JP3039706B2 - How to prevent deterioration of natural fragrances - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing the deterioration of natural fragrances, and more particularly, to the change of fragrance and flavor of natural fragrances and the generation of off-flavors by adding chlorogenic acid to fragrance components derived from natural products. The present invention relates to a method for effectively suppressing the undesirable flavor deterioration.

[0002]

2. Description of the Related Art Natural fragrances such as natural essential oils, oleoresin, and fragrances recovered from natural products and essences obtained by processing them into water-soluble (hereinafter, these are collectively referred to simply as natural fragrances) are relatively unstable. For example, the fragrance is easily changed by light, oxygen, heat, and the like, and deterioration accompanied by coloring, fading, or an increase in viscosity is observed.

[0003] The prevention of deterioration of perfume has been studied for a long time. For example, perfume is prepared by adding phenols such as ionol, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA) and diisoeugenol to citric acid. There has been proposed a method for preventing the deterioration by adding them (Soviet Patent 2
24741, 1968). Conventionally, as antioxidants such as natural essential oils, for example, BHA, BHT, propyl gallate, dl-α-tocopherol and the like have been generally used. However, in recent years, synthetic antioxidants have been said to be unfavorable for human health, and natural antioxidants have been required to replace these chemically synthesized products.

On the other hand, several proposals have been made for prevention of discoloration such as fading or browning of foods and drinks. For example, an anti-fading agent for anthocyanin dyes utilizing antioxidant properties such as chlorogenic acid and caffeic acid ( Japanese Patent Publication No. 1-22872), foods and drinks containing anthocyanin-based dyes
No. 32344) and a method for preventing fading of paprika dyes (Japanese Patent Publication No. 59-50265). Also, a method for preventing browning of saccharides with caffeic acid, ferulic acid, chlorogenic acid and the like (Japanese Patent Application Laid-Open No. 57-115147), a method for producing candy without browning utilizing the browning prevention effect of saccharides (Japanese Patent Publication No. 58-28555). Gazette) has also been proposed. In addition, it is known that substances exhibiting antioxidant properties such as chlorogenic acid, caffeic acid and ferulic acid are contained in coffee beans and the like, and there are some proposals regarding methods for extracting these antioxidant substances. (JP-A-58-138347 and JP-A-62-111)
No. 671).

[0005]

Natural fragrances are generally composed of a collection of extremely unstable compounds, and are susceptible to the effects of heat, light, air, enzymes and the like during storage, and are thereby degraded, It is well known that quality is reduced. Many reactions such as oxidation, reduction, dehydrogenation, hydrolysis, polymerization, ring closure, ring opening, esterification, decarboxylation, and transfer of double bonds are involved in the reaction that causes the deterioration of the natural fragrance. Therefore,
Not all conventionally known antioxidants are necessarily effective in preventing the deterioration of natural fragrances.

[0006] Further, since antioxidant components obtained from conventionally known natural products are usually accompanied by a peculiar aroma and flavor derived from each natural product raw material, a complex composition of fats or oils or general fats and oils-containing foods and drinks is required. Even if it is possible to mix the antioxidant component with a flavor composition or natural flavor for the purpose of flavor or flavor, even if it has antioxidant effect, However, there is a serious problem in that the quality of flavors and natural fragrances to which it is added is deteriorated. The present inventors have found that when blended in a natural flavor, the natural extract does not adversely affect the flavor and flavor of the natural flavor itself and has a sufficient anti-deterioration effect. The method of preventing deterioration was studied diligently.

[0007]

The present applicant has previously described "Method for preventing flavor deterioration of food and drink" (Japanese Patent Application No. Hei 2-131413).
No.). In the proposal, the food or beverage is made to contain at least one selected from the group consisting of chlorogenic acid, caffeic acid and ferulic acid and at least one selected from the group consisting of vitamin C, rutin and quercetin. It has been clarified that undesirable flavor deterioration such as reduction or change of aroma and flavor and generation of off-flavor during the processing or storage of the can be effectively suppressed. The present inventors have added chlorogenic acid to the natural fragrance itself based on the above proposal, and surprisingly, the fragrance naturally retains desirable characteristics such as natural feeling, abundance and the like of natural materials for a long time. It has been found that it can be a highly safe deterioration inhibitor without affecting the aroma and flavor of natural fragrance at all.

Further, for example, a purified chlorogenic acid obtained by contacting an aqueous solvent extract of green coffee beans with a styrene / divinylbenzene-based or methacrylate-based porous polymer resin and then treating the resin with a hydrous alcohol,
Alternatively, purified chlorogenic acid derived from natural products such as purified chlorogenic acid obtained by contacting an aqueous solvent extract of green coffee beans with a strongly acidic cation exchange resin and adsorbing and removing caffeine from the resin is the synthetic chlorogen described above. It was found to have the same effect as the acid. Therefore, an object of the present invention is to add a chlorogenic acid, particularly a purified chlorogenic acid derived from natural raw materials such as coffee beans, to a fragrance composition derived from a natural product, so that the deterioration of the flavor and the total deterioration such as coloring or fading are caused.・ To provide a method for preventing deterioration.

