistence, and then slowly cooled while stirring to promote crystallization to obtain a mass kit.

As described above, the anhydrous crystalline maltitol of the present invention can be easily crystallized by adding high-purity anhydrous crystalline maltitol or relatively low-purity anhydrous crystalline maltitol-containing nectar crystals to a supersaturated maltitol solution as seed crystals. I can do things.

The method for producing anhydrous crystalline maltitol and nectar-containing crystals containing the same from the crystallized mascits may be any method as long as anhydrous crystalline maltitol and nectar-containing crystals containing the same can be collected, such as the molasses method, the block crushing method, the fluidization method, etc. Known methods such as granulation method and spray drying method may be used. For example, in the honey separation method, the honey is usually separated from the anhydrous crystalline maltitol using a basket centrifuge, and if necessary, the crystals can be easily washed by spraying a small amount of cold water. It is suitable for producing higher purity non-hygroscopic anhydrous crystalline maltitol. The other three methods do not separate the nectar, so the maltitol purity of the resulting honey-containing crystals does not improve, but they have the advantage of high product yields. Therefore, in the case of this product, in addition to anhydrous crystalline maltitol, sugar alcohols derived from starch sugar, such as sorbitol and maltotriitol, are usually used as sound components.
This includes maltotetraitol. In the case of spray drying, usually Maskit with a concentration of 70 to 85 degrees and a crystallization rate of 25 to 60 degrees is sprayed from a nozzle using a high-pressure pump, and dried with hot air at a temperature that does not melt the crystal powder, for example, 60 to 100 degrees Celsius. Then, by ripening with warm air at 30 to 60°C for about 1 to 20 hours, non-hygroscopic or hardly hygroscopic honey-containing crystals can be easily produced. In addition, the block crushing method usually has a moisture content of 5 to 5.
15 particles, crystallization rate of 10 to 60 particles is 0.5
If the whole is allowed to stand still for up to 5 days to crystallize and solidify in the form of a block, then crushed by crushing or cutting and dried, non-hygroscopic or hardly hygroscopic honey-containing crystals can be easily produced.

In addition, a maltitol aqueous solution is heated and concentrated to a water content of less than 5z according to a conventional method to obtain a molten supersaturated maltitol solution, and seed crystals are kneaded into this supersaturated maltitol solution at a temperature below the melting point of maltitol. It is also possible to obtain non-hygroscopic or hardly hygroscopic honey-containing crystals by forming the crystals into shapes such as powder, granules, rods, plates, cubes, etc.

The high-purity anhydrous crystalline maltitol and anhydrous crystalline maltitol-containing nectar crystals obtained in this way vary in their non-hygroscopicity depending on the purity of the maltitol;
It is virtually non-hygroscopic, fluid, and can be handled in the same way as sugar without worrying about sticking or sticking, so it can be used in mouth-use compositions such as food and beverages, cosmetics, pharmaceuticals, and molded products, as well as chemical raw materials. Can be used freely for each purpose.

In addition, physicochemical properties such as melting point and specific rotation of the anhydrous maltitol-containing nectar crystal vary depending on the purity thereof. Among these, the melting point decreases as the purity of maltitol decreases, and the range of melting temperatures also increases. For example, the melting point of anhydrous crystalline maltitol-containing honey crystals with a purity of 85.2 is 120-127°C.

Therefore, maltitol purity may be appropriately selected and used depending on the necessity. Furthermore, when the anhydrous crystalline maltitol of the present invention and the honey-containing crystals containing the same are placed on the tongue,
Unlike sugar, it absorbs a large amount of heat of dissolution and dissolves easily, so it has a refreshing and elegant sweet taste and is suitable as a sweetener.

