CN102300477A - Method for producing red pigment and food and beverage products containing red pigment - Google Patents

Abstract

Provided is a method for producing a natural red pigment, particularly a plant-based red pigment. The method involves producing a red pigment by reacting a protein hydrolysis product with an iridoid compound having a carboxyl group at position 4 of an iridoid skeleton. The protein hydrolysis product has an amino acid content of at least 35 wt% in terms of the protein hydrolysis product dry weight, and according to ninhydrin assay, at least 50 wt% of the amino acid is glutamic acid and aspartic acid and the ratio of the leucine weight to the total weight of the glutamic acid and aspartic acid is no greater than 8 wt%. It is also possible to react the protein hydrolysis product and taurine or a taurine-containing substance with the iridoid compound.

Description

Production method of red pigment and food and drink containing the red pigment

technical field

The present invention relates to a method for producing red pigment, in particular to a method for producing red pigment using iridoid compound and protein hydrolyzate. Moreover, this invention relates to the food-drinks containing the red pigment obtained by this method.

Background technique

From the viewpoint of food safety, more and more consumers pay attention to food additives. Under the condition that such consumers are constantly increasing, food additives derived from natural products, especially plants, are welcomed by consumers, and then by those skilled in the field of food manufacturing.

One of the food additives includes red pigment. Red pigments include gardenia red pigment, safflower red pigment, edible red No. 2, edible red No. 3, edible red No. 40, anthocyanin, beet red, and cochineal pigment and other pigments. For example, a red pigment is produced by reacting an aglucone of an iridoid glycoside compound obtained from a gardenia fruit extract with a substance containing a primary amino group under acidic conditions.

Patent Document 1 describes a method for producing a red pigment. This production method is characterized in that an iridoid glycoside compound and a substance having a primary amino group are reacted under acidic conditions. Examples of the substance having primary amino groups include amino acids, soybean protein, and peptone (Table 1, Example IV).

The method for producing a red pigment in Patent Document 2 is characterized in that the substance (A) having a carboxyl group at the 4-position of the iridoid glycoside skeleton in the iridoid glycoside compound is 2 moles relative to the substance (A). An organic acid selected from the group consisting of citric acid, malic acid, succinic acid, tartaric acid, adipic acid, fumaric acid, ascorbic acid, and erythorbic acid (erythorbic acid) in equivalent or more is 0.7 relative to the substance (A) Arginine (arginine), lysine (lysine), aspartic acid (aspartic acid), glutamic acid (glutamic acid) or their salts in molar equivalents or more react within the range of pH 3-6.

The method for producing gardenia red pigment in Patent Document 3 is characterized in that: among the iridoid glycoside compounds, a substance having a carboxyl group at the 4-position of the iridoid glycoside skeleton and a substance containing a primary amino group are placed in the five-carbon sugar In the presence of acidic conditions.

Patent Document 4 describes a method of producing a blue pigment under aerobic conditions by allowing an iridoid glycoside ligand and a substance containing taurine to coexist. This method is characterized in that the blue pigment is produced in the presence of a polyphenol compound, or the polyphenol compound is added after the blue pigment is produced.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 54-86668

Patent Document 2: Japanese Patent Laid-Open No. 3-277663

Patent Document 3: Japanese Patent Laid-Open No. 5-59296

Patent Document 4: Japanese Patent Laid-Open No. 7-111896

Contents of the invention

[Problem to be Solved by the Invention]

From the viewpoint of food safety, the red pigment is required to be derived from natural products, especially plants.

In addition, the color tone of the produced red pigment is required to be bright and vivid. Furthermore, the dye is required to be robust, that is, the dye is required to have sufficient acid resistance, heat resistance, and light resistance. As the use of red pigments continues to expand, it is desired that red pigments maintain their red color under various conditions in order to apply them to various foods.

An object of the present invention is to provide a method for producing a red pigment satisfying these requirements.

[means to solve the problem]

The present invention provides a method for producing a red pigment by reacting an iridoid glycoside compound having a carboxyl group at the 4-position of an iridoid glycoside skeleton with a protein hydrolyzate to produce a red pigment. The method is characterized in that: in the protein hydrolyzate, the amino acid content relative to the dry weight of the hydrolyzate is 35% by weight or more; 50% by weight or more are glutamic acid and aspartic acid, and the ratio of the weight of leucine to the total weight of the glutamic acid and aspartic acid is 8% or less. Furthermore, the weight ratio of proline (proline) to the total weight of glutamic acid and aspartic acid may be 15% or less. In the present invention, the iridoid glycoside compound may be reacted with the protein hydrolyzate and taurine or a taurine-containing substance. The amount of taurine or the amount of taurine contained in the taurine-containing material is preferably more than 0% by weight to 35% by weight relative to the amino acid content of the protein hydrolyzate.

[Effect of the invention]

According to the present invention, a red pigment having a bright and vivid hue can be produced using a protein hydrolyzate as a raw material. That is, the red pigment produced by the method of the present invention is derived from plants. Furthermore, this red pigment has a bright and vivid hue.

In addition, the red pigment produced by the method of the present invention is excellent in acid resistance. In other words, when the pigment is placed under acidic conditions, it is not easy to precipitate. Furthermore, the red pigment produced by the method of this invention is excellent in light resistance and heat resistance. That is, even if the pigment is irradiated with light, the pigment fades little, and even if it is exposed to heat, the color unit of the pigment is maintained. In addition, even when the dye is irradiated with light or exposed to heat, the amount of precipitation of the dye is small. That is, the red pigment produced by the method of the present invention is firm. As a result, the pigment can be used under various conditions, so the pigment can be used for coloring a wide range of foods.

The acid resistance is particularly excellent when a protein hydrolyzate and taurine or a taurine-containing substance are used as raw materials. The red pigment obtained by using protein hydrolyzate and taurine or a substance containing taurine is less prone to turbidity or precipitation even under acidic conditions with a pH value of 3.5 or less. Therefore, the red pigment can be used under a wider range of conditions, so the red pigment can be used for coloring a wider range of foods, especially acidic foods.

Furthermore, in the method of the present invention, even if the red pigment produced by reacting the protein hydrolyzate and taurine or a substance containing taurine is mixed with an anthocyanin pigment, turbidity or precipitation does not easily occur. That is, the red pigment of the present invention can be used together with an anthocyanin pigment. Therefore, by using the red pigment of this invention together with an anthocyanin pigment, the red hue of food-drinks can be adjusted more finely.

The production method of the present invention ensures sufficient yield of red pigment. Thereby, red pigment can be produced efficiently. As a result, manufacturing costs can be reduced.

Detailed ways

The so-called "iridoid glycoside compound having a carboxyl group at the 4-position of the iridoid glycoside skeleton" in the present invention refers to a glycoside represented by the following formula (I) and/or the following formula (II ) represented by the compound. The glycoside represented by formula (I) is, for example, geniposidic acid. The compound represented by formula (II) is, for example, a ligand of geniposide.

[chemical 1]

Gardenia fruit extract contains a large amount of iridoid glycoside compounds. Gardenias are, for example, Gardenia augusta Merrill and Gardenia jasminoldes Ellis. The fruit extract may contain a compound having a carboxyl group (-COOH group) at the 4-position of the iridoid glycoside skeleton such as geniposide, and a compound having a carboxyl group (-COOH group) at the 4-position of the iridoid glycoside skeleton such as geniposide. A compound with a carbomethoxy group (-COOCH ₃ group) in the position. The methyl carboxyl group of the carbomethoxy group-containing compound can be converted into the carboxyl group by ester hydrolysis. This ester hydrolysis is carried out by allowing an alkaline solution, an OH-type ion exchange resin, an enzyme having esterase activity, or the like to act alone or in combination. The fruit extract can be obtained, for example, by extracting with hydrous ethanol or water from the dried fruit of Gardenia jasminoides. With regard to geniposide, commercially available products with increased purity are also available as crude or refined.

The protein hydrolyzate of this invention is obtained by hydrolyzing arbitrary proteins. This hydrolysis can be performed using an acid, an enzyme, or the like. Examples of the acid include hydrochloric acid. Examples of the enzyme include papain, bromelain, thermolysin, red yeast rice or a red yeast rice decomposition product, or other proteases.

In the method of the present invention, the protein hydrolyzate can also be used in the form of a mixture containing an excipient. Examples of the excipient include excipients commonly used in this technical field, such as dextrin, lactose, and starch. This excipient can be added to the protein hydrolyzate before spray drying of the protein hydrolyzate described below, or as a bulking agent after drying, for example. The content of excipients can be determined by conventional techniques in this technical field. The content of dextrin and starch can be measured, for example, by performing a Somogyi-Nelson method or an enzymatic method after hydrolysis. The lactose content can be measured, for example, by a high performance liquid chromatography (High Performance Liquid Chromatography, HPLC) method.

In the present invention, the protein hydrolyzate may contain substances other than amino acids, such as water, salt, peptides, proteins, nitrogen-containing substances that do not affect the amino acid analysis device, and the like. These substances other than amino acids may be produced and/or added during the production of the protein hydrolyzate.

Examples of the protein hydrolyzate of the present invention include gluten (gluten) hydrolyzate. Examples of the gluten hydrolyzate include wheat gluten hydrolyzate, corn gluten hydrolyzate, gluten hydrolyzate derived from cereals such as barley and rye, and mixtures thereof. As the protein hydrolyzate, commercially available wheat gluten hydrolyzate can be used. Gluten is usually obtained as a by-product of making wheat starch from wheat flour. For example, when a kneaded product obtained by adding a small amount of water to wheat flour and kneading it tightly is washed with water, the wheat starch is suspended in water, but solid lumps remain without being suspended in water. This block contains gluten, and furthermore contains about 60 mass % - 70 mass % of moisture. Water can also be removed from the block to improve preservation, or it can be used as it is. Gluten can be in the form of paste, powder or granules.

The "dry weight of the hydrolyzate" in the present invention refers to the weight of the protein hydrolyzate excluding the weight of excipients and moisture. The dry weight is measured by a normal-pressure heating and drying method using an electronic moisture meter (Shimadzu Corporation, MOC-120H) or the like. In this method, heat drying is performed by heating at 120° C. with an infrared heater. The weight of moisture is the amount of reduction when the weight is constant in heat drying. In the present invention, the lower limit of the amino acid content relative to the dry weight of the protein hydrolyzate is 35% by weight, preferably 36% by weight, more preferably 37% by weight, further preferably 38% by weight, further preferably 39% by weight, and still more preferably 40% by weight , Still more preferably 41% by weight, Even more preferably 42% by weight. With this amino acid content, a good red color is achieved, the pigment is firmed, and sufficient color power is achieved. In the present invention, the upper limit of the amino acid content relative to the dry weight of the protein hydrolyzate can be any value, for example, it can be 99% by weight, 98% by weight, 97% by weight, 96% by weight, 95% by weight, 90% by weight, 85% by weight % by weight, 80% by weight, 75% by weight or 70% by weight. In the present invention, the upper limit and lower limit of the amino acid content can be appropriately selected from the above values, for example, it can be 35% by weight to 99% by weight, especially 36% by weight to 98% by weight, and more particularly 37% by weight to 97% by weight. The amino acid content is determined from the analysis results of the amino acid composition by the ninhydrin method. In the ninhydrin method, the amino acid is first separated by HPLC (L-7000, Hitachi High-Technologies Corporation), and then the absorbance of the color developed by the ninhydrin reaction is measured to analyze the amino acid composition ( For example, refer to "Hygienic Test Law Notes 2005, edited by the Pharmaceutical Society of Japan, published in February 2005, Kanehara Publishing").

