JPH0693199A - Antifading agent for gardenian yellow color - Google Patents

Abstract

PURPOSE:To provide an antifading agent for gardenian yellow color which contains polyphenols (chlorogenic acids) such as chlorogenic acid, cafeic acid and ferulic acid as the active ingredient. CONSTITUTION:A gardenian yellow color, which apts to fade due to the light and heat instability, is mixed with bout 0.5-30wt.% of a chlorogenic acid to effectively prevent the color from fading.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-fading agent for gardenia yellow pigments, and more specifically, polyphenols such as chlorogenic acid, caffeic acid, ferulic acid, isochlorogenic acid and neochlorogenic acid (hereinafter referred to as chlorogenic acids). The present invention relates to an anti-fading agent for a gardenia yellow dye, which can effectively prevent fading of a gardenia yellow dye.

[0002]

2. Description of the Related Art Conventionally, tar-based synthetic pigments have been widely used as food pigments, but since the safety of synthetic pigments became a problem, natural pigments collected from natural source materials have been used. Has been replaced by. At present, natural pigments such as gardenia yellow pigments, paprika pigments, red cabbage pigments, safflower yellow pigments, gardenia blue pigments are used in fields such as food and drink, cosmetics, health and pharmaceuticals, and especially coloring of foods and drinks. Widely used in. However, these natural pigments are generally unstable as compared with synthetic pigments, and are associated with changes in color tone and fading over time due to light, oxygen, heat, etc., resulting in a marked decrease in commercial value. I have a problem. Also,
It is also known that natural pigments such as gardenia yellow pigments become significantly unstable in an aqueous solution as the pH approaches from a low acidity side to a neutrality and fading or discoloring.

For the purpose of solving the above-mentioned troubles or instability of natural dyes, some proposals have been made to incorporate specific components effective for preventing fading of the dyes. The safflower yellow pigment is, for example, a cartamine-containing coloring agent in which sorbit, cystine or an acid salt thereof, or glycine or an acid salt thereof is mixed in an amount of about 0.01 part by weight or more with respect to cartamine. Stabilization method (Japanese Patent Publication No. 50-1329)
As for the gardenia blue dye, for example, a method for stabilizing the dye by adding cyclodextrins to a blue dye (gardena blue dye) produced by enzymatically treating a dye of iridoid glycoside (Japanese Patent Laid-Open No. HEI-1) No. 163268) has been proposed. However, a method for effectively preventing discoloration or discoloration of the gardenia yellow pigment by blending a specific component with the gardenia yellow pigment has not yet been known.

On the other hand, it is well known that chlorogenic acids have an effect of preventing fading or discoloration, and some proposals have been made for preventing discoloration such as fading or browning of foods and drinks containing the chlorogenic acids as an active ingredient. Has been done. For example, a method of preventing fading of paprika dye (Japanese Patent Publication No. 59-50265), caffeic acid, ferulic acid,
Method for preventing browning of sugars by chlorogenic acid or the like (Japanese Patent Laid-Open No. 57-57
-115147), a method for producing a candy without browning utilizing the browning-preventing effect of sugars (Japanese Patent Publication No. 58-32).
No. 855) has been proposed. The applicant of the present invention is also an anti-fading agent for anthocyanin dyes utilizing antioxidant properties such as chlorogenic acid and caffeic acid (Japanese Patent Publication No. 1-228).
No. 72), foods and drinks containing anthocyanin dye (Japanese Patent Laid-Open No. HEI-132344), and the like.

[0005]

Conventionally, in order to solve the troubles such as fading or discoloration of natural pigments, many proposals have been made as described above, and some effects are cited. However, no proposal has been made in the past to prevent fading or discoloration of gardenia yellow dye, and the dye is unstable to light, oxygen, heat, etc. in an acidic region, which causes a change in color tone and fading over time. There is a problem to be solved, and development of an anti-fading agent excellent for the dye has been strongly desired.

[0006]

Means for Solving the Problems Following the previously proposed research on anti-fading agents for anthocyanin dyes, the present inventors have been keenly interested in anti-fading agents for gardenia yellow dyes, which have been strongly desired to be developed. I have done research. As a result, it has been discovered that chlorogenic acids, which have hitherto not been known as anti-fading agents for gardenia yellow dyes, exhibit an excellent effect of preventing fading of the dyes. Furthermore, the chlorogenic acids of the present invention are useful as an anti-fading agent in a wide range of fields where dyes such as those mentioned above are used, and can be suitably used particularly in the field of food and drink containing gardenia yellow dye, which is inconvenient for food and drink. It was found that an excellent anti-fading effect can be imparted without causing the flavor modulation. Therefore, an object of the present invention is to provide an anti-fading agent for gardenia yellow pigments containing chlorogenic acids as an active ingredient.

The aspect of the present invention will be described more specifically below.

