JP6969940B2 - Iridoid compound-derived red pigment composition and its production method - Google Patents

Description

The present invention relates to an iridoid compound-derived red pigment composition and a method for producing the same.

Gardenia red pigment is a pigment having a red color tone produced from gardenia fruit extract, and is a natural pigment having a property of relatively high stability to heat. Here, the gardenia red pigment is a pigment compound obtained by reacting the aglycone of the iridoid compound contained in the gardenia fruit extract with the amino group-containing compound. In the development of gardenia red pigment, a pigment compound having a structure derived from an iridoid compound and producing a red color tone has been developed by improving a part of the process of manufacturing a blue pigment (patented patent). Document 1).
Since gardenia red pigment is derived from plant materials, it overlaps with the safety consciousness of consumers in recent years, and instead of insect-derived cochineal pigment and other synthetic red pigments, food and drink, cosmetics, quasi-drugs, pharmaceuticals, etc. Demand is expanding in many areas. In particular, gardenia red pigment is used as an excellent pigment material that can also be used in the food and beverage field.

However, gardenia red pigment has not only its excellent advantages but also problems that narrow the range of applications and practical applications. Specifically, gardenia red pigment is considered to be a red pigment having relatively good stability to light irradiation among natural pigments, but there is a problem that the stability is not always sufficient. That is, the gardenia red pigment undergoes fading and discoloration under the condition of being exposed to light for a long time, and is difficult to use for products that are premised on being exposed to light during storage and display. Therefore, in order to expand the range of applications and practical use of gardenia red pigment, it is necessary to overcome the problem of stability against light irradiation and develop a technique for producing gardenia red pigment having light resistance.

In such a situation, the following reports have been made as prior art regarding the light resistance of gardenia red pigment. For example, as a prior art for imparting light resistance in the manufacturing process of gardenia red pigment, a technique for imparting light resistance to gardenia red pigment by generating sulfite ions at the time of red color development has been reported (Patent Document 2). ). However, sulfite ions such as sodium pyrosulfite and potassium pyrosulfite, which are technical features of the technology, are compounds that have been pointed out to have various effects when used for food and drink, and are therefore removed in the subsequent steps. Even if it is processed, it is a technology that remains a concern for today's consumers who are highly safety-conscious.
Further, as a prior art for achieving the light resistance of gardenia red pigment, there is a technique of adding a taurine-containing substance at the time of red color development (Patent Document 3). However, since the taurine-containing substance added by the technique according to the document is a substance whose price per unit weight is incomparably higher than that of ordinary organic acids, there is a problem in terms of dye production cost. Recognized as technology.

The following technologies can be mentioned as related technologies related to the field. For example, as a prior art for achieving improvement in the color tone of gardenia red pigment, in the presence of 2 mol equivalents or more of an organic acid and 0.7 mol equivalents or more of a specific amino acid such as arginine with respect to an iridoid compound in red color development. Techniques to be performed (Patent Document 4) and the like can be mentioned. However, Patent Document 4 does not touch on a method of imparting light resistance to gardenia red pigment by paying attention to the type and content of the organic acid.

Special Publication No. 55-5778 Japanese Patent No. 5753373 Japanese Patent No. 4605824 Japanese Patent No. 2802451

The present invention has been made in view of the circumstances of the above-mentioned prior art, and the subject thereof is a technique relating to the production of an iridoid compound-derived red pigment composition, and the safety and production cost of the produced dye composition. It is a suitable technique in terms of the above, and an object of the present invention is to provide a technique for producing a red pigment composition derived from an iridoid compound having light resistance.

In the context of the above-mentioned prior art, the present inventors have conducted intensive studies and found that succinic acid or succinic acid or in the step of performing red coloration accompanied by the action of an iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton and an amino group-containing compound. I came up with a method of excessively adding a dicarboxylic acid having a specific structure such as malic acid. The present inventors have found that when red color is developed by a method based on the above idea, a red dye composition derived from an iridoid compound having excellent light resistance is prepared. It has been found that the dye composition has excellent light resistance, and in particular, the color development stability is significantly improved under long-term light irradiation conditions.

Succinic acid used in the above manufacturing process is a compound that is also used as an umami component, an acidulant, a food and drink additive for pH adjustment, and an excipient for pharmaceutical products. Malic acid is a compound widely used as a food and drink additive such as an acidulant, a pH adjuster, and an emulsifier, and is also called oxysuccinic acid. In this respect, since these substances are compounds whose safety to the human body is guaranteed, the technique according to the present invention is a sulfite ion such as sodium metabisulfite and potassium pyrosulfite according to Patent Document 2 which is the prior art document. It is recognized as a technique that overcomes the safety concerns of the dye composition obtained through the production.
Further, since succinic acid and malic acid are a kind of organic acids used for many purposes and are inexpensive raw materials, the taurine-containing compound according to Patent Document 3 which is the above-mentioned prior art document is an expensive raw material. Compared with, it is recognized as a technology that has an advantage in terms of manufacturing cost.

