JP7464967B2 - Manufacturing method of food material or feed material, manufacturing method of food material or feed material, manufacturing method of food or feed, manufacturing method of food or feed, and manufacturing method of vanillin - Google Patents

Description

The present invention relates to a method for producing a food material or feed material, a food material or feed material, a food or feed product, a food or feed product, and a method for producing vanillin.

Natural vanillin, obtained from the Vanilla genus plant of the Orchidaceae family, has a unique sweet aroma and is used in a wide range of vanilla flavoring applications, including as a flavoring in chocolate, ice cream, and other foods. In recent years, the demand for natural vanillin has increased in Europe, the United States, and China, causing the trading price of vanilla beans, the raw material for natural vanillin, to soar. This has led to an increased demand for synthetic vanillin, which is cheaper than natural vanillin.

Synthetic vanillin can be divided into chemically synthesized vanillin and biologically synthesized vanillin, based on the differences in the manufacturing process. Chemically synthesized vanillin was first produced in 1874 by Germany's Tiemann et al., who produced vanillin from the lignin intermediate in the cell walls of bulbous plants, which made industrial production of synthetic vanillin possible. Currently, vanillin is chemically synthesized using raw materials such as safrole (essential oil of sassafras), eugenol (essential oil of clove), lignin (waste liquor from sulfite pulp), and guaiacol.

Regarding chemically synthesized vanillin, Non-Patent Document 1 discloses that vanillin was detected when lignin fractions extracted from corn stalks and poplar were treated with ozone in an organic solvent. Non-Patent Document 2 discloses that vanillin was detected when bermuda grass and its cell wall fraction, and tall fescue and its cell wall fraction were treated with ozone. The cell walls of corn stalks and bermuda grass contain lignin. This lignin is reinforced by diferulic acid, which is made up of two ferulic acids. Vanillin is produced from this diferulic acid, but because diferulic acid is also strongly bound to polysaccharides, a high amount of energy is required to convert it into vanillin.

On the other hand, with regard to biologically synthesized vanillin from biomass-derived compounds, Non-Patent Document 3 discloses the production of vanillin using ferulic acid and phenylalanine as raw materials, using microorganisms or yeast whose metabolism has been altered through genetic engineering.

Incidentally, oryzanol (sometimes called rice oryzanol or γ-oryzanol) contained in rice bran and other foods is widely used in foods and medical products as an antioxidant and neuroactive drug. Rice oryzanol is an ester of ferulic acid, a type of plant sterol. In recent years, it has been discovered that similar components are also found in wheat, rye, corn, millet, and other grains. However, there are almost no industrial uses for rice oryzanol other than that.

Technologies for producing vanillin from this oryzanol have also been disclosed (see Patent Documents 1 and 2). Patent Document 1 discloses a method for producing vanillin by alkaline hydrolysis of oryzanol-containing waste and by-products discharged during the production of rice salad oil, and then oxidizing the alkaline aqueous solution with an oxidizing agent such as nitrobenzene or ozone. Patent Document 2 discloses a method for producing edible oils and fats containing vanillin by heating oryzanol-containing oils and fats to convert a portion of the oryzanol into vanillin, and also discloses that the inclusion of vanillin improves the flavor of fried foods.

However, in Patent Document 1, oryzanol-containing waste materials are treated with alkali to produce a metal ester of ferulic acid, which is then oxidized under high pressure and high temperature to produce and precipitate an alkali metal salt of vanillin. The precipitated alkali metal salt of vanillin is then dissolved again in water, and the aqueous solution is made acidic by adding sulfuric acid or the like to precipitate vanillin, which is then recrystallized from water to purify the vanillin. For this reason, many steps are required to produce vanillin, and the processing is not easy or efficient. Furthermore, in the technology of Patent Document 2, care must be taken when handling oryzanol-containing fats and oils that have been heated to a high temperature.

In addition, when the purpose is to produce vanillin, it is desirable to have a high conversion efficiency of oryzanol to vanillin, but when using it as a food ingredient, etc., there is a demand for imparting a vanillin aroma while retaining sufficient amounts of active ingredients such as oryzanol. In either case, there is a demand for the development of technology that can efficiently produce vanillin using simple procedures without requiring treatments such as high temperature or high pressure.

A new method for producing the sweet aroma component of vanilla, Toshiki Furuya, Journal of Biotechnology, Vol. 95, No. 5, P272 Ozonation Products of Organosolvolytic Extracts from Vegetal Materials. Quesada J et al. Journal of Agricultural and Food Chemistry Vol.46 No.2. Page. 692-697(1998.02) Water-soluble reaction products from ozonolysis of grasses. Morrison W. Herbert III et al. Journal of Agricultural and Food Chemistry Vol. 3 Page. 678-681(1990.03)

Japanese Patent Application Laid-Open No. 6-325530 JP 2006-325530 A

The present invention aims to solve the above problems and produce vanillin simply and efficiently.

In order to solve the above problems, the inventors conducted intensive research and discovered that by treating the fruits or fractions of edible or feed Gramineae plants with ozone, the oryzanol contained in these plants can be easily and efficiently converted to vanillin. Furthermore, they discovered that by treating an oryzanol reagent with ozone, it can be converted to vanillin with high efficiency. Based on these findings, the inventors have completed the present invention.

That is, the method for producing a food material or feed material according to the present invention is characterized by comprising a step of reacting ozone with a raw material containing at least one kind selected from the fruits of edible or feed Gramineous plants and fractions thereof.
Furthermore, the food material or feed material according to the present invention is a food material or feed material imparted with a vanillin aroma, which is obtained by the above-mentioned method for producing a food material or feed material.
Furthermore, the method for producing a food or feed according to the present invention is characterized in that the food material or feed material obtained by the above-mentioned method for producing a food material or feed material is used as a raw material for the food or feed.
Furthermore, the food or feed according to the present invention is a food or feed imparted with a vanillin aroma, which is obtained by the above-mentioned method for producing a food or feed.
Further, a method for producing vanillin according to the present invention includes a step of dispersing oryzanol or at least one of a plant fraction containing said oryzanol in 10 to 35% ethanol to obtain a dispersion, and a step of aerating ozone into the dispersion, wherein in the step of obtaining the dispersion, ethanol is added to the raw material, and then water is added to obtain a 10 to 35% ethanol solution, and in the step of aerating ozone, a pH adjuster is added so that the pH of the dispersion water is 2 to 8.

According to the present invention, ferulic acid esters such as oryzanol in the raw material can be converted to vanillin by applying ozone to the raw material. Therefore, vanillin can be produced simply and efficiently.