Hereinafter, embodiments of the present invention will be described more specifically. Examples of the natural flavors targeted in the present invention include natural essential oils obtained by squeezing plant raw materials such as plant leaves, flowers, bark, roots, twigs, fruits, peels, seeds and the like, performing steam distillation, and the like; Extracts obtained by extracting a raw material with an organic solvent; oleoresins and resinoids obtained by further removing the solvent from the extract;
Concentrate fruit juices and other juices, fermented milk products, other fermented foods and beverages, and recover fragrances obtained when performing steam distillation and the like, and include, for example, essences obtained by extracting citrus oil and the like with aqueous alcohol. Can be. In the present invention, if desired, in addition to the above natural flavors, for example, flavors derived from chemical synthesis or other natural products, such as low molecular weight alcohols, ethers, esters, aldehydes, ketones, and mercaptans And a compound having a fragrance such as a volatile organic acid and a fragrance composition obtained by appropriately mixing the fragrance compounds such as sulfides, etc., to enhance and change the fragrance characteristics of the natural fragrance. it can. If desired, other additives such as coloring agents, sour agents, sweeteners and the like can be added in addition to the flavor composition.

The chlorogenic acid (3-caffeylquinic acid) used in the present invention may be, for example, a chemically synthesized product, but preferably includes natural chlorogenic acid derived from natural products. Such a natural chlorogenic acid is contained in, for example, coffee beans in the form of potassium chlorogenate caffeine, and is distributed in trace amounts in tobacco leaves, sweet potatoes, pear leaves, apple pulp and other plants.
The chlorogenic acid used in the present invention does not necessarily need to be a pure product, but it is preferable that the chlorogenic acid be purified to such an extent that the flavor of the natural flavor to be added is not modulated.

With respect to the method for preparing purified chlorogenic acid, for example, “Method for producing purified chlorogenic acid” (Japanese Patent Application No. 2-265201) and “Method for producing purified chlorogenic acid” (Japanese Patent Application No. 2-265201) filed by the same applicant as the present invention. Hei 2-265202)
In summary, the former method, for example, discloses that the former method uses green coffee beans having a water content of about 5% by weight or more, preferably about 5 to about 90% by weight, methanol, ethanol, A hydrous water-miscible organic solvent such as propanol, acetone or methyl ethyl ketone is used in an amount of about 2 to about 50 parts by weight per 1 part by weight of ground coffee beans, and the temperature is about 20 parts by weight.
Extracted at ~ 80 ° C, the resulting extract is extracted as it is in the case of water extraction, and in the case of an extract containing a water-miscible organic solvent,
The content of the organic solvent is reduced to, for example, about 5% by weight or less by means of distillation or the like, followed by contact treatment with, for example, a styrene / divinylbenzene-based porous polymer resin or a methacrylic acid-based synthetic adsorbent to extract green coffee beans. Chlorogenic acid and its homologues are adsorbed to the adsorbent with chlorogenic acid and its homologues, caffeine and trigonelline in the liquid, and then the synthetic resin adsorbent is desorbed with a dilute alkaline aqueous solution to convert chlorogenic acid and its homologues. It is possible to obtain chlorogenic acid having high purity by selectively eluting and eliminating unnecessary components such as caffeine.

According to the latter method, caffeine in the green coffee bean extract is almost completely removed by subjecting the green coffee bean extract obtained in the same manner as described above to a contact treatment with a cation exchange resin. An extract containing high-purity chlorogenic acid that is adsorbed and removed by the resin can be obtained.

In the present invention, the amount of chlorogenic acid added is
It can be appropriately selected depending on the content or concentration of the fragrance component in the natural fragrance, the content of the solvent, and the like. Generally, the range of about 0.001 to 10% by weight based on the natural fragrance is often adopted. You. If desired, in addition to chlorogenic acid, a conventionally known deterioration inhibitor, synergist or reducing agent, for example, caffeic acid, ferulic acid, L-ascorbic acid, rutin, quercetin and the like can be added. Are similar to the above in total. Hereinafter, the method for preventing the deterioration of the flavor of the natural fragrance of the present invention will be described in more detail with reference to Reference Examples and Examples.

[0014]

REFERENCE EXAMPLE 1 2400 g of 70% methanol was added to 600 g of ground coffee beans and extracted with stirring at 65 ° C. for 3 hours. After cooling, solid-liquid separation was performed, and the extract was concentrated under reduced pressure to remove methanol. 100 g of common salt and water were added to the obtained concentrate to adjust the total amount to 1000 g. This solution is
The extract was adsorbed on a column packed with 400 ml of the synthetic adsorbent (SP-207) at SV = 1.0. Subsequently, water was passed through the column for washing, and 800 g of a 60% aqueous ethanol solution was passed at SV = 1.0 to elute chlorogenic acids. The obtained eluate was dried under reduced pressure to obtain 33 g of purified chlorogenic acid.

