JP4004533B2 - Flavor degradation inhibitor - Google Patents

Description

  The present invention relates to a flavor degradation inhibitor derived from a specific natural product that can be widely applied to foods or oral hygiene agents containing flavor components.

Oral hygiene agents (hereinafter abbreviated as “food” etc.) such as toothpastes and antibacterial agents used in foods and oral cavity can be tasted as soon as they enter the mouth. The flavor such as is an important element as well as various nutritional components.
It is well known that the flavor of such foods gradually deteriorates at each stage of production, distribution, storage and the like. Factors related to deterioration mainly include heat, light, oxygen, and water.
Therefore, in the past, especially as countermeasures against flavor deterioration due to oxygen, development of synthetic resin containers and bags with low oxygen permeability, introduction of food manufacturing processes incorporating deoxygenation conditions, and addition of antioxidants However, other measures of deterioration, particularly measures against deterioration due to light, have not been considered much.

However, recently, production and sales of foods in transparent glass containers, foods in semi-transparent plastic containers, foods in transparent bags, and the like have been increasing in order to improve the product image at store display. Furthermore, the sales form which displays them under a fluorescent lamp for a long time in a convenience store etc. has become common. Therefore, it is more susceptible to light than before, and results in flavor deterioration and the like.
Therefore, it has become necessary to develop a means that has a particularly large suppression effect on the deterioration of flavor due to light, and also has a deterioration suppression effect due to heat during the heat sterilization step and heat storage.

  Flavor degradation due to light becomes a factor in which flavor components are decomposed by light irradiation and aroma / taste is lost, and further, decomposed products are converted into malodorous / taste components. In order to mainly suppress such deterioration due to light, milk-containing acidic beverages (see Patent Document 1) and coffee raw materials that have been added with rutin, morin or quercetin to prevent the generation of malodorous and off-flavor substances and to improve storage stability. A method for preventing flavor deterioration due to sunlight by using chlorogenic acid, caffeic acid, ferulic acid derived from bean extract together with vitamin C, rutin, and quercetin (see Patent Document 2), and a perfume composition derived from natural products A method has been proposed in which chlorogenic acid derived from coffee beans is added to prevent deterioration of natural flavors (see Patent Document 3).

However, the natural product-derived degradation inhibitor in the prior art is generally highly safe and can be recommended, but on the other hand, it is necessary to use a certain amount in order to exert the flavor degradation inhibiting effect. As a result, there was a lack of practicality such as the taste and smell of the degradation inhibitor itself adversely affecting the taste and aroma of the food itself.
In addition, although the deterioration suppression method by the packaging means improvement of the foodstuff etc. which used the container and bag which suppressed light transmittance was proposed, this was not enough from the viewpoint of both cost and a flavor deterioration suppression effect.
Therefore, when added to foods, etc., it is highly safe, has a sufficient effect with a small amount of use without affecting the original flavor of foods, etc. There has been a demand for degradation inhibitors derived from natural products.
Japanese Patent Publication No. 4-21450 JP-A-4-27374 JP-A-4-345893

  The object of the present invention is to provide a flavor deterioration inhibitor that solves the problems in the prior art, has high safety, and does not affect the original flavor of food, such as production, distribution, storage, etc. of food In each stage of the above, a flavor deterioration inhibitor that mainly suppresses the deterioration of flavor due to the effects of light, heat, oxygen, etc., a food having stable quality by adding a predetermined amount of the inhibitor, and a predetermined amount of the inhibitor It is to provide a method of adding to suppress the deterioration of flavor and stabilize the quality.

  As a result of intensive studies on the flavor deterioration-inhibiting activity of a variety of natural product-derived components centered on plants, the present inventors have used long-term exposure to light by using a solvent extract of a specific plant or natural product. On the other hand, it was found that flavor deterioration of foods and the like due to heat, oxygen and the like can be further suppressed, and the present invention has been completed.

  That is, the first of the present invention is characterized by containing a solvent extract of at least one natural product selected from the group consisting of eucalyptus, clove, mirabaran, strawberry, sanshuyu, gennoshouko, pomegranate, velvet, pentaploid and akamegashiwa. And a flavor deterioration inhibitor. Further, the natural product is characterized by eucalyptus, myrobalan, strawberry and pomegranate, and the solvent is characterized by water or a polar organic solvent.

  The second of the present invention is a food or oral hygiene agent to which the above flavor deterioration inhibitor is added in an amount of 0.01 to 500 ppm.