The so-called amino acid content refers to the weight % of free amino acids in the dry weight of protein hydrolyzate, that is to say, aspartic acid, threonine (threonine), serine (serine), glutamic acid, proline, Glycine, alanine, cysteine, valine, methionine, isoleucine, leucine, tyrosine , phenylalanine, lysine, histidine (histidine), arginine, glutamine (glutamine), asparagine (asparagine) and tryptophan (tryptophan) accounted for by weight %. In the present invention, free amino acids do not contain amino acids in proteins or peptides.

In the present invention, the weight of free amino acids contained in a protein hydrolyzate is a value measured by the ninhydrin method. When measured by the ninhydrin method, glutamine is obtained as glutamic acid. That is, the amount of glutamic acid determined by the ninhydrin method is the total amount of glutamine and glutamic acid in free amino acids. Similarly, when measured by the ninhydrin method, asparagine is obtained as aspartic acid. That is, the amount of aspartic acid determined by the ninhydrin method is the total amount of asparagine and aspartic acid in free amino acids.

In the present invention, the lower limit of the total weight of glutamic acid and aspartic acid in the amino acid content is 50% by weight, preferably 52% by weight, more preferably 54% by weight, further preferably 56% by weight, and even more preferably 58% by weight. %. By using the total weight of glutamic acid and aspartic acid, a good red color is achieved, the pigment becomes firm, and sufficient color strength is achieved. The upper limit of the total weight may be any value, for example, 99% by weight, 98% by weight, 97% by weight or 96% by weight. In the present invention, the upper limit and the lower limit are appropriately selected from the above values, for example, 50 to 99% by weight, 52 to 98% by weight, or 54 to 97% by weight.

In the present invention, the ratio of the weight of leucine in the protein hydrolyzate to the total weight of glutamic acid and aspartic acid is 8% or less, preferably 7% or less, more preferably 6% or less. In the method of the present invention, the lower the ratio, the better, and the protein hydrolyzate may not contain leucine. With said ratios, red pigments with bright and vivid hues can be obtained. Furthermore, with the above ratio, a red pigment excellent in acid resistance can be obtained, and a sufficient yield of the red pigment can be ensured. This ratio was determined by analyzing the amino acid composition by the ninhydrin method.

In the present invention, the weight ratio of proline in the protein hydrolyzate to the total weight of glutamic acid and aspartic acid is 15% or less, preferably 12% or less, more preferably 10% or less. In the method of the present invention, the lower the ratio, the better, and the protein hydrolyzate may not contain proline. With this ratio, in particular, a red pigment excellent in heat resistance or light resistance can be obtained. This ratio was determined by analyzing the amino acid composition by the ninhydrin method.

These ratios can be achieved by hydrolyzing, neutralizing and filtering the protein, generating a precipitate by arbitrarily adjusting the pH value or cooling, and then arbitrarily dissolving the precipitate, and the like.

In the case of protein hydrolysis using, for example, acids, the ratio can be achieved in the filtrate of the protein hydrolyzate by neutralizing it and then filtering it. As the acid, hydrochloric acid or the like can be used. The hydrolysis method can be appropriately set according to the protein used and the hydrolyzate to be obtained, for example, 3M-6M hydrochloric acid is used to treat at 80°C-120°C for 10 hours-20 hours.

This neutralization can be performed by adding a base such as sodium hydroxide or potassium hydroxide. The neutralization conditions can be appropriately set according to the acid and protein used in the hydrolysis and the hydrolyzate to be obtained.

This filtration can be performed by natural filtration, reduced-pressure filtration, pressure filtration or centrifugal filtration, and is preferably performed by pressure filtration. This pressure filtration can be performed using a filter press.

This pH adjustment is performed by adjusting the filtrate to pH 2-4. Then, the filtrate is cooled and stirred to form a precipitate, and a cake (cake) obtained by further filtering the filtrate containing the precipitate can be used as a protein hydrolyzate having the above ratio. This pH adjustment can be performed with acids such as hydrochloric acid. The filtrate may also be concentrated to 1.2 to 2 times using an evaporator before the pH adjustment. In the cooling, the temperature of the filtrate is cooled to 40°C or lower, preferably 30°C or lower, more preferably 20°C or lower, even more preferably 10°C or lower. The agitation may be performed in order to avoid a reduction in the amount of the precipitate that continues to be used for filtration due to the sedimentation of the generated precipitate. This filtration can be performed by natural filtration, reduced-pressure filtration, pressurized filtration, or centrifugal filtration. The filter cake is washed again by resuspension in water, filtered again and the resulting filter cake is dried and used as protein hydrolyzate in the stated proportions, but can also be used directly. By repeating this washing and filtration, the ratio can be reduced.

The obtained filter cake was suspended in water, and the pH was adjusted to 4 to 6 to dissolve the filter cake, and then filtered to obtain a filtrate. This filtrate can be used as the protein hydrolyzate. This pH adjustment can be performed with an alkali such as sodium hydroxide.

These filtrates can be spray-dried using a spray dryer. The resulting dry powder can also be used as the protein hydrolyzate. Excipients such as dextrin can be added to the filtrate before spray drying.

Taurine is also known as 2-aminoethanesulfonic acid (2-aminoethanesulfonic acid). Taurine is commercially available, for example, from Nacalai Tesque Co., Ltd., Wako Pure Chemical Industries, Ltd. or Japan Clinic Co., Ltd. The taurine-containing substance in the present invention refers to a substance having a total content of amino acids other than taurine and peptides of 10% by weight or less and a taurine content of 30% by weight or more. Preferably, the so-called taurine-containing substance in the present invention means that the taurine content is 50% by weight or more, 70% by weight or more, 80% by weight or more, preferably 85% by weight or more, more preferably 90% by weight or more, More preferably, it is 95% by weight or more. The substance containing taurine can also be an extract from muscle or viscera of animals or fish and shellfish. Examples of the taurine-containing substance include, for example: a taurine-containing substance extracted from the muscle extract of cuttlefish or octopus, or a taurine-containing substance extracted from a pig or bovine muscle extract, or A taurine-containing substance extracted from oyster meat, or a taurine-containing substance extracted from animal bile. Methods for obtaining these taurine-containing substances are known to those skilled in the art, and are described, for example, in JP-A-2005-179215.

In the method of the present invention, relative to the amino acid content in the protein hydrolyzate, the amount of taurine or the amount of taurine contained in the taurine-containing substance is more than 0% by weight to 40% by weight, Preferably it exceeds 0% by weight to 35% by weight, more preferably 5% by weight to 30% by weight. Utilize the amount of this taurine or the amount of taurine contained in this taurine-containing material, the acid resistance of the produced red pigment, especially the acid resistance below pH 3.5, is obviously improved, and can obtain Nice red pigment. When the upper limit is exceeded, a good red color cannot be obtained. When it is less than this lower limit, the improvement of acid resistance of pH 3.5 or less cannot be aimed at. In addition, when the amount of taurine is more than 35% by weight to 40% by weight, in order to achieve a better red hue in the Lab system described below, for example, in order to make the red hue in the L In particular, glutamic acid and aspartic acid in the amino acid content are required to be 70 or more and a is 30 or more. In particular, in order to make a red hue in the Lab system, L is 70 or more, a is 30 or more, and b is -8 or less. The lower limit of the total weight of the acids exceeds 92%, preferably exceeds 93%. In this case, the upper limit of the total weight may be any value, for example, 99% by weight, 98% by weight, 97% by weight or 96% by weight.

The reaction of the iridoid glycoside compound having a carboxyl group on the 4-position of the iridoid glycoside skeleton and the protein hydrolyzate in the production method of the present invention can be carried out under any conditions, usually including the following (a) to (f) step.

(a) Mixing of iridoid glycoside compound and protein hydrolyzate

Amino acids (especially glutamine, asparagine, glutamic acid, and aspartic acid) in the protein hydrolyzate are 0.5 mol or more, preferably 0.5 mol to 5 mol, relative to 1 mol of the iridoid glycoside compound, More preferably, the iridoid glycoside compound and the protein hydrolyzate are mixed in an aspect of 0.6 mol to 3 mol, still more preferably 0.7 mol to 2 mol. When using an iridoid glycoside compound having a methyl ester group at the 4-position of the iridoid glycoside skeleton, the methyl ester group is converted into a carboxyl group by ester hydrolysis before the mixing. This ester hydrolysis can be carried out by allowing an alkaline solution, an OH-type ion exchange resin, an enzyme having esterase activity, or the like to act alone or in combination. Examples of the alkaline solution include sodium hydroxide solution, and granular or scaly solid sodium hydroxide may be added to the iridoid glycoside compound aqueous solution. For example, by mixing 10% by weight to 40% by weight of NaOH solution and 40% by weight to 60% by weight of iridoid glycoside compound aqueous solution at a weight ratio of 40:60 to 60:40, and then the ratio is Water is added in an amount of 10% by weight to 30% by weight, and the ester is hydrolyzed by heating at 30°C to 70°C for 1 hour to 3 hours. When taurine or a substance containing taurine is also reacted with a protein hydrolyzate, the taurine or a substance containing taurine may be before the heating of the reaction solution in (e) below, more preferably the following ( d) is added to the mixture prior to the enzymatic reaction. When taurine or taurine-containing substances are also reacted with protein hydrolyzate, the moles of amino acids (especially glutamine, asparagine, glutamic acid and aspartic acid) in protein hydrolyzate The total amount of taurine and the molar amount of taurine is 0.5 moles or more, preferably 0.5 moles to 5 moles, more preferably 0.6 moles to 3 moles, and still more preferably 0.7 moles to 2 moles, relative to 1 mole of the iridoid glycoside compound. Way, to add protein hydrolyzate and taurine or taurine-containing substances and iridoid glycoside compounds.

(b) Addition of organic acid

An organic acid may be optionally added to the mixture of the iridoid glycoside compound and the protein hydrolyzate. Examples of the organic acid include citric acid, malic acid, tartaric acid, adipic acid, fumaric acid, ascorbic acid, succinic acid, or a mixture of these acids. The organic acid can be added in an amount of 2 mol or more, preferably 3 mol to 6 mol, based on 1 mol of the iridoid glycoside compound.

(c) pH adjustment using alkali

An alkaline solution is added to the mixture obtained by said (a), or (a) and (b), and pH is adjusted to 3-6, Preferably it is 4-5. Examples of the alkaline solution include a 10% by weight to 40% by weight sodium hydroxide solution, which may be adjusted by adding the above-mentioned solid sodium hydroxide.

(d) Reaction utilizing an enzyme having β-glucosidase activity

An enzyme having β-glucosidase activity is added to the pH-adjusted mixture of (c) to perform an enzyme reaction. Enzymes with β-glucosidase activity include, for example: Cellulase AP5 (Amano Enzyme Co., Ltd.), Cellulase Onozuka 3S (Yakult Pharmaceutical Industry) Co., Ltd.), Sumizyme AC (New Japan Chemical Industry Co., Ltd.), Cellulase (Cellulase) Y2-NC or Cellulase (Cellulase) Y-NC (Yakult Pharmaceutical Industry (Yakult Pharmaceutical Industry) Co., Ltd.), etc. The conditions of the enzyme reaction are appropriately selected according to the selected enzyme. Typically, the enzymatic reaction is carried out at 30°C to 70°C for 1 hour to 30 hours. The iridoid glycoside compound is hydrolyzed by the enzyme reaction to obtain the ligand of the iridoid glycoside compound. The ligand is used as a raw material to carry out steps (a) to (f), and (d) can be omitted.