Gardenia yellow pigment is extracted from gardenia fruits, and the main component of the pigment component is crocin.
Crocin is the digentiobiose ester of crocetin, and when hydrolyzed it becomes crocetin and glucose.
The gardenia yellow dye can be obtained as a commercial product and can also be easily produced by the following procedure. For example, the gardenia yellow pigment extract can be prepared by removing the skin of dried gardenia fruit, pulverizing it, and optionally removing oils and fats with a solvent such as ethanol, and then extracting with water or warm water. Further, when the extract is filtered to obtain a transparent liquid, which is concentrated and then subjected to a sterilization step to obtain an aqueous solution, propylene glycol,
Or as gardenia yellow dye with ethanol added, or in the case of powder form, spray-drying by adding a water-soluble saccharide to a dye stock solution sterilized and concentrated as a dye carrier,
The pigment stock solution can be used in various forms such as a powdery gardenia yellow pigment in which powdered sugar is mixed with the raw powder obtained by spray drying.

Chlorogenic acids used for preventing fading or discoloration of the gardenia yellow pigment obtainable as described above include, for example, chlorogenic acid, caffeic acid, ferulic acid, isochlorogenic acid, Examples thereof include neochlorogenic acid. The chlorogenic acids to be used may be a chemically synthesized product that is easily available as a commercial product, or may be one obtained from a natural product source. Naturally occurring chlorogenic acid is contained, for example, in coffee beans in the form of potassium caffeine chloroformate, and trace amounts are widely distributed in tobacco leaves, sweet potato, pear leaves, apple pulp and other widely used plants. Caffeic acid is present in free form in needle bark, Polygonaceae, tobacco and the like, but it can be widely distributed as chlorogenic acid including coffee beans, and can also be obtained by removing the quinic acid moiety from chlorogenic acid. The chlorogenic acids used in the present invention are not necessarily required to be pure products, but those purified to at least the aroma and flavor of the dye to be added are preferred.

Regarding the method for preparing the purified chlorogenic acids,
For example, “Production method of purified chlorogenic acid” (Japanese Patent Application No. 2-265201) and “Production method of purified chlorogenic acid” (Japanese Patent Application No. 2-265202) filed by the same applicant as the present invention.
However, the former method includes, for example, the former method containing green coffee beans having a water content of about 5% by weight or more, preferably about 5 to about 90% by weight of methanol, ethanol, A water-miscible water-miscible organic solvent such as 2-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.
Extraction at a temperature of about 20 to about 80 ° C., the obtained extract as it is in the case of water extraction, or in the case of a water-containing water-miscible organic solvent extract, the content of the organic solvent is adjusted by means such as distillation. , For example, styrene
By adsorbing the extract components such as chlorogenic acid and its homologues, caffeine and trigonelline in the coffee raw bean extract by contact treatment with divinylbenzene type porous polymer resin or methacrylic acid type synthetic adsorbent. ,
Then, by desorbing the synthetic resin adsorbent with a dilute aqueous alkaline solution, chlorogenic acid and its homologues can be selectively eluted to obtain high-purity chlorogenic acid by removing unnecessary components such as caffeine. .

According to the latter method, the caffeine in the coffee green bean extract is almost completely removed by subjecting the coffee green bean extract obtained in the same manner as 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.

The anti-fading agent of the present invention may contain only the chlorogenic acids obtained as described above,
It may be in the form of a composition of chlorogenic acids and a suitable diluent or carrier. Examples of such diluents or carriers include solid diluents or carriers such as gum arabic, dextrin, glucose and sucrose, and liquid diluents or carriers such as water, ethanol, propylene glycol, glycerin and surfactants. can do. The anti-fading agent of the present invention may be used in any dosage form, and may be in the form of powder, granules, liquid, emulsion liquid, paste or any other suitable dosage form.
For example, gum arabic, dextrin, etc. may be added to use in the form of powder, granules or the like, and for example, ethanol, propylene glycol, glycerin,
Alternatively, it can be dissolved in a mixture thereof and used as a liquid dosage form. Further, in the present invention, it may be in the form of a mixture containing an anti-fading agent, a gardenia yellow pigment and other known anti-fading agents such as L-ascorbic acid, rutin and quercetin.

The anti-fading agent containing chlorogenic acids of the present invention as an active ingredient can prevent fading of the gardenia yellow dye by light, oxygen, heat or humidity by directly adding and mixing the dye. By adding and blending with a product colored with the dye, fading due to light, oxygen, heat or humidity of the product can be effectively prevented. Such products include food and drink
Examples include luxury items, feed and feeds, health / medicine products, and cosmetics. For example, beverages such as fruit juice-free beverages, beverages containing fruit juice, lactic acid bacteria beverages, powdered beverages; frozen desserts such as ice cream, sherbet, and frozen desserts; desserts such as pudding, jelly, bavarois, yogurt; other drops, candy, chocolate, Bean paste, candied chestnut,
Anti-fading agent for processed foods, yakiniku sauce, pickles, seafood pastes, Chinese noodles and other food and beverages / favourites: Health and pharmaceuticals such as tablets, liquid oral medicines, powdered oral medicines, poultices, etc. Anti-fading agents: or, for example,
It is useful as an anti-fading agent for cosmetics such as soap, detergent and shampoo.