  The third aspect of the present invention is a food or oral hygiene agent comprising at least one natural product solvent extract selected from the group consisting of eucalyptus, clove, milobaran, strawberry, sanshuyu, gennoshouko, pomegranate, hoshi, pentaploid and akamegashiwa. In this method, 0.01 to 500 ppm is added to suppress deterioration of flavor.

By using the flavor deterioration inhibitor according to the present invention for foods and the like, it has an effect of suppressing flavor deterioration for those that are easily affected by light, heat, oxygen and the like.
Especially for light, it has a remarkable effect of suppressing deterioration and can maintain a stable flavor for a long period of time, so it can be filled in transparent glass containers, translucent plastic containers, or transparent bags that are easily affected by light irradiation. If it is applied to processed foods, etc., excellent effects are exhibited.
Moreover, since the taste and smell of the degradation inhibitor itself do not affect the original flavor of foods and the like, it can be widely applied.

Hereinafter, the present invention will be described in more detail.
(1) Raw material The natural product used in the present invention is at least one plant selected from the group listed below or a plant-related product such as a pentaploid, and these can be used alone or in combination.

Eucalyptus (scientific name: Eucalyptus globulus Labill.)
Tingji (Choji, scientific name: Eugenia caryophyllata Thunb.)
Myrobalan (scientific name: Terminalia chebula Retz.)
Strawberry (scientific name: Fragaria grandiflora Ehrh)
Sanshuyu (scientific name: Cornus officinalis Sieb. Et Zucc.)
Genokosho (scientific name: Geranium thunbergii Sieb. Et Zucc.)
Pomegranate (scientific name: Punica granatum L.)
Hishi (Scientific name: Trapa japonica Flerov.)
Akamegasiwa (scientific name: Mallotus japonicus Muell. Arg.)
Puploid (a gallbladder formed by infestation of a single dwarf female of Nuldenomimushi furamushi on a young leaf of Nurde)

  The above natural products have been used as pharmaceuticals for a long time and have been confirmed to be safe. For example, pomegranate has been used as a traditional Chinese medicine, and recently, it has been reported that it is also effective as an anti-inflammatory drug or anti-allergic drug (Japanese Patent Laid-Open Nos. 5-310745 and 62-142181). Gazette), there is no report on the relationship with flavor.

Among the above, plants other than the pentaploid are subjected to an extraction process described later using roots, stems (branches), leaves, and fruits.
Among them, for eucalyptus and red-crowned wrinkles, it is preferable to use leaves, myrobalans, strawberries, sanshuyu and hoshi for fruits, leaves and stems for genus shochu, pomegranates for pericarp and root bark, and buds for clove.
Among the above natural products, eucalyptus, myrobalan, strawberry and pomegranate are preferable.

  In addition, although the above-mentioned natural product solvent extract has an excellent effect in suppressing the deterioration of flavor, hydrolyzable tannins such as gallotannins, ellagitannins, and dehydroelagitannins in the extract are mainly the action. It is speculated that it plays a role. Therefore, even if it is a natural product other than the above, if it is a natural product containing a relatively large amount of hydrolyzable tannins, the solvent extract can be expected to have the same effect.

(2) Extraction treatment 1) Solvent The solvent used for the extraction treatment may be water or a polar organic solvent, and the organic solvent may be a hydrate.
Examples of the polar organic solvent include alcohol, acetone, ethyl acetate and the like.
Among these, water or an aliphatic alcohol having 2 to 4 carbon atoms such as ethanol, propanol, and butanol is preferable from the viewpoint of safety to the human body and handleability. Water or ethanol or a mixture thereof is particularly preferable.
In addition, it is preferable to perform a degreasing treatment in advance with a nonpolar solvent such as hexane as a pretreatment for extraction, because it is possible to prevent a large amount of excess lipid from entering during the subsequent extraction treatment. Further, this degreasing treatment may result in purification such as deodorization.

2) Extraction As an extraction treatment method, pulverized various natural products are put in a solvent and extracted by an immersion method or a heating reflux method. In addition, when using the immersion method, any of heating conditions, room temperature, or cooling conditions may be used.
Next, the residue insoluble in the solvent is removed to obtain an extract. As the residue removal method, various solid-liquid separation means such as centrifugation, filtration, and pressing can be used.
The obtained extract can be used as it is by adding it to food or the like, but can be used after appropriately diluted with a food solvent such as water or ethanol. Furthermore, it can be used as an extract in the form of powder or paste by freeze-drying or concentration.

