JP5931370B2 - Citral flavor and method for producing the same - Google Patents

Description

  The present invention relates to a citral flavoring agent and a method for producing the same.

Citral is a flavor component contained in herbs and citrus fruits and has a strong citrus flavor and is used in foods and beverages and cosmetics having a citrus flavor. However, the problem is that it is unstable to heat and light and changes to off-flavor. The off-flavor means a strange odor, a variant odor, a bad odor, etc., which are secondarily produced due to a deterioration in quality due to a chemical change of the component itself contained in the flavoring agent or an external environment. Among these, p-methylacetophenone, which is the final product, emits a strong odor even in a small amount, and is therefore an off-flavor that has been regarded as the most problematic, and it has been a challenge to suppress its occurrence.
The off-flavor generation mechanism from citral is shown below.

  As a method for solving the above problems, development of a stabilizer is being promoted mainly. For example, a method of stabilizing citrus flavor using a caffeic acid derivative as a stabilizer (Patent Document 1) has been proposed.

JP-A-2-203750

  Due to the recent increase in natural orientation, there is a need for natural flavoring agents that do not contain additives such as stabilizers and that are highly safe for consumers, especially for food applications.

  An object of the present invention is to obtain a naturally occurring flavoring agent that does not require a stabilizer, can suppress the occurrence of off-flavor for a long period of time, and contains citral as a main component.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that naturally occurring flavoring agents containing citral as a main component can suppress the occurrence of off-flavor without using a stabilizer. Has been found, and the present invention has been completed.

That is, in the first invention of the present application, the proportion of p-methylacetophenone generated after storage at 55 ° C. for 2 weeks under light shielding is 5.0 % of the citral before storage (area area ratio in GC-MS evaluation). ) A citral flavoring agent consisting of a substance derived from lemon myrtle extraction.
The second invention of this application, and lemon myrtle, solubility parameter 9.0 or more solvents are mixed and gauge pressure 0.01MPa or 50MPa or less under pressure, 0 ° C. or higher, and including over there the step of extracting at 100 ° C. or less The ratio of p-methylacetophenone generated after storage at 55 ° C. for 2 weeks under light shielding is 5.0% (area area ratio in GC-MS evaluation) or less with respect to citral before storage. The present invention relates to a method for producing a flavoring agent.

  According to the flavoring agent according to the present invention, it is possible to impart a citrus-like flavor having high stability to heat, light, etc. to a beverage or the like. Further, since the flavoring agent according to the present invention can be used in a dry state as a raw material, it can be stably supplied and can be used as a substitute for a citrus flavoring agent that is easily affected by the weather. . Furthermore, the flavoring agent according to the present invention can be used as a safe and safe naturally derived flavoring agent that does not contain additives. In addition, according to the method of the present invention, since a flavoring agent that can suppress the occurrence of off-flavor for a long period of time without adding a stabilizer, it is excellent in economic efficiency.

It is the analysis result by HPLC of the lemon myrtle flavoring agent A of Example 1. It is the analysis result by HPLC of the lemon myrtle flavoring agent B of Example 2.

  In the present application, flavor means fragrance (fragrance) and / or taste, and the fragrance includes fragrance (balance of fragrance). The flavor component means a component having a flavor.

In the flavoring agent of the present invention, the proportion of p-methylacetophenone generated after storage at 55 ° C. for 2 weeks under light shielding is 5.0 % or less (area area ratio in GC-MS evaluation) with respect to citral before storage, Preferably, it is a citral flavoring agent composed of a substance derived from lemon myrtle extraction which is 3.0 % (area area ratio in GC-MS evaluation) or less. Here, in this application, a citral flavoring agent means the flavoring agent which contains citral as a main component.

This flavoring agent contains a hydrophilic component simultaneously. This hydrophilic component is, for example, a component that is detected within 10 minutes under the following HPLC analysis conditions.
Column WATERS 5C18-PAQ 4.6 ID x 250 mm
Column temperature 40 ° C
Mobile phase Acetonitrile: 10 mM phosphoric acid = 30: 70
Flow rate 0.7 ml / min
Detection: UV280nm, 0.1AUF
The flavoring agent of the present invention has an advantage that it does not interfere with the flavor because it produces less off-flavor despite having citral as the main component.

