JP5665998B2 - Shellac, taste improver, food and drink, and coating composition - Google Patents

Description

  The present invention relates to shellac that is added to foods and drinks and pharmaceuticals or used as a coating agent.

  Shellac is a refined resinous substance secreted by the scale insect. Since shellac is harmless to the human body and has moisture resistance and good glossiness, it is used for foods such as chocolate and gum, and surface coatings for health foods and pharmaceutical tablets.

  When coating shellac on food or the like, a step of drying and removing the solvent component is performed after shellac is dissolved in an alcohol solvent and applied to the entire surface of the object to be coated (see, for example, Patent Document 1). Moreover, it can also be water-solubilized with an alkali and coated.

JP-A-8-311405

Shellac has a peculiar bitter taste, and the coating of shellac may impair the flavor of foods and the like.
One object of the present invention is to provide shellac with reduced bitterness, a taste improver containing the shellac, a food and drink, and a coating composition. Another object of the present invention is to provide a taste improver and a food or drink containing a bitter component of shellac.

  The shellac of the first aspect of the present invention, which has been made to solve the above-mentioned problems, is a shellac characterized in that the content of the ester compound of jaralic acid and alleuritic acid is 4.0% by weight or less. Note that the above-mentioned jarral acid also includes epi-jararic acid, which is a stereoisomer of jaralic acid.

  The inventors of the present invention have found that among resin acids constituting shellac, an ester compound of gallaric acid (epi-jararic acid) and aleuric acid is a bitter component, and the content of the ester compound It has been found that the bitter taste of shellac is greatly reduced when the content is 4.0% by weight or less.

  Therefore, the shellac having the above-described structure can reduce bitterness when the shellac is added or when a food or drink coated with the shellac is taken or when a medicine coated with the shellac is orally administered.

In addition, like the shellac of the 2nd aspect of this invention, a bitterness reduction can be implement | achieved more notably by making content rate of an ester compound into 3.5 weight% or less.
The taste improving agent according to the third aspect of the present invention is a taste improving agent containing as an active ingredient any shellac of the first aspect and the second aspect of the present invention. Since the bitterness of the shellac of any of the first and second aspects of the present invention is reduced, it is difficult to increase the unpleasant bitterness even when added to food and drink. Furthermore, the taste improvement effect which shellac has can be provided to food-drinks. Although the taste improvement effect of shellac differs depending on the food or drink added, mellowness, sweetness, etc. can be increased as an example.

  The food / beverage products of the 4th aspect of this invention are food / beverage products to which the shellac in any one of the 1st aspect of this invention and a 2nd aspect is added. Such foods and drinks can exhibit a taste improving effect by shellac. In addition, the alcoholic beverage like the 5th aspect of this invention can be considered as an example of food / beverage products. When shellac is added to an alcoholic beverage, mellowness and sweetness can be added to the alcoholic beverage.

  The coating composition according to the sixth aspect of the present invention is a coating composition used for at least one of foods and pharmaceuticals containing shellac according to any one of the first and second aspects of the present invention. Since the bitterness of the shellac of the first and second aspects of the present invention is reduced, it is advantageous that the bitterness is hardly given to foods and pharmaceuticals even when used as a coating agent for foods and pharmaceuticals.

  The taste improving agent according to the seventh aspect of the present invention is a taste improving agent comprising an ester compound of jaralic acid and alleuritic acid as an active ingredient. In addition, epi-jaral acid which is a stereoisomer of jaral acid may be sufficient as the said jaral acid.

  The ester compound has a bitter taste and brings various taste-improving effects to the food and drink when taken together with the food and drink. Therefore, if it is such a taste improving agent, the taste of food-drinks can be improved.

  The food / beverage products of the 8th aspect of this invention are food / beverage products to which the ester compound of a gallaric acid and an allericin acid is added. In addition, epi-jaral acid which is a stereoisomer of jaral acid may be sufficient as the said jaral acid. Such food and drink can exhibit the taste improving effect of the ester compound. In addition, as an example of the food and drink, an alcoholic beverage can be considered like the food and drink of the ninth aspect of the present invention. When the ester compound is added to an alcoholic beverage, alcohol stimulation in the alcoholic beverage can be reduced.