3) Purification The extract obtained by the above method can of course be added to foods and the like as it is, but since such an extract may have a colored state or odor, it is porous, such as styrene. A purified product obtained by fractionation into a fraction eluted with water or an aqueous ethanol solution using a synthetic resin adsorbent comprising a divinylbenzene copolymer is preferred because it is decolorized and deodorized.
As synthetic resin adsorbents for purification, for example, “Diaion (registered trademark) HP-20” manufactured by Mitsubishi Chemical Corporation and “Amberlite (registered trademark) XAD-2” manufactured by Organo Corporation are commercially available. It is.
In some cases, it is also possible to purify, that is, decolorize and deodorize using an ion exchange resin or activated carbon.
In the case of pomegranate, there is an advantage that the activity is improved by purification.

(3) Usage The flavor deterioration inhibitor obtained by the above extraction treatment can be appropriately added at the processing stage of foods and the like. The amount added varies somewhat depending on the concentration of the inhibitor or the type of flavor component contained in the food or the like, or the flavor threshold, but generally an amount of 0.01 to 500 ppm is appropriate for the food or the like. From the viewpoint of adding within the range of a threshold value that does not affect the original flavor of food or the like, 1 to 30 ppm is preferable, and 1 to 10 ppm is particularly preferable.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.
Examples of extraction of each natural product are shown below. However, examples of extraction of natural products other than pomegranate are reference examples.
It is.

[Extraction Example 1-1]
100 g of dried eucalyptus leaves were placed in 1 kg of 70% acetone aqueous solution and refluxed for 1 hour. After cooling, the mixture was centrifuged and filtered through celite to remove insoluble matters. The filtrate was concentrated under reduced pressure and then freeze-dried to obtain 35 g of a powder product.

[Extraction Example 1-2]
The dried eucalyptus leaves were extracted with 50% ethanol to obtain an extract.
As shown in FIG. 1, the physical properties of the extract were as follows.
a) UV absorption spectrum (measured concentration: 20 ppm, diluting solvent: 50% ethanol)
λ _max : 299.8 nm, 272.0 nm
As a measuring instrument, “Spectrophotometer UV-2100” manufactured by Shimadzu Corporation was used.
(The same is true for each example below).
b) Solubility: soluble in water, easily soluble in 50% ethanol, soluble in ethanol

[Extraction Example 2]
After pulverizing 50 g of freeze-dried strawberry fruits, 500 g of water was added and the mixture was extracted by standing at room temperature for 1 day. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was freeze-dried to obtain 32 g of a strawberry powder product.
This powder is dissolved in water, and a porous synthetic resin adsorbent (mentioned above “Diaion HP20”, specific surface area 511 m ² , pore volume 1.18 ml / g by mercury porosimetry, pore volume 1.30 ml by nitrogen adsorption method. / G) and fractionated into water, 50% ethanol aqueous solution and 95% ethanol aqueous solution elution fractions for purification. Yields were 5.1 g, 17 g, and 3.1 g, respectively.
In addition, as shown in FIG. 2, the physical properties of the 50% ethanol extract were as follows.
a) UV absorption spectrum (measured concentration: 8 ppm, diluting solvent: 50% ethanol)
λ _max : 300.0 nm, 279.0 nm
b) Solubility: Easily soluble in water, easily soluble in 50% ethanol, soluble in ethanol

[Extraction Example 3-1]
50 g of dried pomegranate peel was pulverized, placed in 1 kg of 50% ethanol aqueous solution, and heated to reflux for 1 hour.
The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was freeze-dried to obtain 32 g of pomegranate extract (powder product).
This powder is dissolved in water and filled in a porous synthetic resin adsorbent ("Diaion HP-20" mentioned above), and fractionated into water, 20% ethanol aqueous solution, 50% ethanol aqueous solution, and 70% acetone aqueous solution elution fraction. And purified. Yields were 5.8 g, 3.2 g, and 18.6 g, respectively.
In addition, as shown in FIG. 3, the physical properties of the 50% ethanol extract were as follows.
a) Ultraviolet absorption spectrum (measured concentration: 20 ppm, diluting solvent: 50% ethanol)
λ _max : 366.2 nm, 258.2 nm
b) Solubility: soluble in water, easily soluble in 50% ethanol, insoluble in ethanol

[Extraction Example 3-2]
1 kg of water was added to 100 g of dried pomegranate peel and heated to reflux for extraction. After removing solids by Celite filtration, activated carbon was added as a purification treatment of the filtrate, and the mixture was stirred for 30 minutes to decolorize and deodorize.
After the purification treatment, it was freeze-dried to obtain 35 g of a light brown powder.