The amount of chlorogenic acids to be added in the present invention can be appropriately selected depending on the content or concentration of the gardenia yellow dye, but generally, it is about 0.5 to about 30% by weight with respect to the gardenia yellow dye. A range of degrees is often adopted. If desired, in addition to chlorogenic acids, conventionally known anti-fading agents, synergists or reducing agents such as L-
Ascorbic acid, rutin, quercetin and the like can be added, but the total amount of addition in that case is the same as above.

Hereinafter, the anti-fading agent of the present invention will be described in more detail with reference to Reference Examples and Examples.

[0016]

Reference Example 1 Purification of Chlorogenic Acid 600 g of ground coffee beans were mixed with 240% of 70% methanol.
0 g was added and the mixture was extracted with stirring at 65 ° C. for 3 hours. Solid after cooling
Liquid separation was performed, and the extract was concentrated under reduced pressure to remove methanol. 100 g of salt and water were added to the obtained concentrate to adjust the total amount to 1000 g. This solution is used as a synthetic adsorbent (S
P-207) SV = 1.0 in a column packed with 400 ml
The solution was passed through to adsorb the extract. After washing by pouring water through the column, 800 g of 60% aqueous ethanol solution was added to SV.
= 1.0 to elute chlorogenic acids. The obtained eluate was dried under reduced pressure to obtain 33 g of purified chlorogenic acid.

[0017]

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

[0018]

Examples 1 to 6 Anti-fading effect of gardenia yellow pigment Fructose-glucose liquid sugar 160 g, citric acid 1.5 g and sodium citrate 0.17 g were dissolved in water to 1000
Prepare ml syrup solution. A gardenia yellow pigment aqueous solution was prepared by adding 1 g of gardenia yellow pigment to this syrup solution. Next, the anti-fading agent of the present invention was added to this aqueous dye solution, which was then placed in a colorless and transparent 200 ml bottle, and the change in absorbance at 440 nm due to sunlight irradiation was measured over time to determine the residual dye rate. The results are shown in Table 1. From this table, it can be seen that the anti-fading agent of the present invention has a remarkable anti-fading effect on gardenia yellow pigment.

[0019]

[Table 1] Example Type of anti-fading agent Addition amount Dye remaining rate by sunlight irradiation (%) ( Chlorocarboxylic acids) (ppm) 1 hour 2 hours 4 hours 1 Chlorocarboxylic acid 50 73 55 41 2 Chlorocarboxylic acid 100 85 69 58 3 Caffeic acid 100 87 72 61 4 Ferulic acid 100 72 53 38 5 Green coffee extract 150 72 50 35 6 Bitamin C 150 87 70 28 Control additive-free 0 46 20 9

[0018]

[Examples 7 to 9] Anti-fading effect of gardenia yellow pigment Raw material Inventive product (1) Inventive product (2) Inventive product (3) Control wheat flour (semi-strong flour) 250g 250g 250g 250g Citric acid 0.45g 0.45g 0.45g 0.45g Lactic acid 0.25g 0.25g 0.25g 0.25g Salt 1.5g 1.5g 1.5g 1.5g Gardenia yellow pigment 0.15g 0.15g 0.15g 0.15g Water 89.3g 89.3g 89.3g 89.3g Green coffee extract 0.15g Chlorogenic acid 0.15g Caffeic acid 0.15g

A Chinese noodle composition for the present invention (3 products) in which the anti-fading agent of the present invention was added to the raw materials for the Chinese noodles mixed according to the above-mentioned formulation and a Chinese noodle composition for a control product without any additive were prepared. This composition is mixed and kneaded, rolled, cut, steamed, packaged, heat-sterilized, and cooled according to a conventional method for producing Chinese noodles. Noodles were produced. The Chinese noodles thus produced were irradiated with a fluorescent lamp of 3500 lux at room temperature, and after 3 days, 6 days and 10 days, the fading of the Chinese noodles was measured using a color difference meter. The measuring method is L (lightness) of Chinese noodles after each day,
Measure a (degree of redness) and b (degree of yellowness), and
(Color difference) was calculated. The results are shown in Table 2. From this table, it can be seen that the anti-fading agent of the present invention has a remarkable anti-fading effect on gardenia yellow pigment. The color difference (△ E) is ^{△ L 2 + △ a 2 +} △ b it can be calculated by the square root of ^two, indicating that change in color tone as the number is large (fading) is large.

[0020]

[Table 2] Example Sample Fluorescent lamp 3 irradiation days Fluorescent lamp irradiation 6 days Fluorescent lamp irradiation 10 days △ E △ E △ E 7 Invention product (1) 1.8 3.5 5.6 8 Invention product (2) 1.1 2.3 4.1 9 Invention product (3) 1.2 2.1 4.0 Control product 3.2 5.1 7.4

[0021]

The present invention provides chlorogenic acid, caffeic acid,
By containing polyphenols such as ferulic acid as an active ingredient, fading of gardenia yellow pigment due to light, oxygen, heat, etc. can be effectively prevented.

Claims (1)

[Claims] 1. An anti-fading agent for gardenia yellow pigment, which comprises chlorogenic acids as an active ingredient.