Although the anhydrous crystalline maltitol of the present invention and the honey-containing crystalline powder containing the same have high solubility and dissolution rate in water, they are substantially non-hygroscopic powders. It is especially convenient for adding flavor to things. Therefore, by using anhydrous crystalline maltitol and nectar-containing crystals containing the same, it is possible to produce sweeteners such as powdered sweeteners and solid sweeteners that were previously impossible or extremely difficult to produce using maltitol. , fondant, chocolate, chewing gum, instant juice,
Instant soups, granules, tablets, etc. can now be manufactured industrially with great ease.

In addition, the anhydrous crystalline maltitol of the present invention and the honey-containing crystals containing it have good fluidity because they are non-hygroscopic and do not clump. The benefits are immeasurable as the cost can be reduced.

In addition, the anhydrous crystalline maltitol of the present invention and the nectar-containing crystals containing the same are extremely soluble in water, and the inherent properties of maltitol, such as sweetness and body-imparting properties, can be maintained in the same manner as in the case of conventional aqueous solutions. , shine imparting properties, moisturizing properties,
It also has properties such as viscosity, heat resistance, acid resistance, acid fermentability, indigestibility, and non-corrosion properties, so oral compositions such as food and drink, cosmetics, and pharmaceuticals can be manufactured by taking advantage of these properties. You are also free to do so.

The present invention will be explained in more detail below.

The anhydrous crystalline maltitol of the present invention and the honey-containing crystals containing the same cannot be used as is as a seasoning for flavoring. If necessary, for example, powdered candy, glucose, maltose, high fructose sugar, sugar, honey, maple cisgar, sorbitol, dihydrochalcone, stevioside, α-glycosyl stevioside, Lacankase flavor, glycyrrhizin, asparatilto. It may also be used mixed with appropriate amounts of one or more other sweeteners such as phenylalanine methyl ester, saccharin, glycine, alanine, etc. (and also mixed with bulking agents such as dextrin, starch, lactose, etc.) In addition, among the anhydrous crystalline maltitol of the present invention and the honey-containing crystalline sweetener containing the same, the powdered product can be used as is or with fillers, excipients, and binders as necessary. It is also free to use it by mixing it with other substances and forming it into granules, spheres, tablets, rods, plates, cubes, etc.

In addition, since the anhydrous crystalline maltitol of the present invention and the honey-containing crystals containing the same are difficult to digest and absorb like maltitol, the anhydrous crystalline maltitol of the present invention and the honey-containing crystals containing the same are flavored. It is possible to reduce the calorie content of the food and drink consumed. Therefore, the anhydrous crystalline maltitol of the present invention and the honey-containing crystals containing the same can be used as a low-calorie sweetener for people who are on calorie restriction such as diabetics and obese people, and also in low-calorie drinks, such as beauty foods. It is used to add flavor to health foods and diet foods.

In addition, the anhydrous crystalline maltitol of the present invention and the nectar-containing crystals containing the same can be used as a sweetener that is less likely to cause tooth decay, as it is difficult to ferment completely due to caries-inducing flash, etc., similar to maltitol. . For example, chewing gum, chocolate, biscuits, kutsky, kyatsuru,
It is suitable for flavoring low-cariogenic foods and drinks, such as confectionery such as candy, cola, cider, juice, coffee, and drinking water such as lactic acid bacteria drinks. It is also suitable for adding flavor to cosmetics and medicines that prevent tooth decay, such as gargling water and line polishing.

The sweetness of the anhydrous crystalline maltitol of the present invention and the honey-containing crystals containing the same harmonizes well with various substances having other tastes such as sour, salty, astringent, umami, and bitter, and has acid resistance and Because it has high heat resistance, it can be used not only in the special cases mentioned above, but also for flavoring and improving the flavor of general foods and drinks, as well as for improving quality.

For example, soy sauce, powdered soy sauce, miso, powdered miso, moromi, hishio, furikake, mayonnaise, dressing, vinegar, sambai vinegar, powdered sushi vinegar, Chinese base, tempura soup, mentsuyu, sauce, ketchup, yakiniku sauce, curry roux, stew. It can be freely used as a variety of seasonings, such as seasonings, soup bases, dashi bases, compound seasonings, mirin, new mirin, table sugar, coffee sugar, etc.