[Extraction Example 4]
The dried clove buds were extracted with hot water.
As shown in FIG. 4, the physical properties of the extract were as follows.
a) UV absorption spectrum (measured concentration: 20 ppm, diluting solvent: water)
λ _max : 299.6 nm, 256.6 nm
b) Solubility: Easily soluble in water, easily soluble in 50% ethanol, soluble in ethanol

[Extraction Example 5]
The dried quintuplet was extracted with hot water.
As shown in FIG. 5, the physical properties of the extract were as follows.
a) UV absorption spectrum (measured concentration: 10 ppm, diluting solvent: water)
λ _max : 299.6 nm, 275.0 nm
b) Solubility: Easily soluble in water, easily soluble in 50% ethanol, soluble in ethanol

[Extraction Example 6]
The dried myrobalan fruit was extracted with 50% aqueous ethanol.
As shown in FIG. 6, the physical properties of the extract were as follows.
a) Ultraviolet absorption spectrum (measured concentration: 15 ppm, diluting solvent: 50% ethanol)
λ _max : 363.6 nm, 299.8 nm, 274.6 nm
b) Solubility: Easily soluble in water, easily soluble in 50% ethanol, insoluble in ethanol

[Extraction Example 7]
The dried sanshuyu fruit was extracted with hot water.
As shown in FIG. 7, the physical properties of the extract were as follows.
a) Ultraviolet absorption spectrum (measured concentration: 100 ppm, diluting solvent: water)
λ _max : 299.8 nm
b) Solubility: Easily soluble in water, soluble in 50% ethanol, insoluble in ethanol

[Extraction Example 8]
The dried red leaves were extracted with a 50% aqueous ethanol solution.
As shown in FIG. 8, the physical properties of the extract were as follows.
a) Ultraviolet absorption spectrum (measured concentration: 15 ppm, diluting solvent: 50% ethanol)
λ _max : 299.8 nm, 273.8 nm
b) Solubility: Easily soluble in water, easily soluble in 50% ethanol, soluble in ethanol

Next, the inhibitory activity with respect to the flavor deterioration of the obtained extract was evaluated.
[Test Example 1]
A 65% aqueous ethanol solution containing 35 g of sugar, 0.35 g of citric acid and 1 g of citral, which is a flavor component peculiar to citrus fruits such as orange and lemon, was prepared (total amount 1000 ml).
Put this solution in a transparent glass container, add various pomegranate extracts shown in Table 1 to make a sample, and irradiate with a light stability tester (“LST-300” manufactured by Tokyo Rika Kikai Co., Ltd.). It was.
Irradiation conditions were a temperature of 10 ° C., a white fluorescent lamp 40 W × 12 and a 360 nm near-ultraviolet lamp 40 W × 3, adjusted to 4000 lux, and a near-ultraviolet intensity of 0.3 mW / cm (inner center) for 72 hours.

The citral content after light irradiation was measured by high performance liquid chromatography (HPLC). The measurement conditions are as follows.
(Measurement condition)
Equipment: “HITACHI D-7000 HPLC system” manufactured by Hitachi, Ltd.
Column: “Cosmo Seal 5C18-AR-11” manufactured by Nacalai Tesque (column temperature 40 ° C.)
Eluent: A. Acetonitrile, B.I. Water Gradient condition: 0 minutes → 25 minutes
A. Acetonitrile 10% 100%
B. Water 90% 0%
Flow rate: 1 ml / min Detection wavelength: 254 nm

The citral residual amount (%) in Table 1 was calculated according to the following formula.
Citral remaining amount (%) = A / B x 100
(A: Citral content in the sample after light irradiation,
B: Citral content in the sample before light irradiation)

Next, the flavor deterioration inhibitor obtained by the above extraction was added to various foods for evaluation.
Example 1 (yogurt beverage)
94 g of milk and 6 g of skim milk powder were mixed and then sterilized (90 to 95 ° C., 5 minutes). After cooling to 48 ° C., a starter was inoculated. This was put into a glass container and fermented (40 ° C., 4 hours, pH 4.5). After cooling, it was stored at 5 ° C. and used as a yogurt base.
On the other hand, as the sugar solution, 20 g of sucrose, 1 g of pectin, and 79 g of water were mixed, heated at 90 to 95 ° C. for 5 minutes, and filled with a hot pack.
60 g of the above yogurt base, 40 g of sugar solution, and 0.1 g of fragrance were mixed, and this was subjected to a homomixer treatment and a homogenizer treatment.