Here, paragraph 0036 of Patent Document 2, which is a prior art document, lists compounds belonging to organic acids as optional additives in the process of producing an iridoid compound, and succinic acid and malic acid are exemplified as one of them. ing. Further, claim 1 of Patent Document 4 also lists substances belonging to organic acids as additive substances.
However, in the paragraphs relating to these documents, "citric acid" which does not exert the effect according to the present invention is listed, and it is judged whether or not the present invention can be conceived based on the description in the paragraph. It is recognized that the description includes the reason for inhibition. Further, in the examples of these documents, no experimental example in which succinic acid or malic acid is actually added is described, and a method capable of producing a light-resistant dye composition according to the present invention is disclosed. It is not recognized that it has been done.
Further, Patent Documents 2 and 4 are merely documents that disclose an invention based on a technical idea different from the above-mentioned invention, and have an effect of improving the characteristics relating to the addition of a large amount of succinic acid, malic acid, etc. and the light resistance of the iridoid compound. No disclosure or suggestion is made.

The present inventors have completed the present invention based on the above findings. Specifically, the present invention relates to the invention described below.

[Item 1]
In the method for producing a red pigment composition derived from an iridoid compound,
(Step 1) A compound represented by the following structural formula (i) with respect to the total molar equivalent of the iridoid compound, which produces a red color with the action of the iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton and the amino group-containing compound. , The similar compound, or two or more compounds selected from these, in a solution containing 5 mol equivalents or more to produce a light-resistant red pigment compound.
A method for producing a red pigment composition derived from an iridoid compound, which comprises:

(In the formula, R ₁₁ represents a hydrogen atom or a hydroxyl group.).

[Item 2]
Item 1. The step of performing the red color development according to the above (step 1) is performed with a solution containing a larger amount of succinic acid and / or malic acid than 6 molar equivalents with respect to the total molar equivalent of the iridoid compound. The method for producing a red pigment composition derived from an iridoid compound according to the above.
[Item 3]
Item 2. The method for producing an iridoid compound-derived red pigment composition according to Item 1 or 2, wherein the iridoid compound-derived red pigment composition is a gardenia red pigment composition.
[Item 4]
Item 1 to the above-mentioned step (step 1), wherein the reaction for producing iridoid aglycone from the iridoid glycoside by β-glycosidic bond hydrolysis is carried out prior to and / or in parallel with the red color development. 3. The method for producing an iridoid compound-derived red pigment composition according to any one of 3.
[Item 5]
In the method for producing a red pigment composition derived from an iridoid compound,
(Step 1') The red coloration associated with the action of the geniposide ester hydrolyzate aglycon and / or the geniposidate aglycon having a carboxyl group at the 4-position of the iridoid skeleton and the amino group-containing compound was added to the total molar equivalent of the iridoid compound. On the other hand, it was carried out under acidic conditions with a solution containing a larger amount of succinic acid and / or iridoid than 6 mol equivalents.
The process of producing a red pigment compound with light resistance,
Including
The step according to the above (step 1') is to carry out a reaction for producing iridoid aglycone from an iridoid glycoside by β-glycosidic bond hydrolysis prior to and / or in parallel with red color development.
The iridoid compound-derived red pigment composition is a gardenia red pigment composition.
A method for producing a red pigment composition derived from an iridoid compound, which comprises the above.
[Item 6]
In the process for producing an iridoid compound-derived red pigment composition, the above-mentioned (step 1) according to any one of Items 1 to 4 or the above-mentioned (step 1') according to Item 5 is performed. A method for imparting light resistance to a red pigment composition derived from an iridoid compound.
[Item 7]
The iridoid compound-derived red pigment composition obtained by the production method according to any one of Items 1 to 5.
[Item 8]
Iridoid compound-derived red pigment composition having the characteristics described in the following (A) and (B):
(A) The ^{red pigment composition derived from the iridoid compound was contained so as to have a color value E of 10% and a} _{1 cm} value of 50.5 in terms of 0.05% by mass, adjusted to Brix 10 ° with fructose-glucose liquid sugar, and pH 5. When the acid sugar solution adjusted to 0 was stored at 10000 lux irradiated with a white fluorescent lamp and at 10 ° C. for 5 days, the residual dye ratio was 62% or more before storage.
(B) When ^{an aqueous solution containing the iridoid compound-derived red pigment composition so as to have a color value E of 10% and a} _{1 cm} value of 0.05 and having a pH of 5.0 prepared with a McIlvaine buffer solution, the following formula is satisfied:
Equation: C _{1 −} C ₀ ≧ 4
(In the formula, C ₁ indicates the CHROMA value in the aqueous solution containing the iridoid compound-derived red dye composition, and C ₀ indicates the CHROMA value in the aqueous solution prepared in the same manner as described above except that the standard dye is blended. Here, the standard dye indicates a dye composition prepared in the same manner as in Sample 5-1 described in Example 5).
[Item 9]
A dye preparation containing the iridoid compound-derived red pigment composition according to Item 7 or 8.
[Item 10]
A food or drink, a cosmetic, a pharmaceutical product, a quasi-drug, a daily necessities for hygiene, or a feed containing the iridoid compound-derived red pigment composition according to item 7 or 8 or the dye preparation according to item 9.
[Item 11]
A dye preparation, a food or drink, a cosmetic, a pharmaceutical product, or a quasi-drug, which comprises a step of containing the iridoid compound-derived red pigment composition obtained by the production method according to any one of Items 1 to 5. , Hygiene daily necessities, or feed manufacturing method.