In addition, for example, rice crackers, arare, okoshi, rice cakes, manju, uiro, bean paste, yohan, mizuyomi, nishikigami, jelly, castella, hard candy, and various other Japanese sweets, bread, biscuits, crackers, kutsky, and pies. , pudding, putter cream, custard cream, cream puff, Watsuful, sponge cake, donuts, chocolate, chewing gum, caramel, various Western sweets such as candy, ice cream, frozen desserts such as sorbet, crushed fruit syrup, syrups such as honeydew, flowers Pastes such as paste, peanut paste, and fuller paste; processed fruit and vegetable foods such as jam, marmalade, crushed syrup, and confectionery; processed grain foods such as bread, noodles, cooked rice, and artificial meat; Fukujinzuke; Pickles such as bettaramasu, senmaizuke, and pickled radish; pickles such as pickled pickled radish and Chinese cabbage; meat products such as ham and sausage; fish ham, fish sausage, kamaboko, chikuwa, and tempura. various delicacies such as sea urchin, salted squid, vinegar kelp, sakisurume, mirin-dried blowfish, seaweed, wild vegetables,
Tsukuta fish made from dried squid, small fish, shellfish, boiled beans,
Vegetable foods such as potato salad and kelp rolls, dairy products, fish, meat, fruit, and canned vegetables, alcoholic beverages such as synthetic alcohol, fruit alcohol, and Western liquor, coffee, cocoa, juice, carbonated drinks, and lactic acid drinks. As a sweetener for various foods and drinks, such as soft drinks such as lactic acid bacteria drinks, premixed powders such as pudding mixes and pancake mixes, instant food and drinks such as instant juices, instant coffee, instant shiruko, and instant soups. It can be freely used as a taste improver, quality improver, etc.

In addition, the anhydrous crystalline maltitol of the present invention and the honey-containing crystals containing the same are non-hygroscopic and have good fluidity, so that they can be used, for example, in chewing gum, vinegar kelp, etc., by coating the surfaces thereof. It can also be advantageously used to prevent adhesion between the surface of contents and wrapping paper, and as a slip improver.

It can also be used to improve the palatability of feed for livestock, poultry, and other domesticated animals such as bees, silkworms, and fish. In addition, various solid, paste, and liquid forms such as cigarettes, reprimands, lipsticks, lip balms, oral medications, troches, cod liver oil drops, mouth fresheners, mouthwashes, and gargles can be used in recreational foods, cosmetics, and pharmaceuticals. It can be freely used as a taste improver, a flavoring agent, and as a quality improver.

Alternatively, the anhydrous crystalline maltitol of the present invention or the honey-containing crystals containing the same may be sprayed with a small amount of water or a small amount of an aqueous maltitol solution to make it slightly damp, and then subjected to low-pressure compression molding. Like molded sugar produced from granulated sugar, it can be freely molded into various shapes, such as dice, fish, flowers, etc., making it easy to produce molded sweeteners suitable for coffee, tea, and the like. At this time, for example,
α-glycosyl stevioside, saccharin, sugar, L-
It can be increased by adding asparatyl monophenylalanine methyl ester, it can be colored with food coloring such as red or green, it can be molded by adding flavors such as coffee flavor, orange flavor, brandy flavor, etc. You are also free to do so. Also,
It is also free to use it as a clathrate compound of flavor and cyclodextrin in advance as a flavor.

In addition, since high-purity anhydrous crystalline maltitol can be easily collected in giant crystals like sugar, it can also be used as a transparent or translucent non-hygroscopic sweetener such as rock sugar or coffee sugar.

Further, the anhydrous crystalline maltitol of the present invention or the nectar-containing crystalline powder containing the same is mixed with, for example, vitamins, antibiotics, lactic acid bacteria, etc., and molded into various shapes, for example, processed into granules using a granulating machine, or processed using a tablet machine. It is also free to make tablets and use them for various purposes.