The figure which shows an example of the cedrene compound which comprises shellac The figure which shows an example of the oxycarboxylic acid which comprises shellac Diagram showing the structural formula of ester compound of jaralic acid and aleuric acid The figure which shows the 1H-NMR spectrum of the compound 1. The figure which shows the 13C-NMR spectrum of the compound 1 Calibration curve for concentration and peak area of compound 1 by LC / MS-MS measurement

Embodiments of the present invention will be described below.
Shellac is a natural resin and consists of a mixture of a number of resin acids and their ester compounds, waxes and pigments. Examples of main ester compounds include esters of cedrene compounds and fatty acids. An example of a cedrene compound considered to be contained in shellac is shown in FIG. Moreover, an example of oxycarboxylic acid as a fatty acid is shown to FIG. 2A-2C. FIG. 3 shows the structural formula of the ester compound of gallaric acid and alleuritic acid among the above-mentioned cedrene compounds and oxycarboxylic acids. The ester compound shown in FIG. 3 is one of the substances constituting shellac.

1. Isolation of bitter component A method for isolating a bitter component contained in shellac will be described.
(Treatment 1) Ethyl acetate 300 mL was added to 30 g of purified shellac GSN (trade name, manufactured by Gifu Seratech Manufacturing Co., Ltd.), stirred under reflux for 30 minutes, and then cooled to room temperature. After standing for 1 hour, the supernatant was removed by decantation. To the remaining precipitate, 300 mL of ethyl acetate was added again and stirred for 30 minutes under reflux. After cooling to room temperature, the mixture was allowed to stand for 1 hour, and the supernatant was removed by decantation. The obtained supernatants were combined and concentrated to obtain 11.7 g of a fraction (Fr. 1).

  (Process 2) The above Fr. 120 mg of No. 1 was dissolved in a small amount of methanol, and passed through a column (φ2.2 × 45 cm) packed with Sephadex LH-20 (trade name, manufactured by GE Healthcare Japan, Inc.) conditioned with methanol. After passing, the LH-20 column was eluted with methanol, and 5 mL was collected.

  Here, the bitterness evaluation of each fraction taken 5 mL each was performed. A portion of each fraction was concentrated under reduced pressure, vacuum dried to remove methanol, dissolved in ethanol, and adjusted with distilled water so that the final ethanol concentration was 5 vol% and the shellac concentration was 1 mg / mL. Was made. The bitterness was evaluated by sensory evaluation. Evaluators (examiners) were six women in their twenties. The test solution 0.1 mL described above was dropped on the evaluator's tongue, and it was determined that there was a bitter taste if the number of persons judged to feel bitter was 4 or more.

The fractions determined to have bitterness were combined and concentrated to obtain 94.6 mg of fraction (Fr.2).
(Process 3) Fr. 2 was fractionated using the above-described LH-20 column (φ2.2 × 45 cm) in the same manner as in the above treatment 2 and bitterness was evaluated, and the fractions that felt bitter were combined and concentrated. .5 mg fraction (Fr.3) was obtained.

  (Process 4) The above Fr. 3 was purified by silica gel column chromatography (Wakogel C-200 φ2.2 × 20 cm, manufactured by Wako Pure Chemical Industries, Ltd.). Methanol: dichloromethane = 1: 9, methanol: dichloromethane = 1: 4 solvent, and methanol were eluted in this order, and the fraction eluted with methanol: dichloromethane = 1: 4 was concentrated to obtain a 12.0 mg fraction. Minute (Fr.4) was obtained.

(Process 5) Fr. 4 was purified by recycle HPLC to obtain 3 mg of a compound which is a bitter component. In the following description, this bitter component is referred to as Compound 1. The apparatus and measurement conditions of recycle HPLC are shown below.
Column: Nomura Chemical Co., Ltd. Develosil ODS-10 / 20 (φ20 × 250 mm)
Solvent: 80 vol% methanol Detection wavelength: 220 nm
Column oven temperature: 30 ° C
Flow rate: 8mL / min
2. Evaluation of bitterness of isolated bitterness component 0.015, 0.031, 0.063, 0.125, 0.250, 0.500 mg of compound 1 obtained in the above (1. Isolation of bitterness component) A test solution dissolved in 5 vol% ethanol was prepared so as to have a concentration of / mL.