(e) Heating of the reaction solution

After the enzyme reaction in (d), the reaction solution is heated at 80°C to 100°C for 0.5 to 12 hours, preferably for 1 to 6 hours, more preferably for 2 to 3 hours.

(f) Pigment separation

The separation method of the resulting pigment can be appropriately selected by those skilled in the art. Examples of the separation method include centrifugation, filtration, especially ultrafiltration, acid precipitation, addition of a hydrophilic organic solvent or ion exchange, or a combination of these methods.

In the present invention, the so-called hue refers to the hue in the Hunter-Lab color system. The colorimetric system is a three-dimensional colorimetric system composed of the orthogonal coordinates formed by the a and b axes representing the chromaticity and the L axis perpendicular thereto. If the value of a increases to the positive side, it means that the redness increases, and if it increases to the negative side, it means that the greenness increases. When the b value increases to the positive side, it means that the yellowness increases, and when it increases to the negative side, it means that the blueness increases. The L value corresponds to lightness. The color at L=100 is white, and the color at L=0 is black. The larger the L value, the brighter the color. The hue of the red pigment produced by the method of the present invention can be such that L is 70 or more, preferably 71 or more, more preferably 72 or more, and a is 30 or more, preferably 32 or more, more preferably 34 or more in the Lab colorimetric system. The combination of the values of L and a can be appropriately selected from the above-mentioned values, preferably L is 70 or more and a is 30 or more, more preferably L is 71 or more and a is 32 or more, still more preferably L is 72 or more and a is 34 above. More preferably, the hue of the red pigment produced by the method of the present invention can be set to be 70 or more, preferably 71 or more, more preferably 72 or more, and a to be 30 or more, preferably 32 or more, and more preferably in the Lab colorimetric system. Preferably it is 34 or more, and b is -8.0 or less, more preferably -8.2 or less, still more preferably -8.4 or less. The combination of the values of L, a and b can be appropriately selected from the above-mentioned values, preferably L is 70 or more, a is 30 or more and b is -8 or less, more preferably L is 71 or more, a is 32 or more and b is -8.2 or less, more preferably L is 72 or more, a is 34 or more, and b is -8.4 or less. A moderately bright and vivid red color can be realized by using the color tone having the above-mentioned values of L and a, or by using the color tone having the above-mentioned values of L, a, and b. That is, the color tone having the values of L and a or the color tone having the values of L, a, and b is a bright and vivid color tone. Furthermore, the redness of the hue is strong, and the pigment can be used alone to obtain the red color of the food or drink to be added.

The color tone is measured using a measuring device known to those skilled in the art. The measuring device may include a spectrocolorimeter (for example, SD5000 (Nippon Denshoku Industries, Ltd.)), a colorimetric colorimeter (for example, ZE6000, SZ-Σ80 or SE-2000 (all are Nippon Denshoku Industries, Ltd.)) and the like.

The red pigment produced by the method of the present invention is excellent in acid resistance. Because of its excellent acid resistance, even if the pigment solution is placed under acidic conditions, it is not easy to form precipitation or turbidity. In the present invention, the term "acid resistance" refers to the property of maintaining the color strength of the aqueous dye solution with little turbidity or precipitation originating from the dye in the aqueous dye solution under acidic conditions. In the present invention, the so-called excellent acid resistance means that the pigment residual rate after being placed at a pH value of 3.8 for 10 hours, 12 hours, 14 hours, 16 hours or 18 hours is 75% or more, preferably 80% or more, more preferably Preferably it is 85% or more, more preferably 90% or more, most preferably 95% or more. In other words, the red pigment produced by the method of the present invention has a pigment residual rate of 75% or more, preferably 80% or more, more preferably 85% or more, further preferably 90% or more, and most preferably 95% or more. In the present specification, the term "dye remaining rate" refers to the extent to which the dye remains in the supernatant after removing turbidity or precipitate generated in the dye solution. When turbidity or precipitation is generated, a pigment compound may exist in the turbidity or precipitation. In the method of the present invention, when taurine or a taurine-containing substance is also reacted with a protein hydrolyzate, the resulting red pigment is particularly excellent in acid resistance. The so-called particularly excellent acid resistance means that the pigment residual rate after being placed at a pH value of 3.5 for 10 hours, 12 hours, 14 hours, 16 hours or 18 hours is 75% or more, preferably 80% or more, more preferably 85% or more, more preferably 90% or more, most preferably 95% or more. The pigment remaining rate was evaluated by the method described in Example 4 below.

Moreover, this invention relates to the food-drinks containing the red pigment of this invention. That is, the red pigment of the present invention can be added to various food and beverages. Foods and drinks to which the red pigment of the present invention is added include, for example, noodles, liqueur, beverages, snacks, milk drinks, fillings, fish or meat sausages, etc., but are not limited to these food and drinks. In addition, the red pigment of the present invention can also be used together with other pigments. Such other pigments can be appropriately selected by those skilled in the art according to the desired color, and examples thereof include cyan pigments, yellow pigments, red pigments other than the red pigment of the present invention, and the like. In addition, when taurine or a taurine-containing substance is also used in the method of the present invention, the red pigment of the present invention can be used together with an anthocyanin-based dye. Even if the red pigment of the present invention obtained at this time is mixed with the anthocyanin-based pigment, there is little generation of turbidity or precipitation. The anthocyanin-based pigments include, for example, red cabbage pigments, carrot pigments, purple sweet potato pigments, purple corn pigments, elderberry pigments, perilla pigments, and grape peel pigments, but are not limited to these pigments.

The red pigment of the present invention can be added to food and drink under acidic conditions. Acidic food and drink may be acidic alone, or may be acidic as a result of adding various acids. The food and drink to which the red pigment of this invention was added has little discoloration even if it is acidic. Since there is little discoloration, the quality of food and beverages will not be impaired. Examples of the food and drink under acidic conditions include food and drink with a pH of 5 or less, food with a pH of 4.5 or less, food with a pH of 4 or less, or food with a pH of 3.5 or less. Examples of such food and drink include, but are not limited to, jelly, candy, drinks with fruit juice or juice-flavored drinks, frozen snacks, frozen snacks, and pickles.

In particular, the red pigment of the present invention can be added to food and beverages to be subjected to high-temperature treatment. Such food and beverages are, for example, food and beverages that are heated during a manufacturing step or a conditioning/processing step, during transportation or storage, and/or during product display, but are not limited to these. The food and drink to which the red pigment of the present invention is added has little discoloration even when the food and drink is heated during a manufacturing step or a preparation/processing step, during transportation or storage, and/or during a product display. Since there is little discoloration, the quality of food and beverages will not be impaired.

In particular, the red pigment of the present invention can be added to food or drink to be irradiated with light. Such food and beverages are, for example, food and beverages sold in bags or containers that cannot be shielded from light, such as polyethylene bags, PET bottles, and glass bottles, but are not limited to these food and beverages. Even if the food-drinks to which the red pigment of this invention was added is irradiated with light, discoloration is little. Since there is little discoloration, the quality of food and beverages will not be impaired.

The addition amount of the red pigment of the present invention in food and drink can be appropriately set according to the color of the food and drink to be obtained, for example, 0.001% by weight to 15% by weight, preferably 0.01% by weight to 10% by weight, more preferably 0.5% by weight ~5% by weight.

Examples are given below to illustrate the present invention, but the present invention is not limited to these examples.

In the following examples, the color strength and hue of the coloring liquid were measured. Their measurement methods are as follows.

The color power is measured by the color power measurement method, that is to say, the pigment solution is diluted with water or buffer solution as needed, and the maximum absorption wavelength of the visible part is measured by an ultraviolet-visible spectrophotometer (UV-2450, Shimadzu Corporation) The absorbance is obtained by multiplying the measured value by the dilution rate. The unit of color power is u/g, which represents the amount of pigment per 1 g of pigment solution, that is to say, the concentration of pigment expressed by the absorbance at the maximum absorption wavelength. The amount of pigment (u) is expressed by the product of the color power and the weight (g) of the pigment solution. That is, the amount of 1 u of the dye is the amount of the dye contained in 1 g of the dye solution whose absorbance is 1 when measured at the maximum absorption wavelength.

For hue, the obtained dye solution was diluted with water or a buffer solution so that the absorbance at the maximum absorption wavelength became 0.5, and the diluted solution was measured with a color difference meter (SZ-Σ80, Nippon Denshoku Kogyo Co., Ltd.).

Example 1

Manufacture of red pigment

(1) Preparation of wheat gluten hydrolyzate

Put 300 g of wheat-derived gluten (Wako Pure Chemical Industries, Ltd.), 500 g of water, and 350 ml of concentrated hydrochloric acid (special grade, Wako Pure Chemical Industries, Ltd.) into a 3-L two-neck round-bottomed flask with a magnetic rotor. A thermometer and a coil (dimroth) were installed on the flask, and the flask was immersed in an oil bath mounted on a hot stirrer (SR550, Advantec Co., Ltd.). The temperature of the oil bath was set at 130° C. to 140° C., the rotor in the flask was rotated, and the flask was heated for 15 hours while running tap water through the coil. After heating, the hydrolyzate in the flask was left to cool, and then the hydrolyzate was transferred to a beaker with a capacity of 2 L. While cooling the beaker, 620 g of a 25% by weight sodium hydroxide (special grade, Wako Pure Chemical Industries, Ltd.) aqueous solution was added to the hydrolyzate to neutralize the hydrolyzate to about pH 6. 10 g of Celite 500 (Tokyo Konno Shoten Co., Ltd.) was added to this neutralizing solution. A 150 mm No2 filter paper (Advantec Co., Ltd.) was set in a Buchner funnel, and 10 g of Celite 500 was precoated on the filter paper. The neutralized solution added with Celite 500 was suction-filtered using a suction bottle and a vacuum pump (Nihon-Buchi Co., Ltd., Vac. V500 type). The obtained filtrate was concentrated under reduced pressure using a rotary evaporator (N1, Tokyo Rikaiki Co., Ltd.) to a liquid weight of 1070 g. The concentrate was transferred to a 1-L beaker, and about 100 g of concentrated hydrochloric acid was added thereto to adjust the pH of the concentrate to 3.1. After the pH value was adjusted, it was placed in a refrigerator at about 5° C., and stirring was continued slowly for 2 days. The precipitate deposited as a result of this stirring was suction-filtered with a Buchner funnel provided with No2 filter paper of 125 mm. The obtained filter cake was suspended in 150 ml of cold deionized water, stirred, and then suction-filtered in the same manner. Finally, the obtained filter cake is subjected to suction filtration and cleaning with about 20 ml of ethanol. The obtained washed cake of 54.5 g was placed in a desiccator adjusted to 50° C. while being placed on the filter paper, and vacuum-dried for 7 hours. After drying, the filtrate was removed from the filter paper to obtain 35.4 g of a collapsible massive solid. The obtained solid was ground into a fine powder with a mortar. The obtained fine powder was used for the following experiment as a wheat gluten hydrolyzate (henceforth "hydrolyzate 1").