The present invention is a technique for producing a red pigment composition derived from an iridoid compound, which is suitable in terms of safety and production cost of the produced dye composition, and has a light resistant red pigment composition derived from an iridoid compound. It makes it possible to provide the technology for manufacturing things.
INDUSTRIAL APPLICABILITY According to the present invention, for example, it is possible to provide a gardenia red pigment having excellent color development stability under light irradiation conditions, and it can be widely used for applications and products that were difficult with the conventional gardenia red pigment. Become.

It is a flow chart which showed the outline of the main steps in the manufacturing process of the iridoid compound-derived red pigment composition in this Example.

It is a figure which showed the calculation result of the dye residual ratio in the light resistance test of the gardenia red dye composition which concerns on Example 1. FIG.

It is a figure which showed the calculation result of the ΔE value which shows the color tone change in the light resistance test of the gardenia red pigment composition which concerns on Example 1. FIG.

It is a photographic image which showed the observation result of the beverage test liquid filled in the PET bottle in the light resistance test of the gardenia red pigment composition which concerns on Example 1. FIG.

It is a figure which showed the calculation result of the dye residual ratio in the light resistance test of the gardenia red dye composition which concerns on Example 2. FIG.

It is a figure which showed the calculation result of the ΔE value which shows the color tone change in the light resistance test of the gardenia red pigment composition which concerns on Example 2. FIG.

It is a photographic image which showed the observation result of the beverage test liquid filled in the PET bottle in the light resistance test of the gardenia red pigment composition which concerns on Example 2. FIG.

It is a figure which showed the calculation result of the dye residual ratio in the light resistance test of the gardenia red dye composition which concerns on Example 3. FIG.

It is a figure which showed the calculation result of the ΔE value which shows the color tone change in the light resistance test of the gardenia red pigment composition which concerns on Example 3. FIG.

It is a photographic image which showed the observation result of the beverage test liquid filled in the PET bottle in the light resistance test of the gardenia red pigment composition which concerns on Example 3. FIG.

It is a figure which showed the calculation result of the CHROMA value in the color development characteristic evaluation of the gardenia red pigment composition which concerns on Example 4. FIG.

It is a figure which showed the plot result on the Cartesian coordinates of the a-axis and b-axis of the Hunter Lab color system in the color development characteristic evaluation of the gardenia red pigment composition which concerns on Example 4. FIG.

It is a photograph image of the sample bottle filled with the gardenia red pigment composition produced in Example 4.

It is a figure which showed the calculation result of the CHROMA value in the color development characteristic evaluation of the gardenia red pigment composition which concerns on Example 5.

It is a figure which showed the plot result on the Cartesian coordinates of the a-axis and b-axis of the Hunter Lab color system in the color development characteristic evaluation of the gardenia red pigment composition which concerns on Example 5. FIG.

The present invention relates to a light-resistant iridoid compound-derived red pigment composition, a method for producing the same, and its use. Hereinafter, embodiments of the present invention will be described in detail.

1. 1. Production of Iridoid Compound-Derived Red Dye Composition The iridoid compound-derived red pigment composition according to the present invention can be prepared and produced by the steps described below. It should be noted that the production method according to the present invention does not exclude the inclusion of steps other than the steps described below, as long as it does not substantially interfere with the effects of the technical features according to the present invention. No. Further, the technical scope of the present invention is not limited to the embodiment including all of the following steps except for the essential steps.

