JPH0549684A - Deodorizing composition - Google Patents

Abstract

PURPOSE:To provide the deodorizing compsn. which is free from rough, harsh, bitter, and astringent tastes and is useful for drinks, food, etc., by consisting the compsn. of low-mol.wt. chitosan having about <=10000 average mol.wt. and/or the metal complex of this chitosan and/or the org. acid salt, etc., of the chitosan as its effective components. CONSTITUTION:The org. acid salt of the low-mol.wt. chitosan having about <=10000 average mol.wt. is formed by using ascorbic acid and other org. acids or the complex with a metal which can form a complex salt with the org. acid salt, etc., of the chitosan obtd. in such a manner is prepd. A more preferable example includes the deodorizing compsn. formed by combining the ascorbate of the chitosan and bivalent iron compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant composition useful in a wide range of fields such as foods and drinks, pharmaceuticals and cosmetics. More specifically, it is a low molecular weight chitosan having an average molecular weight of about 10,000 or less and / or a metal of the chitosan. The present invention relates to a deodorant composition containing a complex and / or an organic acid salt of chitosan as a deodorant active ingredient and having significantly improved taste.

[0002]

2. Description of the Related Art Chitosan has antibacterial and deodorant properties, and its use in foods and drinks, cosmetics, toiletries and the like is being studied. Regarding deodorant properties, for example, an oral composition effective in preventing caries, preventing alveolar pyorrhea, and preventing bad breath by including at least one of chitin and chitosan in the oral composition (JP-A-59-101416) ;
Foods and drinks having the same halitosis-preventing effect and periodontal disease-preventing effect as described above by blending one or more water-soluble compounds such as partially deacetylated chitin derived from chitin (JP-A-61- No. 216648) is disclosed. In addition, a cosmetic composition containing chitosan as an active ingredient in the form of a water-soluble salt, which is highly deodorant, antibacterial, and has excellent biocompatibility without irritation, toxicity, or allergy (Japanese Patent Laid-Open No. 63-
290808); a deodorant composition comprising a compound of chitosan and an organic acid and / or an inorganic acid (JP-A-1-5553), sardines, saury,
Add chitosan acid treatment to the meat of red fish such as mackerel,
A fish meat food material (Japanese Patent Laid-Open No. 63-116670) in which red fish is deodorized by mixing, molding and heat treatment is disclosed.

[0003]

Chitosan, which has a high degree of purification, is tasteless and odorless, but when dissolved in acid, it exhibits a unique astringent taste and bitterness. This astringent taste is quite strong,
It is known that even a dilute solution of about 0.005% can be felt sensitively in a lactic acid solution. This astringent taste is often a problem when chitosan is added to foods and drinks. It is conventionally known that it can be improved to some extent by increasing the protein concentration in food or raising the pH to near neutrality, but such means may not always be adopted depending on the composition of food and drink. However, its use is extremely limited and the deodorizing effect is not always satisfactory.

On the other hand, the chitosan conventionally used in the above-mentioned proposals generally has a molecular weight of several tens of thousands to several hundreds of thousands, so that it has poor solubility and further has a high viscosity and is inconvenient to handle. A method for producing low molecular weight chitosan has also been proposed for the purpose. As a method for producing such low molecular weight chitosan, for example, an aqueous solution of chitosan,
A molecular weight of 500 to be decomposed by at least one of papain, cellulase and acid protease
Manufacturing method of low molecular weight chitosan of 0-50000
57958); 0.004 to 10% sodium zincate and 0.0 adjusted to pH 8 or less with chitosan.
Method for producing low molecular weight chitosan by treating in an aqueous solution containing 1-3.50% hydrogen peroxide (JP-A-63-
No. 120701 gazette); chitosan obtained by deacetylating natural chitin is used in an amount of 0.1% per hexosamil residue.
Method for producing low molecular weight chitosan which is contacted with 1 to 10 molar equivalents of chlorine gas at a temperature of 10 to 70 ° C (JP-A-60-
186504 gazette); Proposal of a method for producing low molecular weight chitosan by treating natural chitin with cellulase in the form of solution or gel dispersion of chitosan obtained by deacetylation (Japanese Patent Publication No. 2-20292) Has been done.