1 is a graph showing the results of a vanillin production experiment in Experimental Example 1. 1 is a graph showing the results of a vanillin production experiment in Experimental Example 2. 1 shows the experimental results of Experimental Example 3, where (a) is an image of the dispersion immediately after preparation, (b) is an image of the dispersion after two days, and (c) is a graph showing the production rate of vanillin. 1 is a graph showing the results of a vanillin production experiment in Experimental Example 4. This is a high-speed liquid chromatogram of rice bran, wheat bran, and raw corn husks when ozone was bubbled in the vanillin production experiment of Experimental Example 5-1. 1 is a high performance liquid chromatogram showing the change in the amount of oryzanol in wheat bran when ozone was directly sprayed onto the wheat bran in the vanillin production experiment of Experimental Example 6. 1 is a liquid high performance chromatogram for confirming the change in the amount of oryzanol in rice bran when ozone is directly sprayed onto the rice bran in the vanillin production experiment of Experimental Example 6. 1 is a chromatogram for confirming a change in the amount of oryzanol in raw corn husks when ozone is directly sprayed thereon in the vanillin production experiment in Experimental Example 6. 1 is a liquid high-speed chromatogram for confirming the change in the amount of vanillin in wheat bran when ozone is directly sprayed onto it in the vanillin production experiment of Experimental Example 6. 1 is a liquid high-speed chromatogram for confirming the change in the amount of vanillin in hulled foxtail millet when ozone is directly sprayed onto it in the vanillin production experiment of Experimental Example 6. 1 is a liquid high performance chromatogram for confirming the change in the amount of vanillin in quinoa when ozone is directly sprayed onto it in the vanillin production experiment of Experimental Example 6. 1 is a liquid high-speed chromatogram for confirming the change in the amount of vanillin in unpolished buckwheat when ozone is directly sprayed onto the buckwheat in the vanillin production experiment of Experimental Example 6. 1 is a liquid high-speed chromatogram for confirming the change in the amount of vanillin in fresh western grass when ozone is directly sprayed onto it in the vanillin production experiment of Experimental Example 6. 1 is a liquid high-speed chromatogram for confirming the change in the amount of vanillin in fresh western grass when ozone is bubbled in the vanillin production experiment of Experimental Example 6.

The following describes in detail the embodiments of the present invention.

<Method of producing food materials or feed materials, food materials or feed materials, food or feed production methods, and food or feed>
The method for producing a food material or feed material according to the present embodiment includes a step of allowing ozone to act on a raw material containing at least one selected from the fruits of edible or feed Gramineae plants and fractions thereof. The food material or feed material according to the present embodiment is obtained by the method for producing a food material or feed material according to the present embodiment and is imparted with a vanillin aroma.

However, it is impossible or impractical to directly identify the characteristics of such food or feed materials by the structure or properties of the object. In other words, the fruits of grasses and their fractions, which are the raw materials for food or feed materials, contain a wide variety of chemical components such as oryzanol, proteins, carbohydrates, lipids, vitamins, and calcium. By applying ozone to such raw materials without performing alkaline hydrolysis, high-temperature heat treatment, high-pressure treatment, etc., oryzanol and other components are converted into vanillin, and a vanillin aroma is imparted to the food or feed materials. In contrast, in the conventional techniques of Patent Documents 1 and 2, vanillin is produced by performing alkaline hydrolysis, high-temperature heat treatment, high-pressure treatment, etc. on the raw materials, which has a significant effect on the chemical components in the raw materials and may cause various chemical changes in components other than oryzanol, etc. For this reason, the chemical components and their contents are different between the food or feed materials produced by the production method of this embodiment and the food or feed materials produced by the conventional techniques. However, analyzing all of these chemical components and identifying their types and contents is either impossible or would require significantly excessive economic expenditure and time, making it virtually impractical. For this reason, the food or feed material of this embodiment is specified as a food or feed material that has been obtained by a manufacturing method for a food or feed material and that has been imparted with a vanillin aroma.

The food or feed manufacturing method according to this embodiment uses the food material or feed material obtained by the food material or feed material manufacturing method according to this embodiment as a food or feed ingredient. The food or feed according to this embodiment is a food or feed obtained by the food or feed manufacturing method according to this embodiment and imparted with a vanillin aroma. As with the food material or feed material according to this embodiment, it is impossible or impractical to directly identify the characteristics of the food or feed according to this embodiment by the structure or properties of the object, so it is specified as a food or feed obtained by a food or feed manufacturing method and imparted with a vanillin aroma.

In each of the production methods of the present embodiment, ozone (O ₃ ) is applied to the raw material to convert oryzanol, ferulic acid esters such as ethyl ferulate, etc., contained in the raw material (hereinafter, sometimes abbreviated as "oryzanol, etc.") into vanillin. This provides food materials and feed materials imparted with vanillin aroma, and foods and feeds using these. As a result, it is possible to provide food materials that have a good flavor (aroma and taste), are delicious, and can improve human palatability, and foods using the same. It is also possible to provide feed materials that have a good flavor, are delicious, and can be eaten well by livestock such as pigs, thereby improving their appetite, and feeds using the same. Incidentally, when the inventor searched SciFinder ⁿ (registered trademark) for a method of generating vanillin by applying ozone to ferulic acid esters such as oryzanol and ethyl ferulate, the number of searches was zero, and no scientific reports had been published.

Note that "vanillin aroma is imparted" means that oryzanol, etc. are converted to vanillin, causing raw materials, food ingredients, feed ingredients, food, and feed (hereinafter sometimes referred to as "raw materials, etc.") to contain vanillin, and the vanillin aroma is released from the raw materials, etc. into the air. Also, if the raw materials, etc. already contain vanillin, the vanillin content in the raw materials increases as oryzanol, etc. are converted to vanillin, and the vanillin aroma is enhanced. Therefore, "enhanced vanillin aroma" is also included in "vanillin aroma is imparted."

Vanillin is the main component of vanilla flavoring extracted from vanilla beans, and has a sweet aroma. Vanilla flavoring contains various aroma components other than vanillin, so the vanillin aroma is intricately intertwined with the aromas of the various other aroma components to create a unique "vanilla aroma" that is not only sweet, but also spicy, sour, bitter, etc. For this reason, when the raw material used in this embodiment is imparted with a vanillin aroma (vanillin is produced or enhanced), a vanillin aroma or a unique aroma that is a combination of the vanillin aroma and other aroma components contained in the raw material is released. Therefore, when this "unique aroma" is imparted, this is also considered to be included in the fact that "vanillin aroma is imparted."