Hydrolyzate 1 contained 0.61% by weight of leucine, 0% by weight of proline, and 53.45% by weight of (glutamic acid + aspartic acid). The ratio of the weight of leucine in the hydrolyzate 1 to the total weight of glutamic acid and aspartic acid was 1%. In addition, the ratio of the weight of proline in the hydrolyzate 1 to the total weight of glutamic acid and aspartic acid was 0%. The amino acid content relative to the dry weight of the hydrolyzate 1 was 56.36% by weight. The weight ratio of (glutamic acid+aspartic acid) to the total amino acid content in hydrolyzate 1 was 94.84 weight%. These ratios were determined using the ninhydrin method. Table 1 shows the amino acid composition of hydrolyzate 1.

[Table 1]

Table 1. Composition of Amino Acids in Protein Hydrolyzates

sodium glutamate 67.53

Note) "-" means not detected.

Note 2) Sodium glutamate indicates the content when glutamic acid is made into monohydrate of sodium glutamate.

(2) Preparation of iridoid glycoside compounds

280 g of water and 350 g of 24% by weight sodium hydroxide were added to 350 g of the geniposide solution, and saponified at 60° C. for 2 hours to prepare a geniposide solution. 334 g of crystalline citric acid (Wako Pure Chemical Industries, Ltd., special grade citric acid) was added to the obtained geniposidic acid solution. The resulting mixed solution 13 was equally divided into 300 ml Erlenmeyer flasks with a volume of 300 ml.

(3) Manufacture of red pigment

Using one Erlenmeyer flask, hydrolyzate 1 was added thereto and mixed. The addition amount of the hydrolyzate 1 was adjusted so that the average molecular weight of the amino acid contained in the hydrolyzate 1 was 139 so that geniposide and the amino acid were equimolar. The average molecular weight is calculated by weighting the amino acid composition of commercially available gluten hydrolyzate (Nisshin Pharma Co., Ltd., WGH, http://www.wgh.jp/shiryoubako/000010.php) . Then, a 24% by weight sodium hydroxide solution was added to the mixture to bring the pH to 4.8. Water was further added to this mixture so that the liquid amount would be 220 g. Next, the inside of the Erlenmeyer flask was replaced with argon. After the substitution, 1 g of cellulase Y2NC (Yakult Pharmaceutical Industry Co., Ltd.) was added, covered with aluminum foil, and the enzyme reaction was performed at 53° C. to 55° C. for 22.5 hours. After the reaction, the reactant was heated at 85° C. to 95° C. for 3 hours using a heater (Yamato Scientific Co., Ltd., water bath incubator BT-25 (Water bath incubator BT-25)). Afterwards, the reaction was left to cool in a water bath (room temperature) for about 30 minutes. When the reactant becomes about 50° C. by standing and cooling, collect the reactant in a 1.5 ml Eppendorf pipette, and use a cooling centrifuge (Eppendorf (Eppendorf) Co., Ltd., cooling centrifuge 5415R) ) was centrifuged at 12000 rpm for 5 minutes to obtain a supernatant as a red pigment (hereinafter referred to as "red pigment 1").

Example 2

Manufacture of red pigment

(1) Preparation of wheat gluten hydrolyzate

Three types of gluten hydrolyzate (hereinafter referred to as "hydrolyzate 2", "hydrolyzate 3", and "hydrolyzate 4") were prepared in the same manner as hydrolyzate 1. These hydrolyzates were produced by a production method in which the conditions for forming the precipitate and the conditions for washing the precipitate in the method for producing the hydrolyzate 1 of Example 1 were appropriately adjusted.

The weight ratios of the leucine in the hydrolyzate 2 - the hydrolyzate 4 with respect to the total weight of glutamic acid and aspartic acid were 2%, 6%, and 4%, respectively. In addition, the ratio of the weight of proline in hydrolyzate 2-hydrolyzate 4 with respect to the total weight of glutamic acid and aspartic acid was all 0%. The amino acid content with respect to the dry weight of the hydrolyzate 2, the hydrolyzate 3, and the hydrolyzate 4 was 51.59 weight%, 44.66 weight%, and 46.68 weight%, respectively. The weight ratios of (glutamic acid+aspartic acid) to the total amino acid content in hydrolyzate 2, hydrolyzate 3, and hydrolyzate 4 were 88.16% by weight, 92.43% by weight, and 87.38% by weight, respectively.

The amount of amino acids contained in hydrolyzate 2 - hydrolyzate 4 was measured by the ninhydrin method. Table 2 shows the amino acid compositions of hydrolyzate 2 to hydrolyzate 4.

[Table 2]

Table 2. Composition of Amino Acids in Protein Hydrolyzates

sodium glutamate 56.71 52.10 51.05

Note) "-" means not detected.

Note 2) Sodium glutamate indicates the content when glutamic acid is made into monohydrate of sodium glutamate.

(2) Manufacture of red pigment

The red pigment was produced by the method similar to Example 1 except having used the hydrolyzate 2-hydrolyzate 4 instead of the hydrolyzate 1 described in Example 1. Hereinafter, the red pigment produced using the hydrolyzate 2, the hydrolyzate 3, and the hydrolyzate 4 are called "red pigment 2", "red pigment 3", and "red pigment 4", respectively.

Example 3

Manufacture of red pigment

(1) Preparation of wheat gluten hydrolyzate

Wheat gluten hydrolyzate (ML-30G, Shinshin Co., Ltd., hereinafter referred to as "hydrolyzate 5") was prepared. In hydrolyzate 5, the content of leucine was 2.1% by weight, and the content of (glutamic acid+aspartic acid) was 15.69% by weight. The ratio of the weight of leucine in the hydrolyzate 5 to the total weight of glutamic acid and aspartic acid was 13%. The ratio of the weight of proline in the hydrolyzate 5 to the total weight of glutamic acid and aspartic acid was 33%. The amino acid content relative to the dry weight of the hydrolyzate 5 was 35.29% by weight. The weight ratio of (glutamic acid+aspartic acid) to the total amino acid content in hydrolyzate 5 was 44.46 weight%. Table 3 shows the amino acid composition of hydrolyzate 5.

[table 3]

Table 3. Composition of Amino Acids in Protein Hydrolyzates

sodium glutamate 18.04

Note) "-" means not detected.

Note 2) Sodium glutamate is the content when glutamic acid is sodium glutamate monohydrate.

Hydrolyzate 4 and hydrolyzate 5 were mixed at a weight ratio of 80:20, 60:40 and 40:60 to prepare the weight of leucine in the hydrolyzate relative to the total weight of glutamic acid and aspartic acid. Gluten hydrolyzate in proportions of 5%, 6% and 8%. The amino acid content with respect to the dry weight of these hydrolyzates was 44.40 weight%, 42.12 weight%, and 39.85 weight%, respectively. The weight ratios of (glutamic acid + aspartic acid) to the total amino acid content in these hydrolyzates were 80.56% by weight, 73.00% by weight, and 64.57% by weight, respectively.

(2) Manufacture of red pigment

The red pigment was produced by the method similar to Example 1 except having used the hydrolyzate 1 of Example 1 respectively using the three types of gluten hydrolyzate prepared above. Hereinafter, the red pigments manufactured using the gluten hydrolyzate whose ratio is 5%, 6%, and 8% are called "red pigment 5", "red pigment 6", and "red pigment 7", respectively.

(comparative example 1)

Hydrolyzate 4 and hydrolyzate 5 were mixed at a weight ratio of 20:80 to prepare gluten hydrolyzate in which the weight ratio of leucine in the hydrolyzate to the total weight of glutamic acid and aspartic acid was 10%. things. The amino acid content with respect to the dry weight of this hydrolyzate was 37.57 weight%. The weight ratio of (glutamic acid+aspartic acid) to the total amino acid content in this hydrolyzate was 55.13 weight. Red pigment (henceforth "red pigment 8") was produced by the method similar to Example 1 except having used this gluten hydrolyzate instead of the hydrolyzate 1 described in Example 1.

(comparative example 2)

A red pigment (hereinafter referred to as "red pigment 9") was produced by the same method as in Example 1 except that hydrolyzate 5 was used instead of hydrolyzate 1 described in Example 1.

(comparative example 3)

Corn protein hydrolyzate (Amishin C, Shinjin Co., Ltd., hereinafter referred to as "hydrolyzate 6") was prepared. The leucine content of the hydrolyzate 6 was 0.86 weight%, and the (glutamic acid+aspartic acid) content was 5.36 weight%. The ratio of the weight of leucine to the total weight of glutamic acid and aspartic acid was 16%. The amino acid content relative to the dry weight was 12.63% by weight. The weight ratio of (glutamic acid+aspartic acid) to the total content of amino acids was 42.44% by weight. Table 4 shows the amino acid composition of hydrolyzate 6.

[Table 4]

Table 4. Composition of Amino Acids in Protein Hydrolyzates

sodium glutamate 8.62

Note) "-" means not detected.

Note 2) Sodium glutamate indicates the content when glutamic acid is made into monohydrate of sodium glutamate.

Except having used the hydrolyzate 6 instead of the hydrolyzate 1 described in Example 1, the red pigment (henceforth "red pigment 10") was produced by the method similar to Example 1.

Example 4

The color strength, hue and acid resistance of red pigments 1 to 7 of examples 1 to 3 and red pigments 8 to 10 of comparative examples 1 to 3 were measured respectively.

Table 5 shows the measurement results of color power and hue.

[table 5]

Table 5. Measurement results of color power and hue of red pigment

According to the results shown in Table 5, the hues of the red pigments 1 to 7 in Examples 1 to 3 are all such that L is 70 or more, a is 30 or more, and b is -8 or less. On the other hand, L of the red pigments 8 to 10 of Comparative Examples 1 to 3 was less than 70. Therefore, compared with the red pigment 8 - the red pigment 10 of the comparative example 1 - the comparative example 3, it turns out that the red pigment 1 - the red pigment 7 of Example 1 - Example 3 have a bright and vivid hue. Furthermore, the red pigment 1 - the red pigment 7 of the example had higher color power than the red pigment 8 - the red pigment 10 of the comparative example 1 - the comparative example 3.

The acid resistance was evaluated by measuring the color power of the dye solution left overnight under acidic conditions. The evaluation order is as follows. First, a 4-fold concentrated McIlvaine buffer was prepared. The buffer solution is to dissolve citric acid (Wako Pure Chemical Industries, Ltd., special grade citric acid) and disodium hydrogen phosphate dodecahydrate (Wako Pure Chemical Industries, Ltd., special grade disodium hydrogen phosphate dodecahydrate) A citric acid aqueous solution and a disodium hydrogenphosphate aqueous solution were prepared in water, and these aqueous solutions were mixed to prepare 10 g of each aqueous solution of pH 3.0, 3.4, 3.5, 3.8, or 4.0. Red pigment 1 to red pigment 10 were mixed in such a buffer solution (pH 3 to 4) that the color power was 5 u/g. The pH of the mixed solution was adjusted to 3.0, 3.4, 3.5, 3.8 or 4.0 with an 85% by weight aqueous phosphoric acid solution (special grade phosphoric acid from Wako Pure Chemical Industries, Ltd. was used for phosphoric acid). After pH adjustment, these mixtures were left to stand overnight in the refrigerator. After standing still overnight, the mixture was transferred to a test tube, and centrifuged at 3000 rpm for 10 minutes using a centrifuge (Japan Centrifuge Co., Ltd., tabletop centrifuge H-20) to obtain a supernatant. The color power of the supernatant was measured using the color power measurement method described above. Since the color power at the beginning of the acid treatment was 5u/g, the buffer solution with the same pH value as the supernatant after standing was diluted to 5 times accurately, and the absorbance of the diluted pigment solution was measured and multiplied by 100, and the resulting The value of is used as the pigment residual rate. The pigment residual rate is an indicator of acid resistance.