0.1 mL of the test solution described above was dropped on the evaluator's tongue, and the limit concentration at which bitterness was felt was examined. Evaluators (examiners) were six women in their twenties.
As a result of the evaluation, six women felt bitterness at either 0.015 to 0.063 mg / mL for compound 1. On the other hand, the lowest concentration of bitter taste in purified shellac GSN was 0.250 to 0.500 mg / mL.

From this, it was confirmed that the bitter component was extracted in the above operation (1. Isolation of bitter component).
3. 3. Identification of compound 1 (bitter component) and measurement of content of compound 1 in shellac 3-1. Identification of Compound 1 Physical and chemical properties of Compound 1 obtained in the above (1. Isolation of bitter components) are listed in the following (A) to (D).
(A) Appearance: White powder (B) Mass spectrometry spectrum: Analysis in ESI negative mode using Applied Biosystems 3200Q TRAP apparatus m / z = 565.4 [M−H].
(C) Rf value in TLC: solvent Rf value methanol: dichloromethane = 1: 4 (v / v) 0.33 (silica gel)
(D) Nuclear magnetic resonance spectroscopy (NMR) spectrum: CD ₃ OD: D ₂ O using JNM-LA300 manufactured by JEOL Ltd. and using heavy methanol as internal standard (δ, ppm = 3.3). = NMR spectrum recorded in 1: 1 (v / v), (s = singlet; d = doublet; t = triplet; brd = broad doublet m = multiplet), 1H recorded at 300 MHz -NMR (δ, ppm): 9.70 d, 6.27 d, 5.91 d, 5.83 d, 4.47 d, 4.43 d, 3.55 t, 3.40-3.37 m, 3.11 d, 2.71-2.65 m, 2.42-2.36 m, 2.03 brd, 2.05-1.97 m, 1.90-1.74 m, 1. 61-1.31 m, 1.13 s (FIG. 4); 13 C-NMR (δ, ppm) recorded at 75.47 MHz: 177.2, 177. 0, 176.3, 145.7, 131.5, 101.3, 101.1, 79.2, 79.0, 75.0, 70.1, 62.8, 58.2, 58.1, 54.2, 54.1, 36.9, 35.4, 34.0, 32.8, 30.1, 29.9, 29.7, 29.6, 25.7, 25.1, 19 .. 8 (FIG. 5).

Since heavy methanol was used, the aldehyde group was in an equilibrium state with hemiacetal, and the spectrum as a mixture thereof was shown.
From these analysis results, Compound 1 was identified as an ester composed of Jalaric acid and Aleuritic acid.

3-2. Content measurement of compound 1 in shellac by LC / MS-MS
LC / MS-MS was measured by the ESI method using a mass spectrometer (manufactured by Applied Biosystems) connected to a liquid chromatography apparatus (manufactured by Shimadzu Corporation). The measurement conditions for LC and MS are shown in Table 1 below.

Jalaric acidとAleuritic acidから成るエステル（化合物１）のMS測定を行うと、ｍ／ｚ５６５．４に前駆イオンが検出された。この前駆イオンについてさらにMS測定を行うと、ｍ／ｚ２６１．２に強いスペクトルが得られた。

When MS measurement of ester (compound 1) consisting of Jalaric acid and Aleuritic acid was performed, a precursor ion was detected at m / z 565.4. When MS was further measured for this precursor ion, a spectrum strong at m / z 261.2 was obtained.

  LC / MS-MS measurement was performed using m / z 565.4 as a precursor ion and m / z 261.2 as a product ion, and a calibration curve as shown in FIG. 6 was obtained. In addition, when compound 1 in purified shellac GSN was quantified, it was found to be 9.82% by weight.