As mentioned above, the composition for oral use in the present invention is
Not only sweeteners containing the anhydrous crystalline maltitol of the present invention or nectar-containing crystals containing the same, but also general foods and drinks,
It refers to all things that are used orally, such as recreational foods, feed, feedstuffs, cosmetics, and pharmaceuticals.

The method of incorporating the anhydrous crystalline maltitol of the present invention and the nectar-containing crystals containing the same into such a composition for oral use can be carried out by incorporating it in the steps until the product is completed, such as mixing, kneading, dissolving, etc. , melting, soaking, infiltration, spreading,
Known methods such as coating, coating, spraying, injection, crystallization, and solidification are appropriately selected.

Examples of the present invention will be described below.

Example 1 Production of seed crystals of anhydrous crystalline maltitol A suspension of 1 part by weight of potato starch and 10 parts by weight of water was added with commercially available bacterial liquefied α-amylase and gelatinized by heating to 90°C, and immediately heated to 130°C. The enzyme reaction was stopped, and a liquefied liquid with a DE of about 0.5 was obtained. This starch liquefied liquid was rapidly cooled to 55°C to produce Pseudomonas amyloderamosa (Pseudomonas amyloderamosa).
amyloderaw+osa) ATCC21262
Isoamylase (EC3,2,1
, 68) per g of starch and 50 units of soybean-derived β-amylase (EC3, 2, 1, 2) (manufactured by Nagase Sangyo Specialty, trade name #1500) p) 15.
Glucose is maintained at 0°C for 40 hours, and the sugar composition becomes glucose 0°4.
A maltose-rich saccharified solution consisting of 92.5 x maltose, 5.0 x maltotriose, and 2.1 x dextrin with maltotetraose or higher was obtained, which was decolorized with activated carbon and desalted and purified using an ion exchange resin. .

After concentrating this maltose solution to a concentration of 75%, it was placed in a auxiliary crystal can, 1x powdered seed crystals of β-maltose φ monohydrate crystals were added, the temperature was heated to 40°C, and the temperature was slowly cooled with slow stirring for 2 days. The mixture was cooled to 30°C, separated using a basket centrifuge, and the crystals were sprayed and washed with a small amount of water to obtain high-purity crystalline maltose with a purity of 99.0%. This maltose was made into an aqueous solution of 50 parts, put into an autoclave, Raney nickel IOX was added as a catalyst, the temperature was raised to 90-125°C with stirring, and the hydrogen pressure was increased to 20-100 kg/
After raising the temperature to am2 to complete hydrogenation, Raney nickel was removed and purified using activated carbon and ion exchange resin according to a conventional method to obtain high-purity maltitol with a purity of 98.5%. Concentrate this maltitol solution under reduced pressure to a concentration of 75% and put a portion of the maltitol aqueous solution in a soft glass bottle.
When kept at 5°C for about 6 months, anhydrous crystalline maltitol precipitated on the inner wall.

The crystals are added as seed crystals to the 80x concentration aqueous solution of high purity maltitol, and the crystals are auxiliary crystallized while being slowly stirred, and the resulting massitol is separated using a basket centrifuge.
The crystals were washed by spraying a small amount of water to collect high purity anhydrous crystalline maltitol with a purity of 99.8%.

The anhydrous crystalline maltitol thus obtained has a melting point of 14
6.5-147℃, solubility per 100g of water,
It weighed 165 g at 25°C. Furthermore, even when left indoors, no hygroscopicity was observed.

This anhydrous crystalline maltitol can be advantageously used as seed crystals.