Such a flavoring agent is obtained, for example, by the following method.
Examples of the raw material containing a large amount of citral as a flavor component used in the present invention can include plants of the family Myrtaceae, Gramineae, Lamiaceae, Anemoneaceae, Camphoraceae, and these plants are one or two kinds. The above can be used in combination. These related varieties and improved varieties can also be used.

  For example, Astrophyceae plants, for example, Bachousia, Leptospermum, Melaleuca, Eucalyptus, As for gramineous plants, for example, Ogarukaya, As for Lamiaceae, for example, Aspergillus genus Examples of the plant belonging to the family Oleaceae include, for example, the genus Iwadaresou, and examples of the plant belonging to the family camphoraceae include the genus Hamabiwa.

  As plants of the genus Bachousia, for example, Lemon Myrtle, as for the Leptospermum genus, for example, Lemon Tea Tree (Lemon St Tea Tree, Lemon Scented Tea Tree), as the Melaleuca genus, for example, Honey Myrtle, Eucalyptus genus Examples thereof include eucalyptus stigliana (honey lemon eucalyptus). Examples of plants belonging to the genus Ogarkaya include lemongrass, Ceylon citronella, Java citronella, and palmarosa. An example of a plant belonging to the genus Cousi mint is lemon balm (Melissa). An example of the plant belonging to the genus Hydrangea is lemon verbena. As a plant of the genus Hamabiwa, for example, Rize Akebuba (Kubeba, Lithosikbeb, Maychan, Lithsea) can be mentioned. Among these, lemon myrtle, lemon tea tree, honey myrtle, lemongrass, and lychee aqaba are more preferable, lemon myrtle, lemon tea tree, and lychee aqaba are more preferable, and lemon myrtle is the most preferable because of high citral content and rich food experience.

  The raw material used in the present invention is preferably a leaf part from the viewpoint of the balance between flavor intensity and stability, but, for example, a state where a part other than a leaf such as a branch, a trunk (stem), or a root is attached. May be used. In addition, for example, it can be used regardless of the state of the raw material, such as a raw state before drying, a dried state, and a frozen state. From the viewpoint of economical efficiency and storage stability, the dried product is preferred. The drying method is not particularly limited, and examples thereof include known methods such as natural drying, hot air drying, vacuum drying, and freeze drying. Moreover, the storage temperature of the raw material is not particularly limited, and may be appropriately adjusted according to the state of the raw material. For example, 50 ° C. or lower is preferable for the dried state, and 20 ° C. or lower is preferable for the raw state. In the frozen state, −5 ° C. or lower is preferable.

  The raw material can be used as it is or in any state of being chopped, pulverized, or pasted, but in terms of ease of handling, it is roughly chopped to a size of about 0.5 to 50 mm. It is preferable that the powder is pulverized to about 0.5 mm or less. There are no particular limitations on the method of shredding, powdering, and pasting at this time, and known methods such as a food processor, cutter mixer, pulverizer, attritor, and homogenizer can be used.

  In order to efficiently recover the flavor components of the raw material, it is more preferable to perform shredding in a sealed state.

  The said raw material is mixed with a solvent and a flavor component is extracted. From the viewpoint of efficiently recovering the flavor component, it is preferable to further chop the raw material in a solvent. At that time, the raw material may be used as it is, or a raw material preliminarily shredded may be used.

The solvent used for extraction is preferably a solvent having a solubility parameter (hereinafter referred to as “SP value”) of 9.0 or more from the viewpoint of a balance between flavor intensity and stability. The SP value is also called a solubility parameter, a solubility parameter, a Hildebrand parameter, etc., and is an important value for evaluating the solubility of a substance in a solvent. In general, the difference in SP value between a solute and a solvent is The smaller the value, the better the extraction efficiency. The SP value can be calculated from the square root (cal / cm ³ ) ^{1/2 of the} heat of vaporization required to evaporate a 1 molar volume of liquid.