Table 6 shows the evaluation results of acid resistance. With regard to the evaluation criteria of acid resistance, if the color remaining rate at pH 3.8 is 90% or more, it is evaluated as very good (◎), if it is 75% or more and less than 90%, it is evaluated as good (○), and if it is less than 75%, it is evaluated as very good (◎). % was evaluated as poor (×).

[Table 6]

Table 6. Evaluation results of acid resistance

According to the results shown in Table 6, for the red pigments 1 to 6 of Examples 1 to 3, the pigment residual ratio at pH 3.8 was 90% or more, and the acid resistance of these pigments was very good. The red pigment 7 of the example has a pigment residual rate of 80.0% at pH 3.8, and the acid resistance of this pigment is good. On the other hand, the red pigment 1 to the red pigment 3 of the comparative example had a dye remaining ratio of less than 75% at pH 3.8, and these dyes were poor in acid resistance. In addition, the dye remaining ratio at pH 3.4 of red pigment 1 to red pigment 7 was 35% or more. On the other hand, the red pigment 1 to the red pigment 3 of the comparative example had a dye remaining rate of less than 31% at pH 3.4.

Example 5

Manufacture of red pigment

(1) Wheat gluten hydrolyzate

Hydrolyzate 4 used in Example 2 was used as wheat gluten hydrolyzate.

(2) Preparation of iridoid glycoside compounds

100 g of water and 215 g of 24% by weight sodium hydroxide were added to 238 g of the geniposide solution, and saponified at 60° C. for 2 hours to prepare a geniposidic acid solution. 205 g of crystalline citric acid (Wako Pure Chemical Industries, Ltd., special grade citric acid) was added to the obtained geniposidic acid solution. The resulting mixed solution was divided into 8 equal parts and put into 300 ml Erlenmeyer flasks respectively.

(3) Manufacture of red pigment

Using one Erlenmeyer flask, 10.7 g of hydrolyzate 4 was added thereto and mixed. The addition amount of the hydrolyzate 4 was adjusted so that the average molecular weight of the amino acid contained in the hydrolyzate 4 was 139 so that geniposide and the amino acid were equimolar. Then, a 24% by weight sodium hydroxide solution was added to the mixture to adjust the pH to 4.7. Water was further added to this mixture so that the liquid amount would be 220 g. Next, the inside of the Erlenmeyer flask was replaced with argon. After the replacement, 1 g of Cellulase Y2NC (Yakult Pharmaceutical Industry Co., Ltd.) was added, covered with aluminum foil, and the enzyme reaction was performed at 53° C. to 55° C. for 22.5 hours. After the reaction, the reaction solution was heated at 85° C. to 95° C. for 3 hours with a heater (Yamato Scientific Co., Ltd., water bath thermostat BT-25). Thereafter, the reaction solution was left to cool in a water bath (room temperature) for about 30 minutes. When the reaction solution becomes about 50° C. by standing to cool, collect the reaction solution in a 1.5 ml Eppendorf pipette, and use a cooling centrifuge (Eppendorf (Eppendorf) Co., Ltd., cooling centrifuge 5415R) to collect the reaction solution. The reaction solution was centrifuged at 12,000 rpm for 5 minutes to obtain a supernatant as a red pigment (hereinafter referred to as "red pigment 11").

Example 6

Manufacture of red pigment

Hydrolyzate 4 was changed so that the average molecular weight of glutamic acid and aspartic acid contained in hydrolyzate 4 was 139 so that geniposidic acid and the glutamic acid and aspartic acid were equimolar In addition to the addition amount, red pigment (hereinafter referred to as "red pigment 12") was produced in the same manner as in Example 5. The added amount of the hydrolyzate 4 was 12.4 g.

(comparative example 4)

A gluten hydrolyzate (hereinafter referred to as "hydrolyzate 7") was prepared. The ratio of the weight of leucine in the hydrolyzate 7 to the total weight of glutamic acid and aspartic acid was 14%. The ratio of the weight of proline in the hydrolyzate 7 to the total weight of glutamic acid and aspartic acid was 26%. The amino acid content relative to the dry weight of the hydrolyzate 7 was 8.98% by weight. The weight ratio of (glutamic acid+aspartic acid) with respect to the total amino acid content of the hydrolyzate 7 was 47.66 weight%. Hydrolyzate 7 was produced by adding and neutralizing an aqueous sodium hydroxide solution to the hydrolyzate in the method for producing a gluten hydrolyzate described in Example 1, followed by filtration. The amount of amino acids contained in the hydrolyzate 7 was measured by the ninhydrin method. Table 7 shows the amino acid composition of hydrolyzate 7.

Table 7

Table 7. Composition of Amino Acids in Protein Hydrolyzates

Note) "-" means not detected.

Note 2) Sodium glutamate indicates the content when glutamic acid is made into monohydrate of sodium glutamate.

A red pigment (hereinafter referred to as "red pigment 13") was produced in the same manner as in Example 5 except that hydrolyzate 7 was used instead of hydrolyzate 4. The added amount of the hydrolyzate 7 was 55.7 g.

(comparative example 5)

Hydrolyzate 7 was changed so that the average molecular weight of glutamic acid and aspartic acid contained in hydrolyzate 7 was 139 so that geniposidic acid and the glutamic acid and aspartic acid were equimolar A red pigment (hereinafter referred to as "red pigment 14") was produced in the same manner as in Comparative Example 4 except that the amount of addition was increased. The added amount of the hydrolyzate 7 was 116.8 g.

(comparative example 6)

The red pigment (henceforth "red pigment 15") was produced by the method similar to Example 5 except having used the hydrolyzate 6 used in the comparative example 3 instead of the hydrolyzate 4. The ratio of the weight of leucine in the hydrolyzate 6 to the total weight of glutamic acid and aspartic acid was 16%. The ratio of the weight of proline in the hydrolyzate 6 to the total weight of glutamic acid and aspartic acid was 18%. The added amount of hydrolyzate 6 was 39.6 g.

(comparative example 7)

Hydrolyzate 6 was changed so that the average molecular weight of glutamic acid and aspartic acid contained in hydrolyzate 6 was 139 so that geniposidic acid and the glutamic acid and aspartic acid were equimolar A red pigment (hereinafter referred to as "red pigment 16") was produced in the same manner as in Comparative Example 6 except that the addition amount was the same. The added amount of hydrolyzate 6 was 93.3 g.

(comparative example 8)

Instead of hydrolyzate 4, defatted soybean hydrolyzate (Amishin (Amishin) thick type, Shinjin Co., Ltd., hereinafter referred to as "hydrolyzate 8") was used, except that red was produced by the same method as in Example 5. Pigment (hereinafter referred to as "Red Pigment 17"). The ratio of the weight of leucine in the hydrolyzate 8 to the total weight of glutamic acid and aspartic acid was 10%. The ratio of the weight of proline in the hydrolyzate 8 to the total weight of glutamic acid and aspartic acid was 17%. The amino acid content relative to the dry weight of the hydrolyzate 8 was 14.87% by weight. The weight ratio of (glutamic acid+aspartic acid) to the total amino acid content of hydrolyzate 8 was 41.02 weight%. The added amount of hydrolyzate 8 was 33.6 g. Table 8 shows the amino acid composition of hydrolyzate 8.

[Table 8]

Table 8. Composition of Amino Acids in Protein Hydrolyzates

sodium glutamate 4.79

Note) "-" means not detected.

Note 2) Sodium glutamate is the content when glutamic acid is sodium glutamate monohydrate.

(comparative example 9)

When the average molecular weight of glutamic acid and aspartic acid contained in hydrolyzate 8 was set to 139, the hydrolyzate was changed so that geniposidic acid and the glutamic acid and aspartic acid were equimolar Except the addition amount of 8, the red pigment (henceforth "red pigment 18") was manufactured by the method similar to the comparative example 8. The added amount of hydrolyzate 8 was 82.0 g.

Example 7

The color strength and hue of the red pigments 11 to 12 of Examples 5 to 6 and the red pigments 13 to 18 of Comparative Examples 4 to 9 were measured. Table 9 shows the measurement results of color power and hue.

[Table 9]

Table 9. Measurement results of color power and hue of red pigment

Comparative example 9 Red pigment 18 241.4 69.79 28.75 -6.79

According to the results shown in Table 9, the hues of red pigment 11 and red pigment 12 of Example 5 and Example 6 are all L is 70 or more, a is 30 or more, and b is -8 or less. On the other hand, in the red pigments 13 to 18 of Comparative Examples 4 to 9, L was less than 70, and a was also less than 30. Therefore, compared with the red pigment 13 - the red pigment 18 of Comparative Example 4 - Comparative Example 9, it turns out that the red pigment 11 and the red pigment 12 of Example 5 and Example 6 have a bright and vivid hue. Furthermore, the red pigments 11 and 12 of the examples have higher color power than the red pigments 13 to 18 of the comparative examples. Moreover, it is impossible to compare the color strength of the red pigments 1 to 10 of Example 4 and the red pigments 11 to 18 of this example. The reason is mainly that the reaction temperature and reaction time of the enzyme reaction and the pH value of the reaction solution are different.

The acid resistance of the red pigments 11 to 12 of Examples 5 to 6 and the red pigments 13 to 18 of Comparative Examples 4 to 9 were evaluated. Evaluation of acid resistance was performed in accordance with the procedure described in Example 4. Table 10 shows the evaluation results of acid resistance.

[Table 10]

Table 10. Evaluation results of acid resistance

According to the results shown in Table 10, the red pigment 11 and red pigment 12 of Example 5 and Example 6 had a pigment residual rate of 90% or more at pH 3.8, and these pigments had very good acid resistance. Furthermore, the pigment residual rate at pH 3.6 is also above 90%. On the other hand, the red pigment 16 and the red pigment 18 of the comparative example had a good dye remaining ratio at pH 3.8. The red pigment 13 - the red pigment 15 and the red pigment 17 of the comparative example at pH 3.8 were unsatisfactory in the dye remaining ratio.

Example 8

The heat resistance of the red pigments 11 to 12 of Examples 5 to 6 and the red pigments 13 to 18 of Comparative Examples 4 to 9 were evaluated. Evaluation of heat resistance was performed in the following procedure. 0.1 M citric acid and 0.2 M disodium hydrogen phosphate were prepared, and these aqueous solutions were mixed appropriately to adjust the pH value to prepare a buffer solution with a pH value of 4 or 6. Each dye solution of red pigment 11 to red pigment 18 was mixed with each buffer solution of pH 4 and 6, and the color power of the mixed solution was adjusted to about 1 u/g. After the preparation of the coloring liquid, the test tube containing the mixed liquid was immersed in boiling water for 30 minutes. Cool in a water bath after the boiling treatment, filter the turbid test solution with No2 filter paper (Advantec Toyo Co., Ltd.) and measure the color power, and directly measure the color tone of the treatment solution so that the color power is not 0.5. The color power of the coloring liquid after the boiling treatment was divided by the color power of the coloring liquid before the boiling treatment to obtain the coloring matter remaining rate. Table 11 shows the evaluation results of the coloring matter remaining rate and color tone.