However, low-molecular-weight chitosan having a molecular weight of tens of thousands to hundreds of thousands is still unsatisfactory in terms of solubility and deodorizing effect, and further, it has an astringent taste, bitterness, astringency and astringency. The fact that it has a peculiar unpleasant taste has not been solved yet, and the presence of these off-flavors and off-flavors is a major problem especially when it is incorporated into foods and drinks. On the other hand, a low molecular weight chitosan having a molecular weight of several hundred to about 10,000 has never been used as a deodorant, and the low molecular weight chitosan is compared with a conventional chitosan having a molecular weight of several tens of thousands to several hundreds of thousands. There is no description about having excellent properties of not having peculiar unpleasant taste such as astringent taste, bitterness, astringency and astringency,
Further, it is not known at all that it is extremely useful as a deodorant for foods and drinks by utilizing this characteristic.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the drawbacks of the conventionally proposed low molecular weight chitosan. As a result, a commercially available molecular weight of about 50,000 to about 30
It was found that low molecular weight chitosan having a molecular weight of about 10,000 or less can be freely produced by decomposing 0000 chitosan with the enzyme chitosanase and controlling the enzyme concentration and the reaction time. In particular, it has been found that a low molecular weight chitosan having a molecular weight of about 10,000 or less can be produced more efficiently and easily than a conventional enzymatic decomposition method by enzymatically decomposing it using a chitosanase produced by a microorganism belonging to the genus Verticillium, and a patent application has already been applied ( Japanese Patent Application No. 2-2146
64). Further, they have found that low molecular weight chitosan having a molecular weight of about 10,000 or less is significantly improved in taste and solubility as compared with conventional chitosan.
No. 214663. The inventors have found that the molecular weight of about 10,000 or less significantly improves the solubility, deodorizing effect and taste of chitosan, and solves the above-mentioned drawbacks all at once, thus completing the present invention. Therefore, an object of the present invention is to provide a deodorant composition containing a low molecular weight chitosan having a molecular weight of about 10,000 or less and / or a metal complex of the chitosan and / or an organic acid salt of the chitosan as an active ingredient.

The present invention will be specifically described below.

The molecular weight used in the present invention is about 1,000.
Chitosan of 0 or less can be easily produced according to the method described in the above-mentioned Japanese Patent Application No. 2-214664. The outline thereof will be explained. For example, commercially available chitosan is dispersed in water and an organic acid is added to adjust the pH to about 3.5 to about 6.0 to dissolve chitosan, and finally about 0.5 to about Make a chitosan solution of about 5% by weight. To this chitosan solution, for example, chitosanase produced by a microorganism belonging to the genus Verticillium is added and reacted at about 30 to about 37 ° C. The molecular weight of low molecular weight chitosan produced by this enzymatic reaction can be freely controlled by adjusting the concentration of chitosan and the amount of enzyme added, reaction time, reaction temperature and reaction pH. For example, if the enzyme reaction is carried out while keeping the chitosan concentration, reaction time, reaction temperature and reaction pH constant, the molecular weight of about 100 can be obtained only by adjusting the amount of enzyme added.
It is possible to freely produce low molecular weight chitosan having a molecular weight of 00 or less. Such a low molecular weight chitosan has never been used in a deodorant composition, and was first disclosed by the present inventors.

Various organic acid salts of low molecular weight chitosan of the present invention can be prepared by selecting the type of organic acid used for dissolving chitosan during the above-mentioned enzyme treatment. Further, if desired, the organic acid forming a salt can be removed or replaced arbitrarily and easily by a method such as ion exchange. Examples of such a replaceable organic acid include formic acid, acetic acid, propionic acid, lactic acid, hydroxyacetic acid, malic acid, tartaric acid, glyceric acid, citric acid, ascorbic acid, erythorbic acid, α-methylmalic acid, β-hydroxyglutaric acid. Examples thereof include gluconic acid, glucuronic acid, ketogluconic acid, salicylic acid, gallic acid, glyoxylic acid, pyruvic acid, and 2-ketobutyric acid. In particular, organic acids having a reducing ability such as ascorbic acid and erythorbic acid can be preferably mentioned.

The above-mentioned molecular weight used in the present invention is about 10
Chitosan having an amount of 000 or less or an organic acid salt of chitosan has a sufficient deodorizing effect by itself, and further it can be added to the low molecular weight chitosan, for example, iron, zinc, aluminum, copper, cobalt, nickel, chromium. The deodorizing effect can be enhanced by reacting a metal chloride such as manganese or the like, a metal salt capable of forming a complex salt such as a sulfate or a nitrate, to form a complex. Among these metal salts, iron compounds such as ferrous sulfate, ferrous chloride, ferrous nitrate and iron citrate are particularly preferable.