  4). Manufacture shellac with adjusted bitterness content

  100 mL of ethyl acetate was added to 10 g of purified shellac GSN, stirred for 30 minutes under reflux, and then cooled to room temperature. After standing for 1 hour, the supernatant was removed by decantation. 100 mL of ethyl acetate was again added to the remaining precipitate, and the mixture was stirred for 30 minutes under reflux. After cooling to room temperature, the mixture was allowed to stand for 1 hour, and the supernatant was removed by decantation.

The obtained supernatants were combined, concentrated and vacuum dried to obtain 3.7 g of a fraction (Fr.1). Further, the precipitate was concentrated under reduced pressure and dried under vacuum to obtain 6.2 g of fraction (Fr. 2).
Fr. 1 was dissolved in as little methanol as possible and loaded on a column packed with 300 mL of Cosmo Seal 75C ₁₈ -OPN (trade name, manufactured by Nacalai Tesque), and then eluted with a solvent of methanol: water = 4: 1. . This was concentrated under reduced pressure and vacuum dried to obtain 1.3 g of a fraction (Fr. 3). Subsequently, the column was eluted with methanol, and the resulting eluate was concentrated under reduced pressure and dried under vacuum to obtain 2.4 g of a fraction (Fr. 4).

Fr. 2, Fr. 4 was collected together to produce shellac (referred to as shellac A for convenience) with reduced bitterness components.
5. Evaluation of shellac with adjusted bitterness component content Shellac A prepared in Example 1 was dissolved in ethanol to prepare a 100 mg / mL solution. This solution is referred to as Solution B for convenience. When the content (content rate) of Compound 1 in shellac A was measured using LC / MS-MS, it was found to be 1.74% by weight.

  99% of 4 vol% ethanol was added to the above solution B (1 mL) to prepare a 5 vol% ethanol solution in which shellac A had a concentration of 1 mg / mL. This solution is referred to as Solution C for convenience. The isolated compound 1 is added to the solution C, and the content of the compound 1 becomes 3.25% by weight (Test Example 1), the solution becomes 3.50% by weight (Test Example 2), 3.75% by weight % Solution (Test Example 3), 4.00% by weight solution (Test Example 4), 4.25% by weight solution (Test Example 5), 4.50% by weight solution (Test Example 6) )created. In addition, the content rate of the compound 1 said here is not the content rate in a solution but the content rate of the compound 1 at the time of converting into shellac single-piece | unit (shellac A + compound 1).

  0.1 mL of each prepared test solution was dropped on the evaluator's tongue, and the limit concentration at which the bitterness was felt was examined. Evaluators (examiners) were 8 women in their 20s and 9 men in their 20s and 30s. The results are shown in Table 2.

以上の結果より、セラック中の化合物１の含有率が４．０重量％以下となれば苦味が十分に低減されることが分かった。さらに、３．５重量％以下であれば苦味の低減がより顕著となる。なお、溶液Ｃ（セラック単体中の化合物１の含有率１．７４重量％）、および溶液Ｃに単離した化合物１を添加し、化合物１の含有率を２．０重量％とした溶液についても、苦味を感じることはできなかった。

From the above results, it was found that the bitterness was sufficiently reduced when the content of Compound 1 in shellac was 4.0% by weight or less. Furthermore, if it is 3.5 weight% or less, the reduction of bitterness will become more remarkable. In addition, the solution C (content ratio of compound 1 in shellac simple substance 1.74% by weight) and the solution in which the isolated compound 1 was added to solution C and the content ratio of compound 1 was 2.0% by weight were also applied. I couldn't feel any bitterness.

6). Manufacture of foods and beverages and pharmaceuticals using shellac with reduced bitterness components Various foods and beverages and pharmaceuticals can be manufactured using shellac with reduced bitterness components of the present invention.

  For example, the taste improving agent which uses the said shellac as an active ingredient can be added to general food-drinks, and taste can be improved. In addition, when adding to food-drinks, it is good to use shellac dissolved in alcohol solvents, such as ethanol. Of course, it may be crushed and added as a solid.