[Table 11]

Table 11. Evaluation results of heat resistance

According to the results shown in Table 11, when the pH value was 4, the pigment residual ratios of the red pigment 11 and the red pigment 12 of Example 5 and Example 6 were 102.4% and 99.8%, respectively, and these red pigments had good heat resistance. On the other hand, in the red pigment 13 and the red pigment 14 of Comparative Example 4 and Comparative Example 5, when the pH value was 4, the pigment residual ratios were 47.5% and 64.7%, respectively, and the heat resistance was poor. In addition, red pigment 13 and red pigment 14 precipitated due to the boiling treatment at pH 4, but the other red pigments did not precipitate. Furthermore, ΔE is calculated using the calculation formula: ΔE=√((LL′) ² +(aa′) ² +(bb′) ² ). In the calculation formula, L, a, and b are values before processing, and on the other hand, L', a', and b' are values after processing. The ΔE value represents the degree of change in color tone before and after treatment. Compared with red pigment 13 and red pigment 14, the ΔE value of the other red pigments is smaller, and the change in hue is less. These phenomena are especially evident at pH 4.

The light fastness of the red pigment 11 - the red pigment 12 of Example 5-Example 6 and the red pigment 13 - the red pigment 18 of Comparative Example 4 - Comparative Example 9 were evaluated respectively. Evaluation of heat resistance was performed in the following procedure. Each pigment solution of red pigment 11 to red pigment 12 of examples 5 to example 6, and red pigment 13 to red pigment 18 of comparative example 4 to comparative example 9 is mixed with each buffer solution with the pH value of 4 and 6, The color power of this mixed solution was adjusted to about 1u/g. The mixed liquid was irradiated with light of 20000 lx for 20 hours in a photoreaction chamber (incubator with illumination, FLI-2000HT, Tokyo Rikaki Co., Ltd.). After the irradiation treatment, the coloring power of the dye liquid that became cloudy was filtered through No2 filter paper, and the color tone was directly measured for the test liquid whose color power was not adjusted to 0.5. The dye remaining ratio was calculated from the color power before and after the irradiation treatment. Table 12 shows the evaluation results of the coloring matter remaining rate and color tone.

[Table 12]

Table 12. Evaluation results of light resistance

According to the results shown in Table 12, when the pH value was 4, the pigment residual rates of red pigment 11 and red pigment 12 in Example 5 and Example 6 were 74.3% and 72.5%, respectively, and these red pigments had good light fastness. On the other hand, the red pigment 13 and the red pigment 14 of Comparative Example 4 and Comparative Example 5 had a pigment residual rate of 27.6% and 41.1%, respectively, at a pH of 4, showing poor light resistance. In addition, red pigment 13 and red pigment 14 precipitated due to light irradiation treatment at pH 4, but other red pigments did not precipitate. Furthermore, the value of ΔE is calculated using the formula: ΔE=√((LL′) ² +(aa′) ² +(bb′) ² ). The ΔE value represents the degree of change in color tone before and after treatment. Compared with red pigment 13 and red pigment 14, the ΔE value of the other red pigments is smaller, and it can be seen that there is less change in color tone. These phenomena are especially evident at pH 4.

Example 9

Manufacture of red pigment

(1) Preparation of wheat gluten hydrolyzate

Gluten hydrolyzate (henceforth "hydrolyzate 9") was prepared similarly to hydrolyzate 1. This hydrolyzate was produced by a production method in which the conditions for forming the precipitate and the conditions for cleaning the precipitate in the method for producing the hydrolyzate 1 of Example 1 were appropriately adjusted.

The ratio of the weight of leucine in the hydrolyzate 9 to the total weight of glutamic acid and aspartic acid was 0.94%. In addition, the ratio of the weight of proline in the hydrolyzate 9 to the total weight of glutamic acid and aspartic acid was 0%. The amino acid content relative to the dry weight of hydrolyzate 9 was 58.25% by weight, respectively. The weight ratio of (glutamic acid + aspartic acid) to the total amino acid content of hydrolyzate 9 was 95.23% by weight. The amount of amino acids contained in hydrolyzate 9 was measured by the ninhydrin method. Table 13 shows the amino acid composition of hydrolyzate 9.

[Table 13]

Table 13. Composition of Amino Acids in Protein Hydrolyzates

Note) "-" means not detected.

Other than hydrolyzate 9, other wheat gluten hydrolyzates were prepared as follows. Wheat-derived gluten (Wako Pure Chemical Industries, Ltd.) 300 g, water 500 g, concentrated hydrochloric acid (special grade, Wako Pure Chemical Industries, Ltd.) 350 ml, and a magnetic rotor were put into a two-neck round bottom flask with a capacity of 3 L. A thermometer and a coil were installed on the flask, and then the flask was immersed in an oil bath mounted on a heating stirrer (SR550, Advantec Co., Ltd.). The temperature of the oil bath was set at 130° C. to 140° C., the rotor in the flask was rotated, and the flask was heated for 15 hours while running tap water through the coil. After heating, the hydrolyzate in the flask was left to cool, and then the hydrolyzate was transferred to a beaker with a capacity of 2 L. While cooling the beaker, 620 g of a 25% by weight sodium hydroxide (special grade, Wako Pure Chemical Industries, Ltd.) aqueous solution was added to the hydrolyzate to neutralize the hydrolyzate to about pH 6. 10 g of Celite 500 (Tokyo Konno Shoten Co., Ltd.) was added to this neutralizing solution. A 150 mm No2 filter paper (Advantec Co., Ltd.) was set in the Buchner funnel, and 10 g of Celite 500 was precoated on the filter paper. The neutralized solution added with Celite 500 was suction-filtered using a suction bottle and a vacuum pump (Nihon-Buchi Co., Ltd., Vac. V500 type). The obtained filtrate was concentrated under reduced pressure using a rotary evaporator (N1, Tokyo Rikaiki Co., Ltd.), and then dried under reduced pressure. The powder obtained by drying under reduced pressure was used in the following experiments as a wheat gluten hydrolyzate (hereinafter referred to as "hydrolyzate 10"). The leucine content of the hydrolyzate 10 was 1.63 weight%, and the (glutamic acid+aspartic acid) content was 16.38 weight%. The ratio of the weight of leucine in the hydrolyzate 10 to the total weight of glutamic acid and aspartic acid was 9.95%. The ratio of the weight of proline in the hydrolyzate 10 to the total weight of glutamic acid and aspartic acid was 27.41%. The amino acid content relative to the dry weight of the hydrolyzate 10 was 34.10% by weight. The weight ratio of (glutamic acid+aspartic acid) with respect to the total amino acid content of the hydrolyzate 10 was 48.04 weight%. Table 14 shows the amino acid composition of hydrolyzate 10.

[Table 14]

Table 14. Composition of Amino Acids in Protein Hydrolyzates

Note) "-" means not detected.

Hydrolyzate 9 and hydrolyzate 10 were mixed in such a way that the weight ratio of the weight of amino acids contained in hydrolyzate 9 to the weight of amino acids contained in hydrolyzate 10 was 85:15 to prepare a hydrolyzate (hereinafter referred to as "hydrolyzate 10"). Object 11"). The ratio of the leucine in the hydrolyzate 11 to the total weight of glutamic acid and aspartic acid was 1.38%. The amino acid content to the dry weight of the hydrolyzate 11 was 54.63% by weight, and the weight ratio of (glutamic acid+aspartic acid) to the total amino acid content was 90.81% by weight.

(2) Preparation of iridoid glycoside compounds

400 ml of water and 194 g of 24% by weight sodium hydroxide were added to 360 g of the geniposide solution, and saponified at 60° C. for 1 hour to prepare a geniposide solution. 240 g of crystalline citric acid (Wako Pure Chemical Industries, Ltd., special grade citric acid) was added to the obtained geniposidic acid solution. The resulting mixed solution was divided into 12 equal parts, and put into 12 Erlenmeyer flasks with a volume of 300 ml respectively, so as to prepare 12 Erlenmeyer flasks in which the geniposidic acid solution was added.

(3) Preparation of taurine

Taurine extracted from oysters was obtained by the method described in Example 2 of Japanese Patent Laid-Open No. 2005-179215. The purity of the obtained taurine was 80.1%. The resulting taurine does not contain free amino acids other than taurine. The purity was determined by using HPLC according to the method described in "Analysis of Taurine Contained in Foodstuffs" by Teragakauchi, Yamaguchi Toshiya, and Sugimura Toyoyuki (Research Report No. 18, 1812 of the Independent Administrative Agency Agriculture, Forestry and Fisheries Consumer Technology Center) for analysis.

(4) Manufacture of red pigment

Seven of these flasks were taken, and the hydrolyzate 9 and hydrolyzate 11 in the amounts described in Table 15 and the taurine obtained in (3) above were added and mixed. Table 15 shows the addition amount of hydrolyzate 9 or hydrolyzate 11, the addition amount of taurine, the actual taurine addition amount in consideration of the purity of taurine, the amino acid content in the hydrolyzate, and the content of taurine. The ratio (%) of the weight relative to the amino acid content. In Table 15, Production Example 9-0 is an example in which only hydrolyzate 9 was used for the reaction. Production Example 9-1 to Production Example 9-3 are examples in which hydrolyzate 9 and taurine were used for the reaction. Production Example 11-0 is an example in which only the hydrolyzate 11 was subjected to a dry reaction. Production Example 11-1 to Production Example 11-2 are examples in which the hydrolyzate 11 and taurine were used for the reaction.

[Table 15]

Table 15. The amount of hydrolyzate and the amount of taurine used in the preparation of taurine-containing gluten hydrolyzate

Hydrolyzate name Manufacturing example 9-0 Manufacturing Example 9-1 Manufacturing example 9-2 Manufacturing example 9-3 Hydrolyzate 9(g) 9.23 8.30 7.38 6.46 Amino acid content (g) 5.37 4.84 4.30 3.76 Taurine (purity 80.1%) amount (g) 0.00 0.60 1.21 1.81 Actual amount of taurine (g) 0.00 0.48 0.97 1.45 Taurine/Amino Acid Content 0.0% 9.9% 22.6% 38.6%

The addition amount of the hydrolyzate 9 in the manufacture example 9-0～manufacture example 9-3 is when the average molecular weight of the amino acid contained in the hydrolyzate 9 is set as 139, the molar amount of geniposidic acid and the hydrolyzate 9 The total molar amounts of the molar amounts of the amino acid to be contained and the molar amounts of taurine were adjusted so as to be equimolar. The amount of hydrolyzate 11 added in Production Example 11-0 to Production Example 11-2 is also based on the fact that when the average molecular weight of the amino acid contained in Hydrolyzate 11 is set to 139, the molar amount of geniposidic acid is the same as that of Hydrolyzate 11. The total molar amounts of the molar amounts of the amino acid to be contained and the molar amounts of taurine were adjusted so as to be equimolar.