A semi-transparent plastic container was filled with a product to which no flavor deterioration inhibitor was added and a product to which 5 ppm of a flavor deterioration inhibitor was added.
Each was put in a photostability tester and irradiated with a fluorescent lamp (6000 lux, 10 ° C., 5 hours), and 10 skilled panelists were selected for sensory evaluation. In this case, as a control having no change in flavor, an unirradiated yogurt beverage with a fluorescent lamp not added with a flavor deterioration inhibitor was used, and the degree of change (deterioration) in flavor was evaluated.
The results are shown in Table 2.
In addition, the score of evaluation in Table 2 is an average score of each panel scored according to the following criteria.
(Scoring criteria)
Strong taste and smell: 4 points Flavor changed very much: 3 points Flavor changed: 2 points Flavor changed slightly: 1 point Flavors did not change: 0 points

  As shown in Table 2, it was found that the addition of the inhibitor had a higher flavor deterioration inhibiting effect than the additive-free one.

Example 2 (lemon beverage A)
The total amount was adjusted to 100 g with 10 g of granulated sugar, 0.1 g of citric acid, 0.1 g of lemon flavor, and water. A glass container was filled and sterilized with no addition of a flavor deterioration inhibitor and 2 ppm of various flavor deterioration inhibitors. After irradiating them with a light stability tester (15000 lux, 10 ° C., 3 days), ten experienced panels were selected for sensory evaluation. And in this case, the non-irradiated lemon drink of the fluorescent lamp which has not added the flavor deterioration inhibitor was used as a control, and the change (deterioration) degree of flavor was evaluated. The results are shown in Table 3.
In addition, the score of evaluation in Table 3 is the average score of each panel scored on the same basis as in Example 1.

  As shown in Table 3, it was found that the addition of the inhibitor had a higher flavor deterioration inhibiting effect than the additive-free one.

Example 3 (lemon beverage B)
The addition of 3 ppm of pomegranate extract was evaluated. Other conditions are the same as in the second embodiment. The results are shown in Table 4.
In addition, the score of evaluation in Table 4 is the average score of each panel scored on the same basis as in Example 1.

  As shown in Table 4, it was found that the addition of the inhibitor had a higher flavor deterioration inhibiting effect than the additive-free one.

Example 4 (lactic acid bacteria beverage)
A glass container was filled and sterilized with 100 g of lactic acid bacteria beverage without adding a flavor deterioration inhibitor and 10 ppm of a flavor deterioration inhibitor.
After irradiating them with a light stability tester (15000 lux, 10 ° C., 12 hours), ten experienced panelists were selected for sensory evaluation. In this case, a non-irradiated lactic acid bacteria beverage of a fluorescent lamp not added with a flavor deterioration inhibitor was used as a control, and the degree of flavor change (deterioration) was evaluated. The results are shown in Table 5.
In addition, the score of evaluation in Table 5 is the average score of each panel scored on the same basis as Example 1.

  As shown in Table 5, it was found that the addition of the inhibitor had a higher flavor deterioration suppressing effect than the additive-free one.

It is an ultraviolet absorption spectrum figure of the extract of eucalyptus leaves. It is an ultraviolet absorption spectrum figure of the extract of a strawberry fruit. It is an ultraviolet absorption spectrum figure of a pomegranate peel extract. It is an ultraviolet absorption spectrum figure of the extract of a clove bud. It is an ultraviolet absorption spectrum figure of the extract of a quintuplet. It is an ultraviolet absorption spectrum figure of the extract of myrobalan fruit. It is an ultraviolet absorption spectrum figure of the extract of a Sanshuyu fruit. It is an ultraviolet absorption spectrum figure of the extract of a red-knot wrinkle.

Claims (7)

Zac ii solvent extract of pericarp (provided that aqueous acetone excluding eluted fraction in fraction purified with synthetic adsorbent) flavoring deterioration suppressing agent characterized in that it contains. Zac ii solvent extract of pericarp (provided that aqueous acetone excluding eluted fraction in fraction purified with synthetic adsorbent) flavoring deterioration inhibitor by light irradiation, characterized in that it contains.   The flavor deterioration inhibitor according to claim 1 or 2, wherein the solvent is water or a polar organic solvent. A food or oral hygiene agent to which the flavor deterioration inhibitor according to any one of claims 1 to 3 is added in an amount of 1 to 30 ppm.   A food or oral hygiene agent comprising 1 to 10 ppm of the flavor deterioration inhibitor according to any one of claims 1 to 3. A lemon beverage, a yogurt beverage or a lactic acid bacteria beverage to which the flavor deterioration inhibitor according to any one of claims 1 to 3 is added in an amount of 1 to 30 ppm. Zac ii solvent extract of pericarp (provided that aqueous acetone excluding eluted fraction in fraction purified with synthetic adsorbent) method for inhibiting flavor deterioration by adding 0.01~500ppm to food or oral hygiene agents.

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