[0015]

Reference Example 2 1000 g of 70% ethanol was added to 200 g of green coffee beans, and the mixture was extracted with stirring at 75 ° C. for 3 hours. After cooling, solid-liquid separation was performed, and the separated extract was applied to a column packed with 250 ml of cation exchange resin (SK-1B) by SV.
= 1.0, and caffeine was adsorbed and removed. The eluate was dried under reduced pressure to obtain 28 g of the purified chlorogenic acid of the present invention.

[0016]

[Comparative Example 1] 500 g of 65% (v / v) ethanol was added to 50 g of lemon oil, stirred at room temperature for 10 minutes and allowed to stand, the upper terpene layer was removed, and the lower ethanol layer was filtered with filter paper. 495 g of lemon flavor was obtained (Comparative product 1).

[0017]

Example 1 The purified flavor of chlorogenic acid obtained in Reference Example 1 was added to lemon flavor obtained under the same conditions as in Comparative Example.
The lemon flavor of the present invention was prepared by adding and dissolving 05% by weight (Product 1 of the present invention).

[0018]

Comparative Example 2 Vanilla beans from Madagascar 100g
Was charged into a steam distillation still and steam distilled under normal pressure, and 200 g of condensate (recovered scent) was collected as a vanilla flavor (comparative product 2).

[0019]

Example 2 The purified chlorogenic acid obtained in Reference Example 2 was added to vanilla flavor obtained under the same conditions as in Comparative Example 2 in an amount of 0.
04 wt% was added and dissolved to prepare a vanilla flavor of the present invention (Product 2 of the present invention).

[0020]

Comparative Example 3 Roasted and ground coffee beans (Santos NO.2,
100 g of L value 20) was charged into a steam distillation still and steam distilled under normal pressure, and 200 g of condensate (recovered scent) was collected to obtain a coffee flavor (Comparative product 3).

[0021]

Example 3 The coffee flavor of the present invention was prepared by adding and dissolving 2% by weight of the purified chlorogenic acid obtained in Reference Example 2 in the coffee flavor obtained under the same conditions as in Comparative Example 3 (Product 3 of the present invention). .

[0022]

Example 4 The lemon flavors obtained in Example 1 and Comparative Example 1 were stored at a temperature of 37 ° C. for 3 weeks and 2 months, and then a sample stored in a refrigerator at 4 ° C. was used as a standard to alter the flavor. The degree of deterioration was sensory evaluated by a panel of 10 well-trained persons. The results are shown in Table 1 (after 3 weeks and 2 months).

[0023]

[Table 1] (10
(Average value of panels with names) Evaluation score 5 Excellent. 4 Excellent. 3 Normal 2 Inferior. 1 Very poor.

[0024]

Example 5 The vanilla flavor and coffee flavor obtained in Examples 2-3 and Comparative Examples 2-3 were stored at a temperature of 37 ° C. for 3 weeks and 2 months in the same manner as in Example 4.
Using a sample stored in a refrigerator at a temperature of 0 ° C. as a standard, sensory evaluation was performed on the degree of deterioration and deterioration of the sample using a panel of 10 well-trained persons. Table 2 (after 3 weeks)
And Table 3 (after 2 months).

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

Example 6 A vanilla flavor excellent in storage stability was prepared according to the following compounding ratio. Vanilla extract bourbon 800 g Vanillin 15 g Vanilla oleoresin 10 g Ethanol 110 g Water 65 g 0.4 g of purified chlorogenic acid of Reference Example 1

[0028]

Example 7 A coffee flavor excellent in storage stability was prepared according to the following compounding ratio. Ethyl acetate 3 g Diacetyl 2 g Acetic acid 1 g Furfural 10 g Furfuryl mercaptan 1% 3 g Coffee extract 600 g Ethanol 231 g Water 150 g 0.4 g of purified chlorogenic acid of Reference Example 2

[0029]

According to the present invention, natural fragrances such as natural essential oils, extracts of natural products, oleoresins, resinoids, recovered fragrances and essences are mixed with purified chlorogenic acid to produce natural fragrances. Unfavorable deterioration such as reduction or change of flavor, coloration or fading, and generation of off-flavor during storage of the natural flavors can be effectively suppressed without any adverse effect on the flavor.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Osamu Inami 335 Karajuku, Hasegawa, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Inside the Kawasaki Research Laboratory, Inc. In-house (56) References JP-A-58-65761 (JP, A) JP-A-1-132344 (JP, A) JP-A-58-110535 (JP, A) JP-A-60-25914 (JP, A) JP-A-63-48209 (JP, A)

Claims (1)

(57) [Claims] 1. A method for preventing the deterioration of a natural fragrance, comprising adding chlorogenic acid to a fragrance composition derived from a natural product.