In addition, the conversion efficiency of oryzanol, etc. in the raw material to vanillin (vanillin production rate) can be appropriately adjusted by appropriately adjusting the conditions (time, ozone concentration, temperature, etc.) when applying ozone. For this reason, for example, by extending the ozone treatment time or increasing the ozone concentration, oryzanol can be converted to vanillin with high efficiency, and more vanillin can be produced. On the other hand, when the objective is to impart a vanillin aroma while appropriately ensuring the content of oryzanol, etc., it is also possible to convert only a part of oryzanol, etc. to vanillin to an extent that it can be sensed by humans and livestock. For example, the oryzanol content of rice bran is 150 to 200 mg/100 g, that of brown rice is 35 to 40 mg/100 g, that of wheat is 10 to 15 mg/100 g, and that of corn kernels is 6 to 8 mg/100 g. It is sufficient if a part of these can be converted to vanillin. The human odor threshold for vanillin is extremely low at 0.000000032 ppm, or 10 ⁻⁶ ppm. Therefore, by converting only a small portion of the oryzanol in the raw material to vanillin, a sufficient vanillin aroma can be imparted to food ingredients, etc.

Therefore, the vanillin content of the food material, feed material, food, or feed to which the vanillin aroma of this embodiment has been imparted is desirably 70 μg/1g or more. More specifically, it is desirably that 70 μg/1g or more of vanillin is eluted when the sample is immersed in a 50% methanol solution. Alternatively, it is desirably that the vanillin content is such that a vanillin aroma equal to or greater than the threshold of human odor sensitivity to vanillin is released. The threshold is desirably, for example, 0.000000032 ppm or more, and more desirably 10 ⁻⁶ ppm or more, and a product that can improve the palatability of humans, livestock, and the like can be provided.

In addition, it is desirable to carry out the action of ozone under atmospheric pressure at room temperature between 0°C and 30°C, which allows for a more stable reaction. In addition, since the pressure and temperature are not high, there is no need for large-scale cooling equipment or protective equipment, and vanillin can be produced easily with simple equipment and facilities, without requiring a large amount of energy.

Specifically, the process of applying ozone can be any one of the following processes (1) to (3). Alternatively, a combination of these processes can be used. This allows ozone to be applied appropriately depending on the type, form, properties, etc. of the raw material, and allows oryzanol and the like to be converted to vanillin more appropriately and efficiently.

(1) A step of bubbling ozone into a solution obtained by adding a raw material to a solvent.
In this process, the raw material is placed in a solvent and ozone is bubbled through the solution. This process can be applied to both fruits and fractionation. In particular, in the case of fractionation, the raw material can be dispersed in a solvent to improve contact with ozone. Since the raw material is used for the production of food materials, feed materials, food, or feed, it is preferable to use water or alcohol (ethanol) as the solvent.

It is also desirable to aerate ozone at atmospheric pressure and at room temperature between 0°C and 30°C. Furthermore, taking into consideration that the lower the temperature, the higher the solubility of ozone, it is more desirable to cool the container containing the raw material and solvent with ice water or the like and set the solution temperature to about 0°C.

(2) A step of immersing the raw material in ozone water.
In this step, the raw material is immersed in ozone water and allowed to stand. Ozone water can be produced by bubbling ozone into water. The bubbling time can be set appropriately depending on the amount of ozone generated per unit time from the ozone generator, and is preferably about 30 to 60 minutes, taking into consideration that the half-life of ozone is 20 minutes. In addition, both when producing ozone water and when immersing the raw material in ozone water, it is desirable to cool the container with ice water or the like to keep the solution temperature at about 0°C. It is desirable to prepare ozone water so that the ozone concentration is 0.5 to 1.0 ppm with a bubbling time of 30 minutes and the ozone concentration is 1.0 to 1.5 ppm with a bubbling time of 60 minutes.

(3) A process of spraying ozone directly onto the raw material.
In this process, ozone is directly sprayed onto the raw material contained in a container or the like, and the raw material is exposed to ozone while the container is sealed. The spraying time and exposure time vary depending on the state of the raw material and the amount of vanillin required, but for example, ozone is sprayed onto the raw material in the container for 5 minutes under atmospheric pressure at room temperature (0° C. or higher and 30° C. or lower) while the container is cooled in ice water to make the internal temperature 0° C. Next, after sealing the container, the raw material is exposed to ozone for 30 minutes at room temperature while remaining still.

The raw material to be treated with ozone is not particularly limited, but for example, the fruits of plants containing oryzanol and ferulic acid esters such as ethyl ferulate, or fractions thereof are suitable. Among these, the fruits of grasses containing oryzanol or fractions thereof are preferable. These can be used as food or feed materials, and can also be ingested as they are, so they can also be used as food or feed themselves.

There are no particular limitations on the Gramineae plant, so long as the fruit or a fraction thereof contains oryzanol. Specific examples include rice, wheat (wheat, barley, oats, rye, etc.), cereals such as corn, millet, proso millet, and other miscellaneous grains. Of these, rice, wheat, corn, millet, and other miscellaneous grains are more preferred. It is well known that rice, wheat, corn, and other cereals contain oryzanol, and the inventor's research has revealed that miscellaneous grains such as millet, proso millet, and other miscellaneous grains also contain oryzanol.

Fruit fractions are produced by crushing fruit and classifying it into its components. For example, it can be fractionated into endosperm, germ, and outer skin (pericarp), and these are further fractionated into their components. The raw material needs to contain at least one component from these fractions, but it may also contain multiple components or all of them.

Among these fractions, husks (rice bran, wheat bran, corn husks, etc.) are produced in large quantities as by-products when refining and milling grains, etc., and when producing oils, etc., and traditionally these had to be used as livestock feed or fertilizer, or discarded. However, because husks contain a large amount of oryzanol, using them as a raw material for producing vanillin not only makes it possible to efficiently produce vanillin, but also provides the new effect of making effective use (processing) of by-products. In addition, imparting a vanillin aroma makes it possible to provide food ingredients and foods that humans can enjoy, and feed ingredients and feed that livestock can enjoy, which has the special effect of increasing demand.

Oryzanol is a type of phytochemical, and is composed of a mixture of more than 24 different components, so it is considered to be "a general term for components in which ferulic acid is ester-bonded to a plant sterol or triterpene alcohol." Oryzanol is also called "steryl ferulate."

Oryzanol is known to have various physiological functions, including antioxidant effects, improvement of hyperlipidemia and hypercholesterolemia, blood sugar lowering effects, anti-inflammatory effects, and anti-allergic effects. In addition, oryzanol has been found to be effective as a neuroactive drug, and is used in pharmaceuticals such as psychotropic drugs, central nervous system agonists, and antidepressants, and demand for it is increasing. The recommended daily intake of oryzanol for humans is 9 mg.