  Specific examples of the solvent include water (SP value: 23.4), glycerin (16.5), propylene glycol (14.8), methanol (14.5-14.8), ethanol (12.7). ), 1-propanol (12.1), 2-propanol (11.2), acetone (10.0), triacetin (9.0), ethyl acetate (9.0) and the like. In addition, a solvent may be used individually by 1 type and may be used in combination of 2 or more type. The SP value is preferably 9.0 to 23.4, more preferably 12.0 to 23.4, and particularly preferably 15.0 to 20.0.

  Among these solvents, water, propylene glycol, ethanol, triacetin or a mixture thereof is preferably used from the viewpoint of safety. It is more preferable to use water, ethanol or a mixture thereof from the viewpoint of the balance between flavor strength and stability. More preferably, a mixed solvent of water and ethanol is used.

The ratio of ethanol in the mixed solvent of water and ethanol is not particularly limited, but the lower limit is preferably 10 w / w% or more, more preferably 20 w / w% or more, and further preferably 40 w / w% or more. The upper limit is preferably 100 w / w% or less, more preferably 90 w / w% or less, still more preferably 80 w / w% or less, and particularly preferably 60 w / w% or less.
The amount of the solvent used is not particularly limited and may be appropriately adjusted. For example, it is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and most preferably 2 parts by mass or more, based on the raw material dry mass. It is preferably no greater than 200 parts by mass, more preferably no greater than 200 parts by mass, and most preferably no greater than 20 parts by mass.

  In the extraction, the temperature is not particularly limited, but it is preferably performed at a relatively low temperature. Specifically, it is preferably set to −20 ° C. or higher and 150 ° C. or lower. If it is -20 degreeC or more and 150 degrees C or less, the generation | occurrence | production of off-flavor can suppress the citral flavoring agent. More preferably, it is 100 degrees C or less, More preferably, it is 90 degrees C or less, Most preferably, it is 80 degrees C or less. If it is 100 degrees C or less, the production | generation and extraction of unfavorable flavors, such as a burnt flavor and unpleasant flavor, can be suppressed more reliably. As a minimum of extraction temperature, 0 degree or more is more preferred, 20 ° C or more is still more preferred, and 30 ° C or more is especially preferred. If it is 0 degreeC or more, extraction efficiency can be maintained and temperature can be maintained uniformly comparatively easily.

  When heating at the time of extraction, the heating method is not particularly limited, and for example, a known heating method such as heating by steam or heating by electricity can be used.

  The extraction is preferably performed under pressure. Preferably, extraction is performed at a gauge pressure of 0.01 MPa or more and 50 MPa or less. If the said pressure is 0.01 Mpa or more, it will become possible to extract a flavor component more reliably and efficiently, maintaining stability. On the other hand, if the pressure exceeds 50 MPa, the extraction efficiency tends to reach a peak and is not economically preferable. The pressure is more preferably 0.03 MPa or more, further preferably 0.05 MPa or more, more preferably 10 MPa or less, and further preferably 5 MPa or less. The gauge pressure referred to here is a relative pressure where the atmospheric pressure is zero.

The pressurization method is not particularly limited as long as pressurization is possible. Pressurization with water, nitrogen gas, CO ₂ gas, etc. used in a high temperature and high pressure cooking sterilization apparatus generally used for foods It can be carried out by a known method such as pressurization in
Moreover, it is preferable to stir at the time of extraction from a viewpoint of extraction efficiency.

The product of the extraction time of the undesirable flavor from the viewpoint of suppressing, or the head space occurring during extraction replaced with an inert gas such as nitrogen gas or CO ₂ gas, also nitrogen gas or CO ₂ gas in the extract It is preferable to blow in. The extraction time is not particularly limited and may be appropriately adjusted. Depending on the form of the raw material, the extraction temperature, etc., the extraction time is preferably 30 seconds or more, and preferably 120 minutes or less. If it is 30 seconds or more, extraction efficiency can be ensured more reliably, and if it is 120 minutes or less, generation and extraction of unfavorable flavors such as burnt flavor and unpleasant flavor can be more reliably suppressed. The extraction time is preferably 2 minutes or more, more preferably 5 minutes or more, more preferably 60 minutes or less, and further preferably 30 minutes or less.