Example 2 Production of anhydrous crystalline maltitol. A commercially available liquefied α-amylase was added to a suspension of 1 part by weight of yam starch and 10 parts by weight of water, heated to 90°C, and immediately stirred. The enzymatic reaction was stopped by heating to 130°C to obtain a liquefied liquid with a DE of about 0.5. This starch liquefied liquid was rapidly cooled to 50°C, and Escherichia intermedia (Escherichia intermedia)
Pullulanase (EC3,2,1,41
) is 50 units per gram of starch, and soybean-derived β-amylase (EC3, 2, 1, 2) (Nagase Sangyo ■ke, product name 11
1500) was added with the same <30 units and saccharified for 46 hours while keeping the pH at 6.0. The saccharified solution was decolorized with activated carbon, desalted with an ion exchange resin, and then concentrated. The sugar composition was 0.4X glucose, maltose. 92.5%, maltotriose 4
．． 8%, dextrin with more than maltotetraose 2.3
A maltose solution consisting of starch was obtained at a yield (solid matter) of about 97% based on the raw material starch.

This maltose solution was brought to a concentration of 50x, 10% Raney nickel was added as a catalyst to the kernels, and the temperature was lowered to 90% while stirring.
Raise the temperature to 0~125℃ and increase the hydrogen pressure to 20~100kg1C■
2 to complete the hydrogenation, Raney nickel was removed, and the composition was purified using activated carbon and ion exchange resin according to the conventional method, and the composition was sorbitol 0.8 and maltitol 92.2.
A maltitol solution containing 4.6 parts of L-maltotriitol and 2.4 parts of dextrin alcohol higher than maltotetriitol was obtained at a yield of about 92 parts based on the raw material starch.

After concentrating this maltitol solution to a concentration of 80 ml, put it in a auxiliary crystal can, add 1 ml of powdered seed crystals of anhydrous crystalline maltitol, bring it to 50°C, slowly cool it with stirring, and leave it for 3 days. The temperature was lowered to 20℃, the honey was separated using a basket centrifuge, the crystals were sprayed with a small amount of water, and the crystals were collected by washing. It was obtained in a yield of 46'&.

The melting point of the ice crystals was 145.5-147°C.

Ice crystals are highly pure and show no hygroscopicity, and are used in various foods, drinks,
It is advantageously used as a sweetener, taste improver, flavor corrective, quality improver, etc. in cosmetics and pharmaceuticals.

Example 3 Production of honey-containing crystalline powder containing anhydrous crystalline maltitol In a suspension of 3 parts by weight of cornstarch and 10 parts by weight of water,
Commercially available bacterial liquefied α-amylase was added, heated to 90°C to gelatinize, heated to 130°C to stop the enzyme reaction, and DE
This starch liquefied liquid was rapidly cooled to 55°C to prepare Pseudomonas amylodermosa (Pseudomonas amyloderamosa).
as amyloderamosa) ATCC2126
Isoamylase prepared from the culture solution of 2 (EC3°2.
1.68) to 100 units per g of starch and β-
Add 30 units of amylase, maintain the pH at 5.0, and saccharify for 36 hours. Purify in the same manner as in Example 2 to obtain a sugar composition of 2.6L of glucose, 85.4% of maltose, 7.4X of maltotriose, A maltose solution consisting of dextrin 4.6z of maltotetraose or more was obtained, and then hydrogenated and purified in the same manner as in Example 2 to obtain sorbitol 3.6
X, maltitol 85.0, maltotriitol 6.
After concentrating a maltitol solution consisting of 4.6 mols of dextrin alcohol containing 8% maltotetriitol or higher to a concentration of 88 mls, put it in a auxiliary crystal can, add 2x powdered crystals of anhydrous crystalline maltitol, bring it to 50°C, and slowly boil it. After keeping it for 2 hours while stirring, it was placed in a vat and kept at 20°C for 4 days to crystallize and solidify, then it was crushed with a cutting type crusher and dried to obtain anhydrous crystalline maltitol-containing honey crystal powder with a yield of 90%. %
I got it. The melting point of the ice crystals was 120-127°C. Ice crystals exhibit virtually no hygroscopicity, are easy to handle, and can be advantageously used as sweeteners, taste improvers, flavoring agents, quality improvers, etc. in various foods, drinks, cosmetics, pharmaceuticals, and the like.