Oryzanol, for example, has the following structure, with the ferulic acid portion being common, and the plant sterol portion differing depending on the molecular species of steryl ferulate.

In this specification, "oryzanol" is defined as a substance having such a structure and containing "a component in which ferulic acid is ester-bonded to a plant sterol or triterpene alcohol." Oryzanol contained in rice or its fractions is called "rice oryzanol (γ-oryzanol)," oryzanol contained in wheat or its fractions is called "wheat oryzanol," oryzanol contained in corn is called "corn oryzanol," and so on, with the name of the grain or cereal being given to it. When the term "oryzanol" is used simply, it is used as a general term including "rice oryzanol," "wheat oryzanol," etc.

When ozone is applied to oryzanol, the oryzanol is oxidized by ozone, and the double bond of ferulic acid is broken as shown below to produce vanillin.

Specific examples of fruits and fractions thereof that contain oryzanol and are suitable for imparting a vanillin aroma are given below.
Brown rice grains: Grains, the state of rice after threshing when storing it for eating. Some modern people eat it as is. If you cook it, it becomes "brown rice."
・Brown rice flour: ground brown rice.
・Rice bran: This is produced during the rice polishing process and is not crushed any further.
・White rice: Grain, grain, the rice grain that we normally eat.
・White rice flour: White rice grains ground into powder using a mixer.
・Whole wheat grain: Grain, whole wheat, not ground into flour.
・Whole wheat flour: Whole wheat flour ground in a mixer.
・Wheat bran: Instead of using the usual milling method, this is produced by polishing rice in a rice polisher, scraping off the outside of the whole wheat kernel and separating it into powder, the brown part of the wheat kernel other than the white part (commonly known as flour).
・Corn kernel: Cereal grain, yellow kernel of corn.
Corn peel: Corn peel is the thin skin around the yellow kernel of corn. It is a by-product of making cornstarch and baby food. It is sometimes mixed into livestock feed. There are pre-dried and post-dried types, and in this specification, the pre-dried type is referred to as "raw corn peel."
・Brown foxtail millet: A type of grain that includes the outer husk (husk) of the foxtail millet. Usually, the outer husk is removed before it is consumed by humans. Brown foxtail millet with the outer husk is also available commercially as food for small birds.
-Foxtail millet: A cereal grain, commercially available for human consumption, does not have the husk.

As described above, according to this embodiment, by applying ozone to a raw material containing at least one selected from the fruits of edible or feed Gramineae plants and fractions thereof, oryzanol, etc. in the raw material are converted to vanillin, and a vanillin aroma is imparted to the raw material. As a result, a method for producing a food material or feed material that can easily and efficiently produce vanillin, and a method for producing a food or feed, can be provided. In addition, a food material or feed, and a food or feed that are obtained by these production methods and have a vanillin aroma, can be provided. In addition, by changing the conditions for applying ozone, a part or all of the oryzanol, etc. in the raw material can be converted to vanillin. Thus, only the amount of oryzanol, etc. required depending on the purpose can be converted to vanillin.

<Method of producing vanillin>
The method for producing vanillin according to the present embodiment includes the steps of dispersing a raw material containing at least one selected from oryzanol, ethyl ferulate, other ferulic acid esters, and plant fractions containing such ferulic acid esters in an ethanol solution to obtain a dispersion, and aerating ozone through the dispersion. The method for producing vanillin according to the present embodiment is suitable for producing vanillin from oryzanol or a plant fraction containing oryzanol, among ferulic acid esters and plant fractions containing the same.

Each step is described in detail below. In the step of obtaining a dispersion, the raw material is dispersed in an ethanol solution. The higher the concentration of ethanol, the better the water-insoluble oryzanol etc. can be extracted into the solution, and the higher the conversion efficiency to vanillin can be. On the other hand, by using 10% to 35% ethanol, the amount of ethanol used can be reduced while the water-insoluble oryzanol etc. can be well dispersed in the solution. In addition, the oryzanol etc. contained in the plant fraction can be extracted into 10% to 35% ethanol and dispersed in the solution.

In a dispersion using 10% to 35% ethanol, no precipitation occurs even after a long period of time (e.g., 2 days), and stable micelles are obtained. This allows the production rate of vanillin through the action of ozone to be improved.

In the process of obtaining this dispersion, it is preferable to add the ethanol stock solution to the raw material, and then add water to obtain a 10% to 35% ethanol solution. More specifically, the ethanol stock solution is first added to the raw material, and oryzanol is dissolved in ethanol by stirring or ultrasonic treatment. Next, water is added so that the ethanol concentration is 10% to 35%, and stirring or ultrasonic treatment is performed. This allows oryzanol and the like to be well dispersed even in a low-concentration ethanol solution, and the effects of ozone oxidation can be suppressed. In addition, the use of organic solvents is reduced, making it more suitable as a solvent for use in the production of vanillin for food or feed. As the ethanol stock solution, 99.5% ethanol (absolute ethanol) is preferably used, but 95% ethanol can also be used.

In addition, it is desirable to add n-hexane to the raw material as a pretreatment step for obtaining the above dispersion liquid. This can change the orientation of raw materials such as oryzanol. As a result, the dispersibility in ethanol can be improved, and the production rate of vanillin can be further increased. Furthermore, by performing ultrasonic treatment after adding n-hexane, the effect of n-hexane can be improved. By introducing nitrogen and distilling off n-hexane after ultrasonic treatment, n-hexane does not affect the dispersibility of the raw material in ethanol.

In the process of aerating ozone, an ozone generator or the like is used to aerate ozone into the dispersion. This process converts oryzanol and the like into vanillin. If the pH of the dispersion is lowered by ozone oxidation, the production of vanillin may be inhibited. For this reason, in this process, it is desirable to add a pH adjuster so that the pH is between 2 and 8.

Specifically, the pH of the dispersion is measured using a pH detector or a test agent while ozone is being passed through, and when the pH drops, a weak alkali is added as a pH adjuster at an appropriate timing to raise the pH to an alkaline state so that the pH does not become less than 2. At this time, even if the pH becomes 8 or higher, vanillin is not produced, so the amount of alkali added is adjusted so that the pH is kept below 8. The weak alkali is not particularly limited, but by using NaHCO ₃ (sodium bicarbonate), vanillin suitable for use as a food or feed material can be produced.

