JP2001279125A - Coloring material derived from hop - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a red, hop-derived coloring material utilizing as starting materials bracts of hops, cones of hops enveloping bracts of hops, and the like, and to easily apply the hop-derived coloring matter as a coloring material derived from a plant in the fields of foods, beverages, clothes and dyes. SOLUTION: The hop-derived coloring material comprises a red coloring material obtained by an acid- or alkali-treatment of cones of hops, bracts of hops or a polyphenol contained in bracts of hops. Also a manufacturing method of the same is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hop-derived pigment having a red color and obtained from hop cones or hop bracts.

[0002]

2. Description of the Related Art Hops are perennial plants of the mulberry family, and their cones (mature of unfertilized female flowers) are generally called hops. The lupulin portion of this hop (yellow granules formed at the root of the inner bract of the cone) is the main component of the bitterness and aroma of the hop, and is an important beer raw material along with yeast and malt in beer brewing. Hops are also used in folk medicine as a sedative and anti-aphrodisiac.

On the other hand, hop bracts are obtained by removing lupulin from hop cones and are not useful for beer brewing. In some cases, hop bracts are removed during beer brewing and are produced as by-products. At that time, hop bracts have not been found to be particularly effective in use other than being used as a fertilizer for soil improvement, and it has been desired to develop a use method with higher added value. It should be noted that Japanese Patent Application No.
In -173931, Japanese Patent Application No. 7-347151, Japanese Patent Application No. 8-75456, and Japanese Patent Application No. 8-195205, hops, especially polyphenols derived from hop bracts, are described.
It has been confirmed that it has an antioxidant effect, foam stabilizing effect on sparkling malt beverage, anti-cariogenic effect, and deodorant effect.

[0004] However, there is no example in which a pigment having a red color is obtained from polyphenols derived from hops, especially hop bracts, and this is utilized.

[0005]

In recent years, in the fields of foods, clothing, and the like, the sense of repellency for synthetic dyes obtained by chemical synthesis and the sense of expectation for dyes of natural origin have been increasing. However, at present, there are almost no high-quality red pigments that add value such as luxury and appetite to the quality, or they are expensive and difficult to use.

[0006]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have found a method for easily and inexpensively obtaining a good-quality red pigment from hop bracts which are not currently effectively used as waste. The present invention was completed by utilizing this in foods and drinks, clothing and the like.

That is, the present invention is a hop-derived pigment obtained by treating hop cones, hop bracts or polyphenols contained in hop bracts with an acid or alkali, and having a red color.

The present invention also provides a method for producing a hop-derived pigment, characterized in that a hop cone, a hop bract or a polyphenol contained in a hop bract is treated with an acid in the presence of a metal ion to obtain a red pigment. Is the law. Also, the present invention
This is a method for producing a hop-derived pigment, characterized in that a hop cone, a hop bract or a polyphenol contained in a hop bract is treated with an alkali to obtain a red pigment.

Further, the present invention is a food, drink, cosmetic or dye containing the hop-derived pigment.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The method for obtaining a hop-derived natural pigment of the present invention will be described in detail below. The hop-derived natural pigment of the present invention can be obtained by hydrolyzing polyphenols present in bract parts of hops, so that purified hop polyphenols can be used as a raw material. Further, the lupulin part can be removed from the hop cones and used as a raw material as a bract part. Alternatively, the entire hop cone portion can be used as a raw material without extracting the hop bract portion.

When hop polyphenol is used as a raw material, 1 g of hop polyphenol is added to water,
Alternatively, an aqueous solution of an organic solvent miscible with water at an arbitrary ratio
Add 100 to 100 ml, preferably 10 to 20 ml, and dissolve. As the organic solvent, methanol, ethanol, acetone, acetonitrile and the like can be used. About 0.1 equivalent of acid or alkali is added to this solution, and if it is acid hydrolysis, the pH of the solution is 3.5 or less,
Preferably, the pH is 2 or less.
To 8.5 or more, preferably 9 or more, and refluxed at 40 ° C. or more, preferably 80 ° C. or more for 5 minutes to 2 hours. As the acid, any acid generally used industrially, such as hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, acetic acid, and trichloroacetic acid can be used without any particular problem. A particularly preferred example is hydrochloric acid. Sodium hydroxide as the alkali,
Any generally industrially used alkali such as potassium hydroxide or pyridine can be used without any particular problem.
A preferred example is sodium hydroxide. In the case of hydrolysis using an acid, the reaction rate is greatly increased by adding a metal ion such as ferrous ion to the reaction system in a catalytic amount (1 to 10 mg per gram of hop polyphenol) or more. Can be. As metal ions to be added, in addition to iron, cobalt, nickel, copper, zinc,
Metal ions such as manganese can be used as well. When it is actually added to the reaction system, it can be added in the form of a metal chloride or hydroxide such as ferrous chloride or ferrous hydroxide. In the case of hydrolysis using an alkali, the reaction proceeds rapidly without using a metal catalyst, but if necessary, a small amount of metal can be added to the reaction system.