Example 4 Production of honey-containing crystalline powder containing anhydrous crystalline maltitol After concentrating the maltitol solution produced by the method of Example 2 to 8 cm, it was placed in a auxiliary crystal can, and 2x of honey-containing crystalline powder containing anhydrous crystalline maltitol was added. The mixture was slowly cooled from 50° C. with stirring to obtain a mass kit having a crystallization rate of 35. The mixture was sprayed onto the drying tower from a 1.5 mm diameter nozzle at a pressure of 150 kg/cm 2 using a high pressure pump. At the same time, 85°C hot air was blown from the top of the drying tower and collected on the transfer wire mesh conveyor installed at the bottom, and 40°C hot air was sent from below the conveyor and collected on the moving wire mesh conveyor. The crystal powder was gradually moved out of the drying tower and taken out after 40 minutes.The taken out crystal powder was packed into an aging tower and aged for 10 hours to complete crystallization and drying, and anhydrous crystalline maltitol was obtained. A crystal powder containing honey was obtained in a yield of 92 pieces.

Ice crystals are non-hygroscopic, easy to handle, and can be advantageously used as sweeteners and other foods and drinks.

Example 5) Production of Ondant A suspension of 5 parts by weight of corn starch and 10 parts by weight of water was made into a DE5 starch liquefied liquid by the method of Example 3, and this was heated at 55°C.
70 units of isoamylase and 10 units of β-amylase were added per gram of starch, and the mixture was saccharified for 36 hours while maintained at pns, o, and purified in the same manner as in Example 2 to obtain a sugar composition containing 0.9 g of glucose and 0.9 g of maltose. 77.6 pieces, maltotriose 1
Dextrin with 2.5% maltotetraose or higher9.
A maltose solution consisting of 0% was obtained, and then hydrogenated and purified in the same manner as in Example 2 to give 1.4g of sorbitol, 77% of maltitol, 12.3% of maltotriitol,
Dextrin alcohol greater than maltotetriitol 9
．． After concentrating the maltitol solution consisting of 0% to a concentration of 85 ml, it was placed in a auxiliary crystal can, 1 ml of seed crystal was added thereto, and it was cooled to room temperature with vigorous stirring, and then the anhydrous crystalline maltitol obtained by the method of Example 2 was added. A fondant was obtained by mixing and stirring.

Ice crystals are white, paste-like, have a smooth texture, and have a refined sweetness, and can be advantageously used as an ingredient in various confectionery products.

Example 6 Production of sweetener 0.05 part by weight of α-glycosyl stevioside (trade name “α-G Sweet” manufactured by Toyo Seito Co., Ltd.) was added to 1 part by weight of the anhydrous crystal maltitol-containing nectar crystal powder obtained by the method of Example 3. The powdered sweetener obtained by uniformly mixing has excellent sweetness quality,
It is about twice as sweet as sugar and has about 112 calories than sugar.
It dropped to 0.

The present sweetener is suitable as a low-calorie sweetener for adding flavor to low-calorie foods and drinks for people who restrict their calorie intake, such as obese people and diabetics.

In addition, this sweetener does not produce acid or insoluble glucan depending on the country where dental caries is induced, so it is suitable for adding flavor to foods and drinks that inhibit dental caries.

Example 7 Production of solid sweetener 1 part by weight of anhydrous crystalline maltitol obtained by the method of Example 2 was uniformly mixed with 0.01 part by weight of saccharin, and a small amount of maltitol aqueous solution was sprayed onto the mixture to dampen it. After putting it into a sugar cube molding machine and molding it under low pressure, it was cut out to obtain a solid sweetener molded into dice.

Ice crystals are a white sweetener that is about twice as sweet as sugar.
It has sufficient physical strength, is non-hygroscopic, and easily dissolves in cold water.

In addition, ice crystals can be said to be essentially a low-calorie sweetener and a non-corrosive sweetener.