  In addition, foods and pharmaceuticals can be coated with the coating composition containing shellac. Conventionally, foods and the like are coated with a composition containing shellac, but bitterness can be reduced by using the shellac of the present invention. Moreover, it is only necessary to change the shellac as a material to the shellac of the present invention, and the coating can be performed using the conventional equipment without changing.

  Although the manufacture example of food-drinks and a pharmaceutical using the shellac of this invention is shown below, this invention is not limited to this. For example, it can be used for addition of shellac to a supplement, surface coating, and the like.

Shellac A prepared in Example 1 was dissolved in 99 vol% ethanol to produce a 100 mg / mL taste improver (α solution).
This α liquid was added to whiskey to produce whiskey with improved taste.

  The shellac A with reduced bitterness component prepared in Example 1 was dissolved in ethanol, coated with ball-shaped chocolate and dried to produce chocolate coated with shellac with reduced bitterness component. In addition, as a comparative example, purified shellac GSN was dissolved in ethanol, coated with ball-shaped chocolate, and then dried to produce chocolate coated with purified shellac GSN.

  I ate one of these chocolates and evaluated which one was delicious. The evaluators (examiners) were 6 women in their 20s and 6 men in their 20s and 30s. The results are shown in Table 3.

男女とも精製セラックＧＳＮをコーティングしたチョコレートの方がおいしいと感じた評価者はおらず、違いが分からない、もしくは、セラックＡをコーティングしたチョコレートの方がおいしく感じたと答えた。以上のことから、苦味成分を低減していないセラックをコーティングしたチョコレートに比べ、苦味成分を低減したセラックをコーティングしたチョコレートは呈味が良好であった。

There were no evaluators who felt that chocolate coated with refined shellac GSN was more delicious for both men and women, and the difference was not understood, or that chocolate coated with shellac A felt more delicious. From the above, the chocolate coated with shellac with reduced bitterness component had better taste than the chocolate coated with shellac without reduced bitterness component.

  The shellac A prepared in Example 1 was dissolved in ethanol, and the sugar-coated chocolate was coated with the solution and then dried to produce a sugar-coated chocolate coated with shellac.

  Shellac A prepared in Example 1 was dissolved in ethanol, and a plate-like chocolate was coated with the solution and then dried to produce chocolate coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, and the chocolate-coated biscuits were coated with the solution and then dried to produce chocolate-coated biscuits coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, and the chocolate-coated corn flakes were coated with the solution and then dried to produce chocolate corn flakes coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, and the chocolate-coated dry strawberry was coated with the solution and then dried to produce a chocolate-coated dry strawberry coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, and the sugar-coating gum was coated with the solution and then dried to produce sugar-coating gum coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, the gummi was coated with the solution, and then dried to produce a gummi coated with shellac.

  Shellac A prepared in Example 1 was dissolved in ethanol, baked laver was coated with the solution, and then dried to produce baked laver coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, the cheese was coated with the solution, and then dried to produce cheese coated with shellac.

  Shellac A prepared in Example 1 was dissolved in ethanol, and peeled chestnuts were coated with the solution and dried to produce peeled chestnuts coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, and the solution was coated with a soft jelly, followed by drying to produce a soft jelly coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, and a soft candy coated with the solution was dried and dried to produce a soft candy coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, and the chocolate-coated raisins were coated with the solution and then dried to produce chocolate-coated raisins coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, the chocolate-coated cookie was coated with the solution, and then dried to produce a chocolate-coated cookie coated with shellac.

  The shellac A prepared in Example 1 was dissolved in ethanol, and a solid preparation for oral administration was coated with the solution, followed by drying to produce a solid preparation coated with shellac.

7). Verification of the effect of improving flavor in alcoholic beverages of shellac with reduced bitterness components The flavor of the whiskey produced in Example 2 was evaluated. 0.1 mL of the shellac solution (α solution) produced in Example 2 was added to 10 mL of whiskey, and 0.1 mL of this whiskey was dropped on the tongue, and the flavor was evaluated.