The solution is dried to dryness by a usual method such as freeze-drying or spray-drying to obtain the desired hop-derived natural pigment. The solution is passed through the adsorption resin, the hop-derived natural dye is adsorbed on the resin, eluted from the resin using an organic solvent, and the desired hop-derived natural dye is purified.
A brighter red pigment can also be obtained. As the adsorption resin, vinyl polymer, styrene-divinylbenzene,
What is usually used industrially, such as hydroxypropylated dextran, can be generally used. As a solvent for eluting the hop-derived natural dye adsorbed on the resin, a solvent arbitrarily miscible with water, such as acetone, acetonitrile, methanol and ethanol, can be used. As the combination of the resin and the elution solvent, any of the above can be used in any combination.However, when the resin is used for a food or the like, from the viewpoint of food hygiene, particularly after being adsorbed to the hydrophilic vinyl polymer resin, It is preferable to remove the metal by eluting with 30% or more of ethanol. The eluate is dried in a usual manner to obtain the desired hop-derived pigment as a red powder.

When hop bracts are used as a raw material, 1 to 100 ml, preferably 10 to 20 ml, of water or an aqueous solution of an organic solvent miscible with water is added to 1 g of the hop bract portion, and hops are added. Wet the bracts. As the organic solvent, methanol, ethanol, acetone, acetonitrile and the like can be used. The following operation is the same as when hop polyphenol is used as a raw material.

When hop cones are used as a raw material, 1 to 100 ml of water or an aqueous solution of an organic solvent miscible with water in an optional ratio is added to 1 gram of hop cones.
Preferably 10 to 20 milliliters are added to wet the hop cones. As the organic solvent, methanol, ethanol, acetone, acetonitrile and the like can be used. The following operation is the same as when hop polyphenol is used as a raw material.

The main component of the hop-derived pigment thus obtained is an anthocyanidin-based polyphenol, which is naturally the same as that contained in blueberries, grapes, etc., and can be safely used in foods and clothing. . In addition, compared with the case where the same type of pigment is obtained from blueberries or grapes, the present method can provide the pigment at relatively low cost.

When the hop-derived pigment is added to the food or drink, the hop-derived pigment may be added as it is, but preferably, the hop-derived pigment is contained in a 1 to 2% aqueous solution or an aqueous alcohol solution or an alcohol solution. And a final concentration of 1 to 5000 ppm, preferably 1
It is desirable to add so that it may become 0-1000 ppm.

When the dough is colored, the hop-derived pigment is made into an aqueous solution of 1 to 2% or an aqueous alcohol solution or an alcohol solution, and the dough is soaked for about 5 minutes to 1 hour, and then washed with water or dried as it is to form the dough. A preferred red color can be imparted.

When a hop-derived dye is used as a dye,
The hop-derived pigment powder can be dissolved in water or ethanol for use. Further, it can be dissolved in a thinner, a lacquer, or the like, and if necessary, an appropriate excipient can be added and sealed.

[0019]

The present invention is not limited to the following examples.

Example 1 (Preparation of dye containing hop-derived pigment from hop cone using acid) 20 g of hop cone was ground in a mortar, and 10 mg of ferrous chloride was crushed.
And stirring with 1 liter of 0.05 M hydrochloric acid.
The mixture was heated under reflux at 40 ° C. for 40 minutes. After filtration, the mixture was allowed to cool to obtain a dye containing a hop-derived dye having a red color.

Example 2 (Preparation of hop-derived pigment from hop cone using acid) One liter of the dye obtained in Example 1 was freeze-dried, and 6.1 g of a red hop-derived pigment was converted into a red-yellow powder. Obtained.