As described above, according to this embodiment, oryzanol and the like can be converted to vanillin with high efficiency simply by dispersing the raw material in a low-concentration 10% to 35% ethanol solution and aerating ozone through it. Therefore, vanillin can be produced simply and efficiently. Furthermore, the influence of the oxidizing power of ozone can be suppressed. Moreover, vanillin obtained by the vanillin production method of this embodiment can be suitably used as a food material or feed material.

Various experimental examples (embodiments) are explained below.

<Experimental Example 1: Vanillin Production Experiment>
Experiments on the production of vanillin by ozonolysis were carried out using powdered reagents: oryzanol (FUJIFILM Wako Pure Chemical Industries, Ltd.; 152-01272 γ-oryzanol for biochemistry), ferulic acid (Combi-Blocks, Inc.; QA-0504 97% ferulic acid), and ethyl ferulate (Combi-Blocks, Inc.: OR-1951 98% ferulic acid ethyl ester). Table 1 below shows the ethanol concentration of the solution, the type of reagent (sample), and the amount used.

The experimental procedure is explained below. The solutions and reagents shown in Table 1 above were placed in containers, and ozone was bubbled through the containers at room temperature. The ozone was bubbled while the containers were cooled with ice water. Maruko Denki Co., Ltd.'s "Soec300" was used as the ozone generator, and bubbling was performed at an ozone generation rate of 300 mg/hr. The same ozone generator was used in each experiment described below.

After the specified ozone treatment time had elapsed, n-hexane was added to the solution to separate sterols, etc., and then 90% ethanol was added to extract the sample and vanillin into ethanol, after which the sample and the produced vanillin were recrystallized and collected. Graphs showing the results of the vanillin production experiments under each of the conditions No. 1 to 9 in Table 1 are shown in Figure 1 (a) to (i). The horizontal axis of each graph is the ozone bubbling time (ozone treatment time), and the vertical axis is the millimolar concentration of oryzanol and vanillin in the reagent.

From the results of Experimental Example 1, it can be seen that the higher the ethanol concentration, the higher the vanillin production rate. In particular, when 99.5% ethanol was used, it was found that oryzanol, ferulic acid, and ethyl ferulate could all be converted to vanillin at almost 100%. In contrast, when 10% ethanol was used, the vanillin production rate of ferulic acid and ethyl ferulate was high, but the oryzanol production rate was low. This is thought to be due to the low solubility of oryzanol in water. However, it was confirmed that oryzanol was converted to vanillin even with low concentration ethanol. In addition, when three subjects actually smelled the sample after ozone treatment, a vanillin scent was confirmed. Based on the above experimental results and the fact that the human odor threshold of vanillin is 0.000000032 ppm, it was found that even when the vanillin production rate is low, a vanillin scent sufficient to be smelled by humans can be imparted to the material. In addition, when low-concentration ethanol is used, the amount of ethanol used is small, it has less effect on the oxidizing power of ozone, and is more suitable as a solvent for food and feed.

<Experimental Example 2: Dispersion of Oryzanol in Aqueous Ethanol Solution and Production of Vanillin>
An aqueous ethanol solution was added to oryzanol reagent (powder) that had been pretreated with n-hexane and to oryzanol reagent (powder) that had not been pretreated, and the amount of vanillin produced was examined. The specific experimental procedure is shown below. In the following experimental examples, 99.5% ethanol was used as the "ethanol stock solution" unless otherwise specified.

(1) Pretreatment with n-hexane 5.0-10.0 mL of n-hexane was added to 600 mg of oryzanol reagent and stirred by ultrasonication. An IWAKI ultrasonic cleaner "IWAKI ULTRASONICCLEANER" (model: USC-100Z38S-22) was used for ultrasonication. The ultrasonication in the following experiments was also performed using the same equipment. Nitrogen was then introduced to distill off n-hexane, and 50 mL of ethanol stock solution was added to the remaining oryzanol. After ultrasonication, 150 mL of water was added to adjust the ethanol concentration to 25%, and ultrasonication was performed to prepare sample solution B. As a control experiment, 150 mL of water was added to oryzanol, ultrasonication was performed, and 50 mL of ethanol stock solution was added to adjust the ethanol concentration to 25%, and ultrasonication was performed to prepare sample solution C. Sample solution A (0% ethanol) was also prepared by adding only water. As a comparative experiment, alkaline water and a solution (2.0%) of water with 1 monolaurin (surfactant) added thereto were added as solvents instead of the ethanol solution, and ultrasonic treatment was performed to prepare sample solutions D and E. Furthermore, undiluted ethanol was added first, ultrasonic treatment was performed, and then alkaline water and water + 1 monolaurin were added, and ultrasonic treatment was performed to prepare sample solutions F and G.

(2) No pretreatment with n-hexane: 50 mL of ethanol stock solution was added to 600 mg of oryzanol reagent, followed by ultrasonic treatment, and then 150 mL of water was added to adjust the ethanol concentration to 25%, followed by ultrasonic treatment to prepare sample solution H. Also, 150 mL of water was added to the oryzanol reagent, followed by ultrasonic treatment, and then 50 mL of ethanol stock solution was added to adjust the ethanol concentration to 25%, followed by ultrasonic treatment to prepare sample solution I.

Ozone was bubbled into each of the sample solutions A to I prepared as described above for 30 minutes. After that, 480 μL of methanol was added to each of the sample solutions A to I, and the solution was filtered using a filtration device (Advantic, DISMIC-13HP, model number: 13HP045AN). Next, 20 μL of the filtrate was fed to HPLC, and the amount of vanillin produced (peak intensity) was measured. Figure 2 shows the measurement results. From the results in Figure 2, it was found that a high vanillin production rate could be obtained by adding undiluted ethanol to oryzanol and then adding water. It was also found that the vanillin production rate was higher when pretreatment was performed with n-hexane. This is thought to be the result of the pretreatment changing the molecular orientation of oryzanol, making it easier to disperse in an aqueous ethanol solution.

<Experimental Example 3: Experiment on dispersibility of oryzanol and vanillin production using ethanol of different concentrations>
2.0 mg of powdered oryzanol reagent was pretreated with 0.1 mL of n-hexane, and then 20 mL of ethanol at various concentrations from 0% to 99.5% was added as a solvent and stirred by ultrasonic treatment to prepare dispersions. When adjusting the ethanol concentration, undiluted ethanol was added first and ultrasonicated, and then water was added and ultrasonicated. The dispersibility of oryzanol was examined immediately after the dispersion preparation and after 2 days. Figure 3(a) shows images of the dispersions immediately after preparation when water (0%), 10%, 25%, and 50% ethanol were used, and Figure 3(b) shows images of the dispersions after 2 days.