  After performing the extraction operation, for example, solid-liquid separation may be performed using known separation means such as centrifugation, filter press, screw press, etc., and the liquid phase part may be recovered. Thereby, a desired flavoring agent can be obtained.

In the case of performing solid-liquid separation, in order to prevent scattering of volatile flavor components, it is preferable to cool the mixture to about room temperature after extraction and then proceed to the next solid-liquid separation step. Extraction and solid-liquid separation It is more preferable to perform both steps in a continuous sealed state, and it is more preferable to perform the steps of mixing and chopping the solvent and the raw material, the extraction step, and the solid-liquid separation step in a continuous sealed state. When performing each process in a continuous sealed state, for example, using the pressure of an inert gas such as nitrogen gas or CO ₂ gas, after mixing and shredding, transferred to the extraction process, and further after extraction, It can transfer to a solid-liquid separation process and can perform solid-liquid separation. It can also be performed in a sealed state including the filling step into the container. Here, the sealed state means that it is not in direct contact with the atmosphere.
The flavoring agent of the present invention can impart a citrus-like flavor by adding and mixing to food and drink.

  The flavoring agent of the present invention is based on the liquid phase part recovered after extracting the flavor component of the raw material with a solvent and performing solid-liquid separation, but also in a solid-liquid dispersed state before performing solid-liquid separation, It is included in the flavoring agent of the present invention. Moreover, the solid content which arose from the liquid phase part after solid-liquid separation shall also be included in the flavoring agent of this invention.

As a container for the flavoring agent according to the present invention, glass, plastic, aluminum laminated container, metal container, etc. are preferable from the viewpoints of preventing scattering of flavor components, storage property, transportability, etc., but hermetically filling is possible. The material is not particularly limited as long as it is a simple container.
You may add well-known additives, such as a fragrance | flavor, a sweetener, a coloring agent, a thickener, and an emulsifier, to the flavoring agent of this invention as needed.

  The flavoring agent of the present invention is preferably used for foods and drinks, but can also be used in various other fields such as cosmetics, pharmaceuticals, and quasi drugs. Although it does not specifically limit as food / beverage products, For example, it can utilize for fruit drinks, soft drinks, alcoholic drinks, ice cream, yogurt, etc., and can also add just before eating at the time of manufacture. Cosmetics is a generic term for scented products other than food and drink, such as fragrance products and cosmetics, and is not particularly limited, but includes, for example, beauty liquids, creams, hair conditioners, perfumes, fragrances, shampoos, rinses, Examples include soaps, toothpastes, and bath additives. Drugs and quasi-drugs are defined by the Pharmaceutical Affairs Law and are not particularly limited. Examples of forms include beverages, capsules, tablets, transdermal absorbents, and sprays. it can.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

  In the present application, gas chromatography mass spectrometry (GC-MS) was performed as follows.

(Measurement sample preparation)
10 g of sample was put into a pear type two-necked flask (50 ml volume, TOP), nitrogen was blown at a rate of 100 ml / min, and a bubbling was carried out at 40 ° C. for 15 minutes (TENAX-TA, Gester) The flavor component was adsorbed on the surface. After adsorption, the collection tube was set again in an empty pear-type two-necked flask (50 ml, TOP), and nitrogen was blown in at a rate of 100 ml / min for 5 minutes to remove moisture.

(Heat desorption of flavor components)
The obtained collection tube is set in a heat desorption apparatus (TDSA, Gester), and the flavor components are heat desorbed (initial temperature: 20 ° C., initial temperature holding time: 1 minute, temperature rising speed: 60 per minute) ℃, final temperature 240 ℃, final temperature holding time: 5 minutes, and flavor components were collected with a cold trap (silica capillary) (initial temperature: -100 ° C, initial temperature holding time: 0.2 minutes, temperature rising speed) : 12 ° C per second, final temperature 240 ° C, final temperature holding time: 10 minutes).