The molecular weight provided by the present invention is about 100.
A low molecular weight chitosan having a molecular weight of 00 or less and / or an organic acid salt of the chitosan and / or a metal complex of the chitosan (hereinafter, these may be collectively referred to as simply low molecular weight chitosans) are compared with conventional chitosan. In addition to being excellent in solubility, clarity and deodorant property, it is particularly remarkable in terms of taste, that is, it does not have the unique astringent and bitter tastes unavoidably associated with conventional chitosan. It is excellent in that it can efficiently remove offensive odors such as ammonia, mercaptans and hydrogen sulfide, and is excellent in sustainability. It is especially useful as a general deodorant, not only because of its improved taste. Moreover, it can be effectively used for deodorizing and smelling foods and beverages.

The deodorant composition provided by the present invention is
For example, carbonated drinks, fruit drinks, dairy drinks, nutritional drinks,
Beverages such as sports drinks, favorite beverages, soy milk, alcoholic drinks; confectionery such as candies, jellies, chewing gum, snacks; frozen desserts; processed meat products such as ham, bacon, sausages; In addition to food and drink products such as processed marine products, oral products such as toothpaste, mouthwash, troche, etc .; toiletry products such as soap, detergent, shampoo, rinse, antiperspirant, etc. be able to.

The molecular weight provided by the present invention is about 100.
There is no particular restriction on the amount of low molecular weight chitosan having a value of 00 or less, but for example, as a compounding ingredient in the deodorant composition, it is about 0.001 to about 50% by weight, preferably about 0.01 as a dry matter. To about 10% by weight. The amount added to cosmetics, pharmaceuticals and foods and drinks is, for example, about 0.01 to about 10% by weight as a dried product.
Such ranges are often adopted.

In the present invention, if desired, in addition to the above-mentioned low molecular weight chitosans having a molecular weight of about 10,000 or less, conventionally known components having a deodorizing effect, for example, flavonoids, catechins, various spices / herbs extracts, etc. It is also possible to use plant extracts of the above; cyclodextrin, activated carbon and the like in combination. Although the mixing ratio of such a conventionally known deodorant (denoted as A) and chitosan having a molecular weight of about 10,000 or less (denoted as B) can be arbitrarily selected,
Generally, a range of about (A) :( B) = about 1:10 to about 10: 1 is adopted. Hereinafter, the embodiments of the present invention will be described more specifically by reference examples and examples.

[0015]

[Reference Example 1] Low molecular weight chitosan having a molecular weight of 10,000 or less
Method of preparation .

Chitosan LLWP manufactured by Kimitsu Chemical Industry Co., Ltd.
(Deacetylation degree 85%, molecular weight 50,000 or more) 50
suspension in 890 g of pure water, and Verticillium sp. AF9
-Add chitosanase produced by V-156 strain (Microtechnology Research Institute No. 11374) so as to be 20 mU / ml.
The reaction was carried out at ℃ for 18 hours. The enzymatic reaction was stopped by heating at 80 ° C. for 15 minutes, and the molecular weight of chitosan after the reaction was measured by gel filtration. As a result, the average molecular weight was about 2000 (converted to dextran).

[0017]

Example 1 0.01 ppm solution of methyl mercaptan
5% aqueous solution of low molecular weight chitosan lactate having an average molecular weight of about 2000 (as glucosamine equivalent 0.25)
M) (Solution B), 0.1 mM ferrous chloride aqueous solution (Solution C) and 0.1 mM aqueous L-ascorbic acid solution (D
Samples 1 to 4 as described below were prepared by appropriately combining and adding the required amounts of the liquids).

Sample 1 Solution A 10 ml: Solution B 1 ml Sample 2 . Solution A 10 ml: Solution B 1 ml: Solution C 1 ml Sample 3 . Solution A 10 ml: Solution B 1 ml: Solution C 1 ml: Solution D 1 ml Sample 4 . Solution A 10 ml: Solution C 1 ml: Solution D 1 ml Each sample was subjected to a sensory evaluation of the deodorizing effect of solution A on methyl mercaptan by eight panelists. The results are shown in Table 1.

[0019]

[Table 1] As is clear from the results of Table 1, the lactate salt of low molecular weight chitosan having an average molecular weight of about 2000 according to the present invention was used alone (Sample 1).
However, a remarkable deodorizing effect was exhibited, but by further combining it with ferrous chloride, L-ascorbic acid and the like (Samples 2 to 4), the deodorizing effect is synergistically enhanced.