Then, a 24% by weight sodium hydroxide solution was added to these mixtures with stirring to adjust the pH to 4.6. Water was further added to this mixture so that the liquid amount would be 200 g. Next, 0.9 g of Cellulase AP5 (Amano Enzyme Co., Ltd.) was added, and the inside of the Erlenmeyer flask was replaced with argon, covered with aluminum foil, and the enzyme reaction was carried out at 53°C for 22 hours. . After the reaction, the reactant was heated at 90° C. for 1 hour using a heater (Yamato Scientific Co., Ltd., water bath thermostat BT-25). The reaction was then left to cool in a water bath (room temperature) for about 30 minutes. When the reactant becomes about 50° C. by standing to cool, collect the reactant in a 1.5 ml Eppendorf pipette, and utilize a cooling centrifuge (Eppendorf (Eppendorf) Co., Ltd., cooling centrifuge 5415R). The reactant was centrifuged at 12000 rpm for 5 minutes to obtain a supernatant. The obtained supernatant is red pigment (hereinafter, the red pigment of Manufacturing Example 9-0 to Manufacturing Example 9-3 is respectively referred to as "Red Pigment 19-0" to "Red Pigment 19-3", and the red pigment of Manufacturing Example 11- 0 to the red pigments of Production Examples 11-2 are respectively referred to as "red pigment 20-0" to "red pigment 20-2").

(comparative example 10)

Various amounts of hydrolyzate 9, hydrolyzate 11, and taurine were added to each of the above-mentioned flasks. Table 16 shows the added amount of hydrolyzate 9 and hydrolyzate 11, the added amount of taurine, the amino acid content in the hydrolyzate, and the ratio (%) of the weight of taurine to the amino acid content. The red pigment was manufactured by the method similar to Example 9 except having changed the addition amount of the hydrolyzate 9 and the hydrolyzate 11, and the addition amount of taurine like following Table 16.

[Table 16]

Table 16. Amount of hydrolyzate and amount of taurine

Hydrolyzate name Comparative example 9-4 Hydrolyzate 9(g) 5.54 Amino acid content (g) 3.22 Taurine (purity 80.1%) amount (g) 2.41 Actual amount of taurine (g) 1.93 Taurine/Amino Acid Content 59.9%

Hydrolyzate name Comparative example 11-3 Comparative example 11-4 Hydrolyzate 11(g) 7.14 6.12 Amino acid content (g) 3.76 3.22 Taurine (purity 80.1%) amount (g) 1.81 2.41 Actual amount of taurine (g) 1.45 1.93 Taurine/Amino Acid Content 38.6% 59.9%

The red pigment obtained in Comparative Example 9-4 is called "Red Pigment 19-4", and the red pigments obtained in Comparative Example 11-3 and Comparative Example 11-4 are called "Red Pigment 20-3" and "Red Pigment 20-3", respectively. Red Pigment 20-4".

Example 10

To the red pigment 19-0～red pigment 19-3 of example 9, the red pigment 20-0～red pigment 20-2 and the red pigment 19-4 of comparative example 10, the red pigment 20-3 and the red pigment 20-4 Color strength, hue, and acid resistance are measured, and color strength reduction due to turbidity or precipitation when mixed with anthocyanin pigments is tested

Table 17 shows the measurement results of color power and hue.

[Table 17]

Table 17. Measurement results of color power and hue of red pigment

From the results shown in Table 17, L of the red pigment of the example is 70 or more and a is 30 or more. b is -8 or less. Therefore, the red pigments of the Examples have bright and vivid hues compared with the red pigments of the Comparative Examples. That is, when the ratio of the weight of taurine to the amino acid content in the hydrolyzate is 40% by weight or less, the resulting red pigment has a bright and vivid hue. However, as the amount of taurine added increases, the color strength tends to decrease, and the hue also tends to decrease the values of L, a, and b. That is, the brightness decreases, the redness decreases, and the blueness increases.

To the red pigment 19-0～red pigment 19-3 of example 9, the red pigment 20-0～red pigment 20-2 and the red pigment 19-4 of comparative example 10, the red pigment 20-3 and the red pigment 20-4 Acid resistance was evaluated. In the acid resistance evaluation, it carried out by the method similar to the method described in Example 4 except having set the pH value at the time of diluting a red pigment to 3.0, 3.2, and 3.5. Table 18 shows the evaluation results of acid resistance. With regard to the evaluation criteria of acid resistance, if the color remaining rate at pH 3.5 is 90% or more, it is evaluated as very good (◎), if it is 75% or more and less than 90%, it is evaluated as good (○), and if it is less than 75% Then, it was evaluated as poor (×).

[Table 18]

Table 18. Evaluation results of acid resistance

According to the results shown in Table 18, when the pH value was 3.5, the pigment residual rate of red pigment 19-0 was 40.9%. The pigment remaining rate of pigment 19-4 was 100%. That is, the red pigments 19-1 to 19-3 of the examples and the red pigment 19-4 of the comparative example had very good acid resistance. When the pH value was 3.2, the acid resistance of the red pigment 19-1 was also good, and the acid resistance of the red pigments 19-1 to 19-3 of the examples and the red pigment 19-4 of the comparative example were very good. When the pH was 3.0, the red pigment 19-3 of the example and the red pigment 19-4 of the comparative example had very good acid resistance. That is, it turned out that there exists a tendency for acid resistance to improve so that the quantity of taurine contained in a protein hydrolyzate increases. The same tendency was also observed for red pigment 20-0 to red pigment 20-4.

Considering the result of the color tone and the result of acid resistance, in the production method of the present invention, when the ratio of the weight of taurine to the amino acid content in the protein hydrolyzate is 35% by weight or less, a bright and vivid color can be obtained. A red pigment with a good hue, and the acid resistance of the obtained red pigment is also good. When the ratio of the weight of taurine to the amino acid content in the protein hydrolyzate exceeds 35% to 40% by weight, the lower limit of the total weight of glutamic acid and aspartic acid in the amino acid content of the protein hydrolyzate exceeds 92 %, preferably more than 93%, a red pigment with a bright and vivid hue can be obtained, and the acid resistance of the obtained red pigment is also good.

The formation of precipitates when red pigments and anthocyanin-based pigments were mixed was evaluated. The anthocyanin-based dye used in this evaluation was red cabbage dye (KC red (Red) AC, Kobe Chemical Co., Ltd.). The red dye of the present invention used in this evaluation was the red dye produced in Example 9. The experimental sequence is as follows.

In a 10 ml scaled test tube with a cover, 5 ml of the McIlvaine buffer solution with a pH value of 3.5 was added in advance, and 50 u of the red pigment (based on the amount of pigment at 530 nm at a pH value of 3.5) was added respectively. Then, 50u of anthocyanin pigment (based on the amount of pigment at 530nm at pH 3.5) was added to the test tube, and the buffer solution was further added to reach the scale of 10ml of the test tube, followed by sufficient shaking and mixing. Let the mixture of the two pigments stand overnight in the refrigerator. Then, after shaking this mixed solution, the absorbance at 720 nm was measured. Next, the mixture was centrifuged at 3000 rpm for 10 minutes, the supernatant was diluted 4-fold with the above-mentioned buffer, and the absorbance at 530 nm was measured. Among the measurement wavelengths, the measurement wavelength of 720 nm is a wavelength for measuring turbidity or precipitation formed in the mixed liquid. That is, the larger the absorbance at the measurement wavelength of 720 nm, the more turbidity or precipitates are generated in the mixed liquid. On the other hand, the measurement wavelength at 530 nm is the wavelength for measuring red pigment. That is, the larger the absorbance at the measurement wavelength of 530 nm, the more red pigment remains in the mixed liquid without forming a precipitate. Table 19 shows the measurement results of absorbance. In addition, since the absorbance measurement was performed on a liquid diluted 4 times, the data in Table 19 are obtained by multiplying the measured value itself by 4.

[Table 19]

Table 19. Measurement results of the absorbance of the mixture of red cabbage pigment and the red pigment of the present invention

At the measurement wavelength of 720 nm, compared with the absorbance of red pigment 19-0, the absorbance of red pigment 19-1 is smaller, and the absorbance of red pigment 19-2, red pigment 19-3 and red pigment 19-4 is even smaller. This phenomenon is also the same for the red pigments 20-0 to 20-4. At the measurement wavelength of 530 nm, compared with the absorbance of red pigment 19-0, the absorbance of red pigment 19-1 is larger, and the absorbance of red pigment 19-2, red pigment 19-3 and red pigment 19-4 is larger. This phenomenon is also the same for the red pigments 20-0 to 20-4. That is, in the production of red pigment, compared with the case of not using taurine in the reaction, when taurine is used, even if it is mixed with red cabbage pigment, the generation of turbidity or precipitation is also less, and the mixed solution The amount of residual red pigment in the supernatant was more.

In addition, considering the test results of red cabbage pigment and the measurement results of the hue, in the production method of the present invention, when taurine and protein hydrolyzate are reacted with iridoid glycoside compounds, and the content of taurine When the amino acid weight contained in the protein hydrolyzate is 40% by weight or less, a red pigment with a bright and vivid hue can be obtained, and even if the obtained red pigment is mixed with red cabbage pigment, the generation of turbidity or precipitation is less, and The amount of red pigment remaining in the supernatant of the mixture was greater.

Next, the precipitation formation of the mixed solution of various anthocyanin pigments and the red pigment of this invention was tested. The anthocyanin pigments used in this evaluation are red cabbage pigment (KC red (Red) AC, Kobe Chemical Co., Ltd.), purple sweet potato pigment (KC red (Red) NNK, Kobe Chemical Co., Ltd.), carrot pigment (KC red (Red) NNK, Kobe Chemical Co., Ltd.), carrot pigment (KC red (Red) RD-2, Kobe Chemicals Co., Ltd.), purple corn pigment (TS Red (Red) MZA, Taisho Technos Co., Ltd.), elderberry pigment (Kobe Chemicals Co., Ltd.) and grape peel pigment (TS Red (Red), Taisho Technos Co., Ltd.). The red pigments of the present invention used in this evaluation are red pigments 19-0, 20-0, 19-2, and 20-2 among the red pigments produced in Example 9. The test sequence is the same as the test of the mixed solution of the red cabbage pigment and the red pigment of the present invention. Table 20 shows the measurement results of absorbance.

[Table 20]

Table 20. Measurement results of the absorbance of the mixture of anthocyanin pigments and the red pigment of the present invention

Absorbance at A720nm

red cabbage Purple sweet potato carrot Red Pigment 19-2/Red Pigment 19-0 0.784/1.417 1.389/2.181 1.307/1.917 Red Pigment 20-2/Red Pigment 20-0 0.972/1.389 1.896/2.241 1.610/1.931

purple corn elderberry grape peel Red Pigment 19-2/Red Pigment 19-0 0.508/1.777 0.480/0.549 2.205/2.223 Red Pigment 20-2/Red Pigment 20-0 1.116/1.964 0.492/0.646 2.270/2.301

Absorbance at A530nm

red cabbage Purple sweet potato carrot Red Pigment 19-2/Red Pigment 19-0 8.600/7.184 8.132/5.736 8.132/5.748 Red Pigment 20-2/Red Pigment 20-0 7.616/6.612 6.976/5.608 7.000/5.064

purple corn elderberry grape peel Red Pigment 19-2/Red Pigment 19-0 8.820/6.828 7.956/7.724 7.336/5.408 Red Pigment 20-2/Red Pigment 20-0 7.856/6.292 7.652/7.320 6.916/3.876

At the measurement wavelength of 720nm, no matter which anthocyanin pigment is mixed with, the absorbance of red pigment 19-2 is smaller than that of red pigment 19-0. This phenomenon is the same for red pigment 20-0 and red pigment 20-2. At the measurement wavelength of 530nm, no matter what kind of anthocyanin pigment is mixed, the absorbance of red pigment 19-2 is greater than that of red pigment 19-0. This phenomenon is the same for red pigment 20-0 and red pigment 20-2. That is, not only red cabbage pigments but also other anthocyanin-based pigments, the effect of reducing the amount of precipitate generation shown in Table 18 was confirmed.