Example 3 (Preparation of Hop-Derived Pigment from Hop Bract Using Acid) 20 g of hop bract and 100 mg of ferrous chloride were added in an amount of 0.1%.
The mixture was heated and refluxed for 40 minutes under stirring with 600 ml of a 50% aqueous ethanol solution containing hydrochloric acid. After filtration, the solution was concentrated under reduced pressure until the volume reached 300 ml. The concentrated solution was placed on a column filled with 80 ml of styrene-divinylbenzene resin (Sepabeads 825 manufactured by Mitsubishi Chemical Corporation).
The solution was passed over time, and then washed with 400 ml of water. Further, an 80% aqueous ethanol solution 40 is added to the column.
After passing through 0 ml, the eluate was collected and freeze-dried to obtain 1.5 g of a hop-derived pigment as a red powder.

Example 4 (Preparation of hop-derived pigment from hop polyphenol) 20 g of hop bracts were extracted with 600 ml of a 50% aqueous ethanol solution at 80 ° C. for 40 minutes with stirring. After filtration, concentrate under reduced pressure until the volume becomes 300 ml,
The concentrate was passed through a column filled with 80 ml of a styrene-divinylbenzene resin (Sepabeads 825 manufactured by Mitsubishi Chemical Corporation) for 1 hour, and then washed with 400 ml of water. Further, 400 ml of an 80% aqueous ethanol solution was passed through the column, and the eluate was collected and freeze-dried to obtain 1.6 g of hop bract polyphenol as a pale yellow powder having an odorless and slightly bitter taste. .
The yield from hop bracts was 8%. 2 g of 1 g of the obtained hop bract polyphenol and 50 mg of ferrous chloride
The mixture was heated and refluxed in a 30% methanol solution containing hydrochloric acid for 40 minutes. After cooling, the solution was dried under reduced pressure to obtain 0.9 g of a hop-derived pigment as a dark red powder.

Example 5 (Preparation of Hop-Derived Pigment from Hop Bract Using Alkali) 10 g of hop bract was stirred with 300 ml of water containing 0.5% sodium hydroxide at 60 ° C. for 3 hours with stirring. After filtration, the solution was neutralized with hydrochloric acid, passed through a column filled with 40 ml of styrene-divinylbenzene resin (Sepabeads 825 manufactured by Mitsubishi Chemical Corporation) over 30 minutes, and then washed with 150 ml of water. Further, 150 ml of a 60% aqueous ethanol solution was passed through the same column, and the eluate was collected and freeze-dried to obtain 0.1% of hop-derived dye.
9 g were obtained as a red powder.

Example 6 (Preparation of Beverage) 0.2 g of the hop pigment obtained in Example 2 was dissolved in 100 ml of water together with 1.5 g of fructose and 0.2 g of a fragrance to give a cool color reminiscent of grapes and blueberries. Drinking water.

Example 7 (Preparation of clothing) A cotton cloth was soaked in 1 liter of the hop pigment obtained in Example 1,
After washing with water and drying, a red-yellow cloth was obtained. The fabric was processed into a red-yellow shirt.

Example 8 (Preparation of Dye) The hop-derived dye obtained in Example 3 was dissolved in a thinner and sealed to form a dye.

[0028]

According to the present invention, a hop-derived pigment having a red color can be obtained from hop bracts and hop cones containing the hop bracts as raw materials. Furthermore, as a plant-derived hop-derived pigment, it can be easily used in foods and drinks, clothing, and dyes.

Claims (9)

[Claims] 1. A hop-derived pigment obtained by treating hop cones, hop bracts or polyphenols contained in the hop bracts with an acid or alkali, and having a red color. 2. A method for producing a hop-derived pigment, characterized in that a hop cone, a hop bract or a polyphenol contained in a hop bract is treated with an acid in the presence of a metal ion to obtain a red pigment. 3. A method for producing a hop-derived pigment, wherein a red pigment is obtained by treating a hop cone, a hop bract or a polyphenol contained in a hop bract with an alkali. 4. The method according to claim 1, wherein the metal ions are iron, cobalt, nickel,
3. The method according to claim 2, wherein the ion is a copper, zinc or manganese ion. 5. An acid comprising hydrochloric acid, nitric acid, sulfuric acid, perchloric acid,
An acetic acid or trichloroacetic acid is used.
Production method as described. 6. The method according to claim 3, wherein sodium hydroxide, potassium hydroxide or pyridine is used as the alkali. 7. A food or drink comprising the hop-derived pigment according to claim 1. 8. A cosmetic comprising the hop-derived pigment according to claim 1. 9. A dye comprising the hop-derived dye according to claim 1.