  As a comparative example, decolorized shellac PEARL-N5 (trade name, manufactured by Gifu Serask Manufacturing Co., Ltd.) in 99 vol% ethanol was dissolved in 100 mg / mL shellac solution (β liquid) and 99 vol% ethanol (blank liquid). ) And prepared. The β solution and 0.1 mL of the blank solution were added to 10 mL of whiskey, and 0.1 mL of this whiskey was dropped on the tongue to evaluate the flavor. The results are shown in Table 4.

表４から分かるように、α液を添加したウイスキーはまろやかさ、甘みが増すのに対して、β液を添加したウイスキーは苦味が増した。ブランク液ではウイスキーの味が変化せず、α液を添加したウイスキーよりは強く、β液を添加したウイスキーよりは弱い苦味を有していた。

As can be seen from Table 4, whiskey to which the α solution was added increased in mellowness and sweetness, whereas the whiskey to which the β solution was added had increased bitterness. The taste of whiskey did not change in the blank solution, and it had a bitter taste stronger than the whiskey to which the α solution was added and weaker than the whiskey to which the β solution was added.

Thus, in shellac with reduced bitterness components, the taste could be improved so that the bitterness of whiskey was reduced and the mellowness and sweetness increased.
8). Manufacture of the foodstuff which uses the bitterness component of shellac Various food-drinks can be manufactured using the bitterness component (compound 1) removed from shellac.

  For example, the taste improving agent which uses the said compound 1 as an active ingredient can be added to general food-drinks, and taste can be improved. Although the manufacture example of the food / beverage products using the compound 1 is shown below, this invention is not limited to this.

Compound 1 was dissolved in 99 vol% ethanol to prepare a 100 mg / mL solution (γ solution). This γ liquid was added to whiskey to produce whiskey with improved taste.
9. Verification of Alcohol Stimulation Reduction Effect of Bitter Taste The flavor of the whiskey produced in Example 18 was evaluated. 0.1 mL of the solution (γ liquid) produced in Example 18 was added to 10 mL of whiskey, and 0.1 mL of this whiskey was dropped on the tongue, and the alcohol stimulation felt was evaluated.

  In addition, as a comparative example, 0.1 mL of 99 vol% ethanol (blank solution) was added to 10 mL of whiskey instead of γ solution, and 0.1 mL of this whiskey was dropped on the tongue, and the alcohol stimulation felt was compared. The results are shown in Table 5.

表５から分かるように、γ液を添加したウイスキーはアルコールの刺激を低減して、ウイスキーの風味を強く感じることができるように呈味を改善することができた。
［発明の効果］
実施例１のようにセラックを処理することで、苦味を大きく低減したセラックを製造することができた。また、苦味成分を大きく低減したセラックをアルコール飲料に添加することにより、アルコール飲料の呈味を改善することができた。

As can be seen from Table 5, whiskey to which the γ solution was added was able to reduce the alcohol stimulation and improve the taste so that the whiskey flavor could be felt strongly.
[Effect of the invention]
By treating shellac as in Example 1, shellac with greatly reduced bitterness could be produced. Moreover, the taste of alcoholic beverages could be improved by adding shellac with greatly reduced bitterness components to alcoholic beverages.

  Moreover, the alcohol irritation | stimulation of alcoholic beverages was able to be reduced by adding the compound 1 (ester which consists of Jalaric acid and Aleuritic acid) extracted as a bitterness component of shellac to alcoholic beverages.

Claims (9)

A shellac characterized in that the content of the ester compound of jaralic acid and alleuritic acid is 4.0% by weight or less. The shellac according to claim 1, wherein a content of the ester compound is 3.5% by weight or less.   The taste improving agent which uses the shellac of Claim 1 or Claim 2 as an active ingredient.   A food or drink comprising the shellac according to claim 1 or 2 added thereto.   The food / beverage product according to claim 4, wherein the food / beverage product is an alcoholic beverage. The coating composition used for at least any one of the foodstuffs and pharmaceuticals characterized by including the shellac of Claim 1 or Claim 2.   A taste improver comprising, as an active ingredient, an ester compound of jaralic acid and alleuritic acid.   A food or drink comprising an ester compound of jaralic acid and alleuritic acid.   The food / beverage product according to claim 8, wherein the food / beverage product is an alcoholic beverage.

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