As shown in Figure 3(a), immediately after preparation, oryzanol was dispersed in the solution, and in the solution containing ethanol, micelles were formed. Since oryzanol is insoluble in water, when water (0%) was used, oryzanol was temporarily dispersed by stirring, but micelles were not formed. As shown in Figure 3(b), two days after preparation, oryzanol precipitated in 0% and 50% ethanol, but micelles were confirmed in 10% and 25% ethanol, indicating that stable micelles could be obtained.

Figure 3(c) shows the vanillin production rate when ozone was bubbled for 30 minutes into each sample solution prepared by adding 0% to 99.5% ethanol to the oryzanol reagent. The horizontal axis of the figure is the ethanol concentration (%), and the vertical axis is the vanillin production rate (%). The vanillin production rate was calculated using the following procedure. Figure 3(c) shows the vanillin production rate for 0% to 99.5% ethanol calculated using the following procedure.

(1) Prepare vanillin/methanol solutions of known concentrations in the range of 0.1 ng-10 ng.
(2) Analyze 10 μL of each solution by HPLC. For example, when 10 μL of a 1 ng/mL solution is injected, 0.01 ng of vanillin is provided in the HPLC.
(3) Calculate the peak area of vanillin from each HPLC chart.
(4) Draw a calibration curve using the amount of vanillin and peak area of each solution provided.
(5) Vanillin is extracted from the ozone-treated sample and the sample before and after ozone treatment with methanol, and 10 μl of the extracted solution is analyzed by HPLC.
(6) Calculate the vanillin production rate based on the analysis results of (5) and the calibration curve of (4).

Specifically, for example, 1 g of sample is immersed in 2 mL of methanol solvent, and vanillin is extracted from the sample into a solution using an ultrasonic device. 10 μL of the extracted solution is analyzed by HPLC. The vanillin production rate of each solution is calculated based on the analysis results and the calibration curve. Specifically, the amount of vanillin extracted from 1 g of sample x 10 μL/2 mL = 0.005 g of sample, that is, 5 mg of sample, is calculated. To do this, the peak area of vanillin in HPLC is calculated, and the amount of vanillin contained in 5 mg of sample is calculated using the calibration curve. For example, when the amount of vanillin in 10 μL subjected to HPLC is calculated to be 1 ng, the amount of vanillin extracted from this sample (equivalent to 5 mg) is 1 ng/5 mg = 1 μg/5 g = 20 μg/100 g. In other words, 20 μL of vanillin is extracted from 100 g of sample.

According to the results of Experiment 3, vanillin is produced even when the only solvent added to oryzanol is water, and when 99.5% ethanol is used, nearly 100% of the oryzanol can be converted to vanillin. It was also confirmed that by setting the ethanol concentration of the solvent to 10% to 35%, stable micelles are obtained and the conversion efficiency of oryzanol to vanillin is higher than when only water is used. It was also confirmed that even when the ethanol concentration is high, the conversion efficiency to vanillin may be lower than when the ethanol concentration is 10% to 35%. In view of the above, it was found that by using 10% to 35% ethanol as the solvent in which oryzanol is dispersed, excellent conversion efficiency to vanillin can be obtained while minimizing the use of organic solvent.

<Experimental Example 4: Experiment on vanillin production by addition of pH adjuster>
5.0-10.0 mL of n-hexane was added to 600 mg of powdered oryzanol reagent and sonicated. After distilling off n-hexane with nitrogen, 50 mL of ethanol stock solution was added to the oryzanol reagent and sonicated. Then, 150 mL of water was added to adjust the ethanol concentration to 25% to prepare a sample solution. Ozone was bubbled into this sample solution to generate vanillin. In addition, _{20 mg} of NaHCO3 was added as a pH adjuster to the sample solution at 40, 60, and 80 minutes after bubbling to prevent the pH from becoming less than 2 due to the oxidizing power of ozone. The generated vanillin was collected in the same manner as in Experimental Example 1, and the amount of vanillin generated was measured. In addition, as a control experiment, a vanillin generation experiment was performed using only water as the solvent in the same manner, and the amount of vanillin generated was measured. All experimental results are shown in Figure 4. The horizontal axis indicates the ozone bubbling time (minutes), and the vertical axis indicates the amount of vanillin generated (mmol).

The experimental results in Figure 4 confirm that the conversion efficiency to vanillin is significantly higher when a 25% ethanol aqueous solution is used than when water alone is used. It was also confirmed that the inhibition of vanillin production can be suppressed by adding a pH adjuster.

<Experimental Example 5: Vanillin production experiment using fruit and plant fractions>
Using the fruit and plant fractions shown in Tables 2 to 8 below as samples, vanillin production experiments were carried out using any of the following methods A, B, or C.
A: A method of immersing a sample in water and bubbling ozone into the water. B: A method of immersing a sample in ozone water. C: A method of spraying ozone directly onto a sample.

<Experimental Example 5-1>
A: Method of immersing a sample in water and bubbling ozone into the water 20 mL of water was added to 1 g of a sample of the type and state (granules, powder, etc.) shown in Table 2 below. The container was cooled in ice water until the internal temperature reached 0°C. After that, ozone was bubbled into the solution at an ozone generation rate of 300 mg/hr for the time shown in Table 2 (0 min to 60 min) in an atmosphere of 0°C or room temperature of 20°C, to perform ozone treatment.

After the ozone treatment was completed, 20 mL of methanol was added to each solution to confirm the state of vanillin production, and the solution was ultrasonically treated for 5 minutes and then filtered using a filtration device (13HP045AN). 20 μL of the filtrate was then submitted to HPLC for analysis of the components. Based on the analysis results, the amount of vanillin dissolved in the filtrate is shown in Table 2 below. In addition, the relative amount of oryzanol was calculated for wheat bran, rice bran, and raw corn husk. The relative amount is the relative value (%) of the amount of oryzanol dissolved in the filtrate after ozone treatment, when methanol and water were added to the sample before ozone treatment in a ratio of 50 wt%:50 wt%, and the amount of oryzanol dissolved in the filtrate after filtering was taken as 100%.

From the results in Table 2, vanillin was detected even without the action of ozone on each sample (ozone bubbling time 0 minutes), but this is because each sample contains a small amount of vanillin. It was also confirmed that the vanillin content in the sample increased due to the action of ozone. In other words, it was confirmed that vanillin was produced by ozone treatment. It was also confirmed that vanillin can be produced even in whole wheat, brown rice, and dried corn even when the kernels are still in the state, and that the vanillin production rate is higher in plant fractions such as wheat bran, rice bran, and raw corn husk. In addition, when comparing the relative amount of oryzanol before and after ozone treatment in these plant fractions, the relative amount of oryzanol decreased after ozone treatment, proving that oryzanol was converted to vanillin. In addition, as a comparative experiment (comparative example), nitrogen was bubbled instead of ozone under the same conditions, but there was no change in the amount of vanillin before and after bubbling.