Example 8 Production of Freemuraf Earth Anhydrous crystalline maltitol-containing honey crystal powder obtained by the method of Example 3 2.0
00 parts by weight, 1°000 parts by weight of shortening, 1 part by weight of lecithin, 1 part by weight of lemon oil', 1 part by weight of vanilla oil
A cream obtained by blending parts by weight in a conventional manner is heated to give 4 parts by weight.
It was maintained at -45°C and sandwiched between wafers to produce a free mulch earth.

Example 9 Production of custard cream 500 parts by weight of cornstarch, 500 parts by weight of anhydrous crystalline maltitol-containing honey crystal powder obtained by the method of Example 4, 400 parts by weight of maltose
Thoroughly mix parts by weight and 5 parts by weight of table salt through a sieve, add 1.400 parts by weight of chicken eggs and stir, gradually add boiled milk S and 5 parts by weight of OOO, and mix coarsely over a simmering heat. Stirring was continued, and when the corn starch was completely gelatinized and the whole mixture became translucent, the fire was stopped, the mixture was cooled, and a small amount of vanilla flavoring was added to produce custard cream.

Ice crystals are smooth, shiny, and delicious without being too sweet.

Example 10 Production of chocolate 40 parts by weight of cocoa paste, 10 parts by weight of cocoa butter,
50 parts by weight of anhydrous crystalline maltitol obtained by the method of Example 2 was mixed and passed through a refiner to reduce the particle size, and then put into a contier and kneaded at 50° C. for 2 days and nights. During this time, 0.5 parts by weight of lecithin was added and sufficiently dispersed.

Next, adjust the temperature to 31℃ with a temperature controller, pour it into the mold just before the butter hardens, and remove the fluff with a vibrator.
It was solidified by passing through a cooling tunnel at 10° C. for 20 minutes. This was cut out and packaged to obtain a product.

Ice crystals are non-hygroscopic, have good color and gloss, have a good internal structure, melt smoothly during the day, and have an elegant sweetness and mellow flavor. In addition, ice crystals are useful as low-calorie, low-corrosion chocolate.

Example 1 Production of ball-filled chocolate Anhydrous crystalline maltitol-containing nectar crystal powder 95 obtained by the method of Example 3
Juyabe, 5 parts by weight of starch syrup, and a small amount of water are stirred and mixed to give it fluidity, and a small amount of fragrance and coloring matter are added to this, then it is filled into a starch mold with a depositor and semi-solidified, and the starch is sieved. It was made into a center of chocolate ball.

This center was coated with unsolidified chocolate produced by the method of Example 1o, cooled and solidified, and packaged to give a product.

Example 12 Production of chewing gum Gum base 25
parts by weight and 40 parts by weight of the fondant obtained by the method of Example 5 were kneaded at 60°C with a mixer, and then 30 parts by weight of anhydrous crystalline maltitol obtained by the method of Example 2,
1.5 parts by weight of calcium phosphate and Z-menthol β
- 0.1 part by weight of a cyclodextrin clathrate compound was mixed, and finally a small amount of seasoning was mixed and kneaded thoroughly, followed by rolling and cutting to obtain a product.

This product is suitable as a non-corrosive chewing gum.

Example 13 Production of powdered juice To 33 parts by weight of orange juice powder produced by spray drying, 60 parts by weight of anhydrous crystalline maltitol-containing honey crystal powder obtained by the method of Example 4 and 0.65 parts by weight of anhydrous citric acid. , 0.1 part by weight of malic acid, 0.1 part by weight of ascorbic acid, 0.1 part by weight of sodium citrate, 0.6 part by weight of powdered fragrance, and 0.5 part by weight of pullulan were thoroughly mixed and stirred. Pour into granulator, exhaust air temperature 40℃, air volume 150cm/min
3, and sprayed with maltitol solution obtained by the method of Example 3 at a concentration of 50 ml as a coating liquid or binder at a rate of 1°Ol/min, and granulated for 30 minutes to produce powdered juice. did.