(GC-MS analysis)
Then, it applied to the gas chromatograph apparatus (6890N, Agilent Technologies), and analyzed the flavor component of the sample. The analysis conditions are as follows.
Column: HP-INNOWAX 60m x 0.25mmI. D.
Initial temperature: 40 ° C
Initial temperature holding time: 2 minutes Temperature rising speed: 3 ° C per minute up to 100 ° C, then 5 ° C per minute up to 240 ° C
Final temperature: 240 ° C
Final temperature holding time: 30 minutes Carrier gas: helium 206 kPa
Carrier gas flow rate: 2.1ml / min
MS detector conditions: MS ion source temperature 230 ° C, MS quadrupole temperature 150 ° C

  In the present invention, high performance liquid chromatograph (HPLC) was performed as follows.

(Measurement sample preparation)
To 100 μl of sample, 900 μl of ethanol (99% (w / w)) was added and mixed well. After centrifugation at 10,000 rpm for 2 minutes, the supernatant was used as an HPLC sample.

(HPLC analysis)
The obtained sample was subjected to HPLC. The HPLC analysis conditions are as follows.
Column: WATERS 5C18-PAQ 4.6I. D. × 250mm
Column temperature: 40 ° C
Mobile phase: (acetonitrile: 10 mM phosphoric acid) = 30: 70
Flow rate: 0.7 ml / min
Detection: UV280nm, 0.1AUF

Example 1
Lemon Myrtle 30 g and 60% (w / w) ethanol aqueous solution 300 g were added to Oster Blender (Osterlizer Inc .; Junk pulse magic 10_wh), and the mixture was shredded for 30 seconds and mixed at the same time. The obtained shredded mixture was transferred to a portable reactor (manufactured by Pressure Glass Industrial Co., Ltd .; TEM-U1000N). Extraction was performed with stirring at 40 ° C. for 30 minutes under a gauge pressure of 0.2 MPa. After extraction, the solid content was removed by filtration through a filter paper (ADVANTEC; No1 filter paper) to obtain Lemon Myrtle flavoring agent A (250 g).

(Example 2)
Lemon myrtle flavoring agent B (267 g) was obtained in the same manner as in Example 1 except that 95% (w / w) ethanol was used as the extraction solvent.

(Comparative Example 1)
A citral preparation (Sigma, E-form / Z-form mixture) was diluted 200 times with a 60% aqueous ethanol solution to prepare a citral flavoring agent.

(Comparative Example 2)
Lemon Myrtle Essential Oil (Lemon Myrtle Farms) was diluted 200 times with 60% ethanol aqueous solution to prepare Lemon Myrtle Essential Oil Flavoring Agent.

(Test Example 1) Sensory evaluation 7 kg of granulated sugar, 2 g of citric acid and 0.4 g of citric acid 3Na were dissolved per 1 kg to prepare 2 kg of a beverage for evaluation of flavoring agents. 100 g of the beverage was filled into a retort bag and subjected to a retort sterilization treatment at 121 ° C. for 10 minutes. The obtained sterilized beverage for evaluation was poured into a 120 ml aluminum bottle capable of shading in a hot state, and 0.15 g (0.15 mass) of each flavoring agent in Examples 1 and 2 and Comparative Examples 1 and 2 above. %) Was aseptically added and then stored at 55 ° C. for 2 weeks in the dark. After storage, the aroma and taste were sensorially evaluated by 10 panelists according to the following criteria.

Aroma and taste 1-Aroma and taste with a degree of change smaller than that of Comparative Example 1-Aroma and taste with a degree of change slightly smaller than that of Comparative Example 1-10 people with the same degree of change as Comparative Example 1 It shows in Table 1 as an average value of evaluation by.