Figure 5 shows high-speed liquid chromatograms obtained by bubbling ozone into rice bran, wheat bran, and raw corn husks for 0 minutes (before ozone treatment), 30 minutes, and 60 minutes from the above experiment. As shown by the arrow in Figure 5, an increase in the vanillin peak due to the action of ozone was confirmed.

In addition, using the same procedure as above, a vanillin production experiment was conducted on fresh western grass (Bermuda grass, oryzanol content: 0.12 mg/100 g), which contains almost no oryzanol. In this experiment, 20 mL of water was added to 1 g of fresh western grass, and the grass was cooled to 0°C. Ozone was bubbled into the solution for 0, 30, and 60 minutes to perform ozone treatment, and the amount of vanillin was measured using the same procedure as above. The measurement results are shown in Table 3 below.

<Experimental Example 5-2>
B: Method of immersing raw material in ozone water 20 mL of distilled water was cooled to 0°C in ice water. Ozone was bubbled into the cooled distilled water for 30 or 60 minutes at an ozone generation rate of 300 mg/hr to prepare ozone water. The following experiment was carried out using the prepared ozone water. Distilled water was used for the control experiment (comparative example). When the ozone concentration of the ozone water was measured using a simple ozone water checker "DOC-05A" (manufactured by Ebara Jitsugyo Co., Ltd.), the ozone concentration was 0.5 to 1.0 ppm for the ozone water bubbled for 30 minutes and 1.0 to 1.5 ppm for the ozone water bubbled for 60 minutes.

20 mL of ozone water was added to 4-5 g of the sample shown in Table 4 below. The same amount of distilled water was added to the sample in the control experiment. After the addition of the ozone water, the container was sealed with a lid and ultrasonicated for 30 minutes to bring the sample into contact with ozone (ozone treatment). After the ozone treatment, 20 mL of methanol was added to the sample, which was then ultrasonicated for 5 minutes and filtered using a filtration device (13HP045AN). 20 mL of the filtrate was then fed to HPLC to measure the content of the components. The amount of vanillin in the filtrate is shown in Table 3 below.

From the results in Table 4, it was confirmed that the amount of vanillin in the samples increased and vanillin was produced by immersion in ozone water. When a similar experiment was performed using a magnetic stirrer instead of ultrasonic treatment, the amount of vanillin after ozone treatment increased and similar results were obtained. In addition, when the brown rice and rice bran after ozone treatment were smelled, not only was the vanillin scent detectable, but the so-called "bran smell" disappeared and the vanillin scent was further enhanced, a special effect was obtained. This is presumably because the odor components such as the bran smell were decomposed and deodorized by the ozone treatment. Therefore, it was confirmed that in addition to imparting the vanillin scent, the deodorizing effect of the bran smell and the like can provide food ingredients that are more preferred by humans and livestock.

<Experimental Example 5-3>
C: Method of spraying ozone directly onto raw materials Samples shown in Table 5 below were prepared, and 100 mg of powder samples and 20-30 grains of grain samples were placed in 20 mL glass vials. At room temperature (around 20°C), while the containers were cooled with ice water, ozone was sprayed onto each sample in the containers at an ozone generation rate of 300 mg/hr for 5 minutes. The containers were then sealed with lids and left to stand at room temperature for 30 minutes (ozone treatment).

After leaving it for 30 minutes, a small hole was opened in the lid, 1 mL of methanol was poured in, and the mixture was ultrasonicated for 5 minutes, followed by centrifugation for 5 minutes. Next, 100 μL of the supernatant was taken and fed to a solid-phase separation column (Phenomenex, 8B-S001-EAK) to remove fats and oils. 300 μL of methanol was added to the separated material, and 20 μL was taken from the 400 μL fraction and fed to HPLC to measure the amount of each component. The measured amount of vanillin is shown in Table 5 below. The relative amount of oryzanol was also calculated for wheat bran, rice bran, and raw corn husk.

The results in Table 5 confirm that vanillin can be produced even when ozone is sprayed directly onto the samples. Furthermore, the change in the relative amount of oryzanol confirmed that oryzanol was converted to vanillin by ozone treatment. It was also confirmed that the vanillin content increased in millet such as hulled foxtail millet, millet, and barnyard millet, proving that these millet also contain oryzanol. When the aroma of each sample after ozone treatment was confirmed, a vanillin scent was confirmed. Of these, it was confirmed that rice bran, wheat bran, and raw corn husks had a pleasant aroma, with a vanillin scent rising from the sample when water was added to it. It was also confirmed that the bran odor and fishy odor of the samples were reduced.

According to Table 5, among the cereals, foxtail millet has the highest vanillin production rate, followed by barnyard millet and then millet, in which the production rate decreases. This is thought to be because the oryzanol content is lowest in foxtail millet, barnyard millet, and millet, in that order. Table 6 below shows the oryzanol content in foxtail millet, barnyard millet, and millet.

Next, a vanillin production experiment was conducted by changing the ozone spraying time. 20-30 grains of the samples shown in Table 7 below were placed in 20 mL glass vials, and ozone was sprayed onto them for 1 minute, 5 minutes, and 10 minutes at room temperature or while cooled with ice water (0°C) at an ozone generation rate of 300 mg/hr. The amount of vanillin was then measured using the same procedure as above. The measurement results are shown in Table 7 below.

In addition, using the same procedure as above, vanillin production experiments were conducted by directly spraying ozone onto buckwheat (oryzanol content: 0.08 mg/100 g) and fresh western grass (Bermuda grass, oryzanol content: 0.12 mg/100 g) which contains almost no oryzanol, for 1 minute, 5 minutes, and 10 minutes at room temperature, and the amount of vanillin was measured. The measurement results are shown in Table 8 below.

From the results in Table 7, it was confirmed that the amount of vanillin produced depends on the time of ozone spraying, regardless of whether the treatment temperature is room temperature or in ice water, and the longer the ozone spraying time, the greater the amount of vanillin produced. Since oryzanol is localized on the outside of the fruits of grains and other foods, it can be assumed that by spraying ozone on the grains as they are, oryzanol is preferentially decomposed by ozone over the oil and fat components contained therein. For this reason, vanillin can be produced even from the grains as they are, and various food materials, feed materials, foods, and feeds with vanillin aroma can be provided. In addition, compared to the case of bubbling ozone or immersion in ozone water, the process of removing the solvent and drying can be omitted, and the decrease in vanillin aroma can be suppressed. In contrast, as shown in Table 8, in unpolished buckwheat and fresh western grass, which contain almost no oryzanol, the amount of vanillin did not increase after ozone spraying compared to before ozone spraying.