Example 11

(drinking fruit jelly)

The drinking fruit jelly containing the red pigment of the present invention is manufactured according to the following formula. First, 0.8 g of a gelling agent, sugar (4 g) and water in an amount 5 times that of the gelling agent were mixed. Then, the gelling agent and sugar were dissolved while heating the liquid mixture to 90°C. After dissolution, the mixture was cooled to 75°C. After cooling, the remaining raw materials were added, and then citric acid was added so that the pH of the mixed liquid was 3.8, and water was added so that the total weight of the mixed liquid was 100 g. The obtained liquid mixture was filled in the container for drinks, and it sealed and sterilized at 83 degreeC for 20 minutes. After sterilization, the mixed liquid is cooled to obtain drinking fruit jelly.

<recipe>

Granulated sugar 18 parts by weight

1/5 concentrated fruit juice 6 parts by weight

White liquor (white liquor) 2 parts by weight

Gelling agent 0.8 parts by weight

The red pigment 1 of example 1 0.05 parts by weight

(color value E10% corresponds to a pigment with a concentration of 100)

Water makes the whole amount 100 parts by weight

Citric acid Amount to make pH = 3.8

The color value E10% refers to a value obtained by converting the absorbance at the maximum absorption wavelength of the colorant solution into the absorbance of a 10% by weight/volume solution.

Example 12

(yokan)

The yokan containing the red pigment of the present invention is manufactured according to the following recipe. First, agar was mixed with water, and the agar was dissolved while boiling the mixture for 15 minutes. After cooling the solution to 70° C., the remaining raw materials were added, stirred and dissolved. Finally, after drying until the total amount of the solution becomes about 100 g, it is filled in a container. Yokan is obtained by cooling after filling.

<recipe>

Raw stuffing 44 parts by weight

Granulated sugar 51 parts by weight

Syrup (millet jelly) 5 parts by weight

Agar 0.6 parts by weight

The red pigment 2 of example 2 0.1 parts by weight

(color value E10% corresponds to a pigment with a concentration of 100)

Water 25 parts by weight

Example 13

(cool drink)

The refreshing drink containing the red pigment of the present invention is manufactured according to the following formula. After dissolving the ingredients in hot water, fill it into a beverage container. The pH of the solution after dissolving in hot water was 3.8.

<recipe>

Granulated sugar 30 parts by weight

Liquid sugar 25 parts by weight

Sodium citrate 1 part by weight

Vitamin C 0.5 parts by weight

The red pigment 3 of example 2 0.05 parts by weight

(color value E10% corresponds to a pigment with a concentration of 100)

Hot water makes the whole 100 parts by weight

Citric acid Amount to make pH = 3.8

Spices Appropriate amount

Example 14

(jelly)

The jelly containing the red pigment of the present invention is manufactured according to the following recipe. The 1.2-g gelatinizer, the sugar (6g) of 5 times the quantity of this gelatinizer, and water were mixed. Then, the gelling agent and sugar were dissolved while heating the liquid mixture to 90°C. Next, this solution was cooled to 75°C. After cooling, add remaining ingredients and stir to dissolve. The pH of the solution was 3.8. This solution was filled into a jelly container, sealed, and sterilized at 83° C. for 20 minutes. After sterilization, the solution was cooled to obtain jelly.

<recipe>

Granulated sugar 16 parts by weight

Sodium citrate 1 part by weight

Malic acid 1.35 parts by weight

Gelling agent 1.2 parts by weight

The red pigment 4 of example 2 0.05 parts by weight

(color value E10% corresponds to a pigment with a concentration of 100)

Water makes the whole amount 100 parts by weight

Citric acid Amount to make pH = 3.8

Spices Appropriate amount

Example 15

(chewing gum)

Chewing gum containing the red pigment of the present invention was manufactured according to the following recipe. Chewing gum is made by mixing other raw materials into the chewing gum base.

<recipe>

Chewing gum base 99.5 parts by weight

Ascorbic acid 0.1 parts by weight

The red pigment 5 of example 3 0.05 parts by weight

(color value E10% corresponds to a pigment with a concentration of 100)

50% by weight citric acid water 0.35 parts by weight

Example 16

(hard candy)

The hard candy containing the red pigment of the present invention is manufactured according to the following recipe. Add the granulated sugar and gardenia red coloring to the syrup and mix. Next, the mixture was heated to 120°C. Afterwards, the mixture was cooled to 70° C., and then the remaining raw materials were mixed. Finally, the mixture is shaped to produce hard candies.

Granulated sugar 45 parts by weight

Syrup 55 parts by weight

Citric acid 1.5 parts by weight

Ascorbic acid 0.5 parts by weight

The red pigment 11 of example 5 0.1 parts by weight

(color value E10% corresponds to a pigment with a concentration of 100)

Spices Appropriate amount

Example 17

(agar jelly)

The agar jelly containing the red pigment of this invention was manufactured according to the recipe of the following Table 21.

[Table 21]

Table 21. Recipe for agar jelly

Note) Adjust with citric acid or sodium citrate so that the final pH is 3.7 to 3.8.

Water was added to the pot, and agar, erythritol (5 g), acesulfame K, and sucralose were added little by little without agglomeration while stirring. Then, heat the pot and boil for 5 minutes. The remaining erythritol and trisodium citrate were further added and dissolved. The solution was cooled to 75° C., and L-ascorbic acid, coloring material, fragrance, sugarcane extract, and pH adjuster were added and mixed. Confirm final weight, fill into containers and seal. Then, it sterilized at 85 degreeC for 30 minutes. Cool rapidly after sterilization to obtain agar jelly.

Example 18

(hard candy)

Hard candies containing the red pigment of the present invention were produced according to the formulations in Table 22 below.

[Table 22]

Table 22. Recipe for Hard Candies

Add granulated sugar, syrup, and water to the pot, and heat it on the fire while mixing. Boil it dry and remove it from the fire when it reaches 155°C. Then, when the temperature becomes below 100°C, add the mixture of citric acid, pigment and flavor, and mix well until the whole is uniform. The resulting candy prototype is stretched, put into a mold, and shaped to obtain a hard candy.

Example 19

(Carbonated drinks)

Carbonated beverages containing the red pigment of the present invention were produced according to the formulations in Table 23 below.

[Table 23]

Table 23. Recipe for carbonated beverages

※Acidity 0.08%, gas capacity 3~4.

Mix ingredients other than carbonated water and sterilize at 60°C for 30 minutes. After sterilization, the mixed solution is cooled, and carbonated water is mixed with the mixed solution after cooling.

Example 20

(Beverages below pH 3.5)

Drinks containing the red pigment of the present invention were produced according to the formulations in Table 24 below.

[Table 24]

Table 24. Recipes for Low pH Beverages

The raw materials are mixed and dissolved. Cans were filled in units of 195 g and sealed. The pH of the beverage is below 3.5.

Example 21

(Beverages below pH 3.5)

Drinks containing the red pigment of the present invention were manufactured according to the formulations in Table 25 below.

[Table 25]

Table 25. (Beverages with low pH)

The raw materials are mixed and dissolved. Cans were filled in units of 195 g and sealed. The pH of the beverage is below 3.5.

Claims (16)

1. A method for producing a red pigment, which comprises reacting an iridoid glycoside compound having a carboxyl group at the 4-position of an iridoid glycoside skeleton with a protein hydrolyzate to produce a red pigment, wherein the method is characterized in that: In the protein hydrolyzate, the amino acid content relative to the dry weight of the hydrolyzate is 35% by weight or more, and when measured by the ninhydrin method, 50% by weight or more of the amino acids are glutamic acid and aspartame amino acid, and the ratio of the weight of leucine to the total weight of the glutamic acid and the aspartic acid is 8% or less. 2. The manufacture method of red pigment according to claim 1, characterized in that: when utilizing the ninhydrin method to measure, the weight of proline is relative to the total weight of said glutamic acid and said aspartic acid The ratio is below 15%. 3. The method for producing a red pigment according to claim 1 or 2, wherein the red pigment has a hue in which L is 70 or more and a is 30 or more in the Lab color system. 4. The method for producing a red pigment according to claim 1 or 2, wherein the red pigment has a hue in which L is 70 or more, a is 30 or more, and b is -8 or less in the Lab color system. 5. The method for producing red pigment according to any one of claims 1 to 4, characterized in that: the protein hydrolyzate is gluten hydrolyzate. 6. The manufacturing method of red pigment according to claim 1 or 2, characterized in that: the red pigment has a hue that L is more than 70 and a is more than 30 in the Lab colorimetric system, and the protein hydrolyzate For gluten hydrolyzate. 7. The method for producing red pigment according to claim 1 or 2, characterized in that: the red pigment has a hue in which L is 70 or more, a is 30 or more, and b is -8 or less in the Lab colorimetric system, And the protein hydrolyzate is gluten hydrolyzate. 8. A food or drink characterized by containing a red pigment obtained by the method for producing a red pigment according to any one of claims 1 to 7. 9. A method for producing a red pigment by reacting an iridoid glycoside compound having a carboxyl group at the 4-position of the iridoid glycoside skeleton with a protein hydrolyzate and taurine or a substance containing taurine. Red pigment, the method is characterized in that: in the protein hydrolyzate, the amino acid content relative to the dry weight of the hydrolyzate is 35% by weight or more, and when measured by the ninhydrin method, the amino acid 50% by weight or more are glutamic acid and aspartic acid, and the ratio of the weight of leucine to the total weight of the glutamic acid and the above-mentioned aspartic acid is 8% or less, and relative to the protein The amino acid content in the hydrolyzate, the amount of taurine, or the amount of taurine contained in the taurine-containing substance exceeds 0% by weight to 35% by weight. 10. The method for producing red pigment according to claim 9, wherein when the ninhydrin method is used for measuring, the weight of proline is relative to the total weight of the glutamic acid and the aspartic acid The ratio is below 15%. 11. The method for producing a red pigment according to claim 9 or 10, wherein the red pigment has a hue in which L is 70 or more and a is 30 or more in the Lab color system. 12. The method for producing a red pigment according to claim 9 or 10, wherein the red pigment has a hue in which L is 70 or more, a is 30 or more, and b is -8 or less in the Lab color system. 13. The method for producing red pigment according to any one of claims 9 to 12, characterized in that: the protein hydrolyzate is gluten hydrolyzate. 14. The manufacturing method of red pigment according to claim 9 or 10, characterized in that: the red pigment has a hue of more than 70 and a of more than 30 in the Lab color system, and the protein hydrolyzate For gluten hydrolyzate. 15. The method for producing red pigment according to claim 9 or 10, characterized in that: the red pigment has a hue in which L is 70 or more, a is 30 or more, and b is -8 or less in the Lab color system, And the protein hydrolyzate is gluten hydrolyzate. 16. A food or drink characterized by containing a red pigment obtained by the method for producing a red pigment according to any one of claims 9 to 15.