From Table 1, Lemon Myrtle flavoring agent A of Example 1 evaluated that all 10 panel members had a smaller degree of change than Comparative Example 1. It is clear that the occurrence of off-flavor is suppressed. Moreover, also in the lemon myrtle flavoring agent B of Example 2, all evaluated that the degree of change was smaller or slightly smaller than that of Comparative Example 1. The effect of extraction with a hydrophilic solvent is obvious. On the other hand, in the lemon myrtle essential oil of Comparative Example 2, the degree of change was large.
Moreover, also in the comparison before a preservation | save, Example 1, 2 had little bitterness and astringency with respect to the comparative example 2, and was excellent in sensuality.

(Test Example 2) GC-MS Evaluation Each flavorant-added beverage obtained in Test Example 1 was evaluated by GC-MS.
The evaluation of the ratio of citral in the flavor component was made by taking the area area of the flavor component total area area before storage excluding the area area of ethanol as a solvent as 100, and the area area of citral (area area of E body and Z body) The sum was calculated by calculating the ratio (Table 2).
Evaluation of the off-flavor generation rate is p-methylacetophenone generated after storage at 55 ° C. for 2 weeks in the dark, with the area area of citral before storage (the sum of the area areas of E and Z bodies) being 100. This was done by calculating the area area ratio (Table 3).

  As can be seen from Table 2, it was confirmed that the lemon myrtle flavoring agent A of Example 1 contained citral at a high ratio.

  From Table 3, compared with the citral flavoring agent of Comparative Example 1, the lemon myrtle flavoring agent A of Example 1 had a lower proportion of p-methylacetophenone, which is the final product of citral oxidation. From this, it is clear that in the lemon myrtle flavoring agent A of Example 1, the production of p-methylacetophenone is inhibited. It is also clear from Test Example 1 that the occurrence of p-methylacetophenone, which has a low threshold and a completely different flavor from citrus fruits, appears as a sensory difference.

(Test Example 3) HPLC Evaluation Lemon Myrtle flavoring agents A and B of Examples 1 and 2 were evaluated by HPLC.
As can be seen from FIGS. 1 and 2, the flavors obtained in Examples 1 and 2 have a peak before the retention time of 10 minutes, and both Lemon Myrtle flavors A and B of Examples 1 and 2 are hydrophilic. It was confirmed that a high component was obtained. In the flavoring agents obtained in Comparative Example 1 and Comparative Example 2, since almost the same components were not confirmed, the hydrophilic component derived from the raw material may be involved in the stability of citral in some form. Inferred.

(Test Example 4)
300 g of yogurt (plain), 200 g of milk and 50 g of granulated sugar were mixed together, 0.5 g of the lemon myrtle flavoring agent A prepared in Example 1 was added, and further mixed little by little. It put into the -20 degreeC freezer and cooled for 3 hours, and produced the yogurt sherbet. The obtained sherbet had a citrus flavor, and a sorbet having a citrus flavor could be easily obtained without using citrus fruits.

Claims (6)

  From a lemon myrtle extract-derived product in which the ratio of p-methylacetophenone generated after storage at 55 ° C. for 2 weeks under light shielding is 5.0% (area area ratio in GC-MS evaluation) or less with respect to citral before storage. Citral flavoring.   The flavoring agent according to claim 1, comprising a hydrophilic component derived from a raw material.   Including a step of mixing lemon myrtle and a solvent having a solubility parameter of 9.0 or more and extracting the mixture at 0 to 100 ° C. under pressure of 0.01 to 50 MPa. The manufacturing method of the citral flavoring agent whose ratio of p-methylacetophenone which generate | occur | produces after 2 degreeC preservation | save for 2 degreeC is 5.0% (area area ratio in GC-MS evaluation) or less with respect to the citral before storage.   The method for producing a flavoring agent according to claim 3, wherein the extraction solvent is a solvent having a solubility parameter of 12.0 to 23.4.   The method for producing a flavoring agent according to claim 4, wherein the extraction solvent comprises water, ethanol, propylene glycol, triacetin, or a mixture thereof.   The method for producing a flavoring agent according to claim 5, wherein the extraction solvent comprises water, ethanol, or a mixture thereof.

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