<Experimental Example 6: Experiment to confirm changes in the amount of oryzanol and vanillin in a sample>
Figures 6 to 8 show high performance liquid chromatograms obtained before and after ozone treatment for wheat bran, rice bran, and raw corn husks containing oryzanol for 10 minutes in the same manner as in Experimental Example 5-3. The results shown in these figures confirmed that the peaks of oryzanol (wheat bran oryzanol, rice bran oryzanol, and raw corn husk oryzanol) were reduced by ozone treatment of each sample. In other words, it was confirmed that the oryzanol in the samples was converted to vanillin, resulting in a decrease in the amount of oryzanol.

Figures 9 and 10 show high-performance liquid chromatograms of wheat bran and foxtail millet containing oryzanol before and after ozone treatment by directly spraying ozone onto them for 5 or 10 minutes in the same manner as in Experimental Example 5-3 above. As a comparative experiment, the same experiment was also conducted by directly spraying ozone onto quinoa (Chenopodium quinoa, Peruvian quinoa, oryzanol content: 0.06 mg/100 g), buckwheat with husks, and fresh western grass (Bermuda grass), which contains almost no oryzanol. 300 mg of fresh western grass was used. High-performance liquid chromatograms of quinoa, buckwheat, and fresh western grass are shown in Figures 11 to 13, respectively. For fresh western grass, 1 g of fresh western grass was placed in water and ozone was bubbled into the solution for 10 minutes (see the procedure in Experimental Example 5-1 above). The high-performance liquid chromatogram from this experiment is shown in Figure 14.

From the results of Figures 6 to 14, it was confirmed that in wheat bran and unhulled foxtail millet, which contain oryzanol, the vanillin peak (elution time 11.5-7 minutes) increased by ozone treatment, and vanillin (wheat bran vanillin, foxtail millet vanillin) was produced. In contrast, in quinoa, unhulled buckwheat, and fresh western grass, which contain almost no oryzanol, the vanillin peak did not change even after ozone treatment, and it was confirmed that vanillin was not produced. From these experimental results and the result shown in Figure 6 (the oryzanol peak of wheat bran decreased), it was confirmed that vanillin was produced from oryzanol by ozone treatment. In addition, since vanillin was not produced from quinoa, unhulled buckwheat, and fresh western grass, which contain almost no oryzanol, it was confirmed that the vanillin produced by ozone treatment was produced from oryzanol, not from diferulic acid in the lignin of the cell wall.

<Experimental Example 7: Sensory Evaluation Test>
The following samples were treated with ozone and then subjected to a sensory evaluation test.
・Rice bran: 100 mg (ozone treatment time: 0 minutes, 1 minute, 5 minutes)
Raw corn husks: 100 mg (ozone treatment time: 0 min, 1 min, 5 min)
・Brown rice grains: 30 grains (ozone treatment time: 0 minutes, 1 minute)
・Whole wheat grains (whole wheat grains): 20 grains (ozone treatment time: 0 minutes, 1 minute)
Corn kernels: 10 kernels (ozone treatment time: 0 min, 1 min)
The above samples were each placed in a glass vial, and a sample before ozone treatment (0 minutes) and a sample directly sprayed with ozone for the above treatment time were prepared. The glass vials were then sealed with lids and left to stand at room temperature for 3 hours for rice bran and raw corn husks, and for 2 hours for brown rice grains, brown wheat grains, and corn grains. After standing, three panelists opened the lids of the glass vials and confirmed the aroma of each sample. Next, 1 mL of water was added to the glass vial, and the aroma was confirmed. The results are shown in Table 9 below.

The results in Table 9 confirm that ozone treatment can impart a vanillin scent or other pleasant aroma to the sample. It is speculated that this pleasant aroma is a unique aroma released as a result of the vanillin produced by ozone treatment intertwining with other aroma components contained in the sample. Furthermore, it was confirmed that the unique odors of the sample, such as the rice bran smell and fishy smell, were eliminated, resulting in an aroma that leaves an overall favorable impression.

Although the embodiments and examples (experimental examples) of the present invention have been described in detail above, the specific configuration is not limited to these embodiments and examples, and design changes that do not deviate from the gist of the present invention are included in the present invention.

Claims (9)

The method includes a step of reacting ozone with a raw material containing at least one selected from the fruits of edible or feed Gramineous plants and fractions thereof,
The method for producing a food material or feed material, wherein the step of applying ozone is at least any one selected from the group consisting of a step of passing the ozone through a solution of the raw material in water, alcohol, or a mixture of water and alcohol, a step of immersing the raw material in ozone water, and a step of spraying the ozone directly onto the raw material . 2. The method for producing a food material or feed material according to claim 1 , wherein the Gramineae plant is any one of rice, wheat, corn, foxtail millet, and barnyard millet, and the fruits or fractions thereof contain ferulic acid esters. 3. The method for producing a food material or a feed material according to claim 1 , wherein the step of reacting with ozone is carried out under atmospheric pressure at a temperature of 0° C. or higher and 30° C. or lower. A food material or feed material imparted with a vanillin aroma, which is obtained by the method for producing a food material or feed material according to any one of claims 1 to 3 . 5. The food or feed material having a vanillin aroma according to claim 4 , which contains 70 μg/1g or more of vanillin. The food material or feed material obtained by the method for producing a food material or feed material according to any one of claims 1 to 3 is used as a raw material for food or feed.
A method for producing a food or feed comprising the steps of: A food or feed imparted with a vanillin aroma, obtained by the method for producing a food or feed according to claim 6 . a step of dispersing at least one raw material selected from oryzanol and a plant fraction containing said oryzanol in a 10% to 35% ethanol solution to obtain a dispersion;
and bubbling ozone through the dispersion,
In the step of obtaining the dispersion, ethanol is added to the raw material, and then water is added to obtain a 10% to 35% ethanol solution;
In the step of aerating ozone, a pH adjuster is added so that the pH of the dispersion liquid is 2 or more and 8 or less.
1. A method for producing vanillin, comprising the steps of: 9. The method for producing vanillin according to claim 8 , wherein the oryzanol is extracted from the plant fraction, the plant fraction being any one of rice bran, corn husk, wheat bran and whole foxtail millet.