[0020]

Example 2 Test tube (outer diameter 16.5 mm x length 165 m
m) was injected with 5 g of a 0.1 ppm methyl mercaptan aqueous solution, and three pressure-bonded rubber stoppers for vials were prepared. One of them was used as a control. Flavonoid (Shiraimatsu Shinyaku) was added to the other one at 2% by weight (comparative product), and the remaining one
2% by weight of chitosan having an average molecular weight of about 2000, 2% by weight of vitamin C and 0.1% by weight of Fe ²⁺ were added to the book (product of the present invention). Each test tube is placed in a 50 ° C water bath for 10 minutes, and head gas is 5.0 ml with a gas tight syringe.
Collected and subjected to gas chromatography (GC) analysis.

GC conditions Column: Supelco SPB-1 0.53 mm × 30 m Column temperature: 70 to 220 ° C. (8 ° C./min) Inlet temperature: 250 ° C. Detector temperature: 250 ° C. Detector: FID Head gas of each aqueous solution Perform GC measurement 3 times each
The average of the integrator values was calculated. The results were as follows.

Control: 14539 Comparative product: 4770 Inventive product: 6216

[0023]

[Example 3] 300 ml Erlenmeyer flask (capacity: 365 m
10 ml of each of the following deodorants of Samples 5 to 9 was added to l), 200 μl of an ammonia aqueous solution having a concentration of 1000 ppm was added thereto, and the mixture was immediately sealed and stirred, and then incubated at 25 ° C. for 2 hours. The ammonia concentration of each of these samples was measured using an ammonia detector tube manufactured by Gastec.

Sample 5 (invention product 1): average molecular weight 200
0% chitosan lactate 2% solution Sample 6 (Comparative product 1): Flavonoid (Shiraimatsu Shinyaku Sankarto) 0.2% solution Sample 7 (Comparative product 2): Based on JP-B-61-43091 An aqueous solution prepared by dissolving 27.5 g of iron heptahydrate in water to make 100 ml, adding 0.5 g of L-ascorbic acid, and diluting 10 times with water.

Sample 8 (Invention Product 2): A solution in which Sample 5 and Sample 7 are mixed at a ratio of 1: 1. Sample 9 (control): distilled water

The measurement with the ammonia detector tube was performed twice each. The results are shown in Table 2.

[0027]

[Table 2] * Deodorization rate was calculated by the following formula. [Control (sample 9) concentration-measured concentration] / control (sample 9) concentration x 100 (%)

[0028]

[Example 4] 30 g of salt and MS in 1000 g of frozen ground
10 g of G, 50 g of sugar and 30 g of egg white were added and kneaded uniformly to prepare a kamaboko dough. To this dough, 20 g of a solution of chitosan lactate having an average molecular weight of about 2000 dissolved as chitosan in an amount of 5% by weight was added and uniformly mixed to prepare a kamaboko (invention product 3).

[0029]

Comparative Example 1 50 g of commercially available chitosan LLWP (manufactured by Kimitsu Chemical Co., Ltd.) was dispersed in 890 g of pure water on the same kamaboko dough as in Example 4, and 60 g of 50% lactic acid was added to 20 g of a dissolved chitosan solution to homogenize. After mixing, kamaboko was prepared (Comparative product 3).

A sensory evaluation was carried out by a panel of eight people on the kamaboko (invention product 3) obtained in Example 4 and the kamaboko (comparative product 3) obtained in Comparative Example 1 with the kamaboko containing no chitosan as a control. went. The results are shown in Table 3.

[0031]

[Table 3]

[0032]

According to the present invention, the average molecular weight is about 1000.
A low molecular weight chitosan having a molecular weight of 0 or less and / or an organic acid salt of the chitosan and / or a metal complex of the chitosan, which is excellent in stability and durability and has an astringent taste, an astringent taste,
Provided is a chitosan-based deodorant composition having no bitterness and astringency and excellent in taste. In particular, a deodorant composition in which an ascorbate of chitosan and a divalent iron compound are combined is incorporated into a food or drink by taking advantage of the above properties to remove or reduce the off-flavor of the food or drink, and improve the flavor of the food or drink. It is also extremely useful as an agent.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Minor Yamashita 2-45, Akabanedai, Kita-ku, Tokyo (72) Minor Iwamoto 335 Kayajuku, Nakahara-ku, Kawasaki-shi, Kanagawa Hasegawa Kaori Co., Ltd. 72) Inventor Junichi Ide 335 Kasejuku, Nakahara-ku, Kawasaki City, Kanagawa Prefecture

Claims (1)

[Claims] 1. A deodorant composition comprising a low molecular weight chitosan having an average molecular weight of about 10,000 or less and / or a metal complex of the chitosan and / or an organic acid salt of the chitosan as an active ingredient.