This product is a powdered juice with a fruit juice content of 30%.

In addition, this product was stable over a long period of time, with no unpleasant odor, no moisture absorption, and no caking.

Example 14 Production of instant corn potage soup α
30 parts by weight of -ized corn powder, 95 parts by weight of alpha-ized wheat, α
4 parts by weight of -converted bote starch, 12 parts by weight of pregelatinized waxy corn starch, 8 parts by weight of anhydrous crystalline maltitol-containing honey crystal powder obtained by the method of Example 3, 5 parts by weight of sodium glutamate, 8.5 parts by weight of common salt. After grinding and thoroughly mixing 7 parts by weight of skim milk powder and 0.5 parts by weight of onion powder, 0.5 parts by weight of sorbitan fatty acid ester and 9 parts by weight of vegetable hydrogenated oil were heated and melted. 1110 parts by weight of milk was added to the colander and mixed, and this was placed in a fluidized bed granulator in the same manner as in Example 13, sprayed with a small amount of water, granulated, and then granulated with hot air at 70°C. It was dried and sieved to prepare instant corn potage soup.

This product easily dissolves and disperses when poured with boiling water, creating a soup with excellent flavor.

Example 15 Production of Uiro no base 90 parts by weight of rice flour, 20 parts by weight of cornstarch, 120 parts by weight of anhydrous crystalline maltitol-containing honey crystal powder obtained by the method of Example 4, and 4 parts by weight of pullulan were uniformly mixed. Manufactured Uiro base.

After adding water to 200 g of Uiro base and 1 g of Matcha powder and kneading them thoroughly, the mixture was placed in a container and steamed for 60 minutes to produce Matcha Uiro.

This product had a good shine, texture, and flavor. In addition, starch retrogradation was suppressed and it was stable for a long period of time.

Example 16 Production of Bettarazuke no moto Parts by weight, 0.03 parts by weight of potassium sorbate, and 0.2 parts by weight of pullulan were uniformly mixed to produce a base for Betta-Kusa.

30 kg of daikon radish was mashed with salt according to the usual method, and then pickled with sugar, and then mixed with 4 kg of Honbetara Mashinomoto.
Bettara-zuke was prepared by soaking it in the prepared seasoning liquid.

This product had good color, luster, and aroma, moderate sweetness, and good crispness.

In addition, this product was resistant to rancidity and was stable for a long period of time.

Example 17 Manufacture of tablets 50 parts by weight of aspirin, 14 parts by weight of anhydrous crystalline maltitol-containing honey crystal powder obtained by the method of Example 3, and 4 parts by weight of cornstarch were thoroughly mixed, and the mixture was then processed using a tablet machine according to a conventional method. The tablets were compressed into tablets with a thickness of 5.25 mm and a weight of 680 mg each.

Ice crystals are not hygroscopic, have sufficient physical strength, and disintegrate extremely well in water.

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of anhydrous crystalline maltitol. FIG. 2 shows the infrared absorption spectrum of anhydrous amorphous maltol. FIG. 3 is a photograph showing an example of the shape of anhydrous crystalline maltitol magnified 150 times with a microscope. FIG. 4 is a photograph showing an example of the shape of anhydrous crystalline maltitol magnified 600 times with a wI microscope. FIG. 5 is a schematic diagram of the three-dimensional structure of molecules in anhydrous crystalline maltitol. 3rd picture length, 1, Isao, 9-Otori

Claims (4)

[Claims] (1) A composition for oral use containing anhydrous crystalline maltitol or nectar-containing crystals containing the same. (2) The composition for use in the mouth is powdered, granular, rod-shaped, spherical,
The composition for oral use according to claim 1, wherein the composition is shaped into a tablet, a plate, or a cube. (3) The composition for oral use according to claim 1 or 2, wherein the composition for oral use is a food or drink. (4) The composition for oral use according to claim 1 or 2, wherein the composition for oral use is a sweetener.