The method for producing a red pigment composition derived from an iridoid compound according to the present invention is (step 1) to produce a red color by the action of an iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton and an amino group-containing compound. A dicarboxylic acid having a specific structure with respect to the total molar equivalent, a similar compound thereof, or two or more compounds selected from these is carried out in a solution containing 5 molar equivalents or more to produce a light-resistant red pigment compound. It relates to a method characterized by including a step of making a compound.

[Iridoid compound]
As used herein, the term "iridoid compound" refers to a compound having an iridoid skeleton. The compound having an iridoid skeleton refers to a compound having a structure consisting of a complex 6-membered ring containing oxygen and a 5-membered ring, and specifically, a compound having a basic skeleton structure represented by the structural formula (I). .. Here, in the structural formula (I), the iridoid skeleton constituent atoms are numbered and shown.
As the iridoid compound in the present specification, it is used as a term including not only the iridoid glycoside but also the iridoid aglycone which is the aglycone thereof. Further, the iridoid compound in the present specification includes a compound in an ionic state at the time of dissolution.
_{Here, R 1} , R ₂ , R ₃ , R ₄ , and R ₅ in the structural formula refer to arbitrary functional groups, but in the reaction substrate for red color development according to the present invention, R ₁ is a carboxyl group. Will be. Further, when R ₁ is a lower alkylated functional group such as a methyl ester group, it can be used as a reaction substrate by converting it into a carboxyl group via ester hydrolysis.
Iridoid compounds contained in plants, fruits, etc. usually have an inert and stable glycoside structure in many cases. In this case, R ₂ becomes a sugar molecule bound via a β-glycosidic bond. In the case of aglycone, which is the reaction substrate for red color development according to the present invention, the structure is such that a hydroxyl group (-OH) is added to the 1-position of the iridoid skeleton. Specifically, the structure is represented by the structural formula (II).
Many of R ₃ , R ₄ , and R ₅ contain a hydrogen atom (-H) as a functional group, but examples of compounds such as a functional group containing a hydroxyl group, an alkyl group, and a phenyl compound have also been reported. Here, in the carbons at the 6-position and the 7-position of the iridoid skeleton and / or the carbons at the 7-position and the 8-position of the iridoid skeleton, the structure having the double bond represented by the structural formula (III) or the structural formula (IV). Is also included. Further, the carbons at the 6-position and the 7-position of the iridoid skeleton and / or the carbons at the 7-position and the 8-position of the iridoid skeleton may have a structure bonded via a common atom or molecular structure. For example, a structure such as a structural formula (V) or a structural formula (VI) bonded via oxygen can be mentioned.
Further, the iridoid compound in the present invention is allowed to be a compound having various functional groups as long as the stability and color development characteristics of the red dye composition according to the present invention are not substantially impaired.

[Reaction substrate]
The method for producing a red pigment composition according to the present invention is a method for producing red color by the action of an iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton and an amino group-containing compound. Here, the "iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton" refers to an aglycone produced from an iridoid glycoside having a structure having a carboxyl group at the 4-position in the iridoid skeleton.
Specific examples of the compound include genipic acid and the like. Genipinic acid is an aglycone of geniposidic acid that is abundant in gardenia fruits. It is also a compound obtained by hydrolyzing the methyl ester group at the 4-position of the iridoid skeleton of genipin into a carboxyl group.

Raw Material Plants As a method for producing a red pigment composition according to the present invention, it is preferable to use a plant containing an iridoid compound as a raw material as a raw material. Examples of the raw material according to the present invention include gardenia, wit, catalpa ovata, and eucommia ulmoides. Further, as the raw material part of the plant body, any part above ground or underground part constituting the plant body can be used, but it is preferable to use fruits. From the viewpoint of producing a pigment composition having excellent red color-developing characteristics, it is preferable to use gardenia fruits.
Here, the term "gardenia fruit" in the present specification may include the fruit of a plant belonging to the genus Gardenia of the family Rubiaceae, but more specifically refers to the fruit of a species belonging to the gardenia. Examples of the plant belonging to Gardenia include Gardenia jasminoides, Gardenia augusta and the like. In addition, plants belonging to gardenia include related species and hybrids with related species. As a plant belonging to gardenia, Gardenia jasminoides can be mentioned in particular.
From the viewpoint of producing a pigment composition having excellent red color-developing characteristics, it is preferable to use the fruits of Gardenia jasminoides.

When a plant raw material is used in the method for producing a red pigment composition according to the present invention, an iridoid compound-containing extract from a plant can be used as the raw material. The method for extracting the iridoid compound from the plant can be a known method and is not particularly limited, but it is preferable to adopt a method in which the yield of the iridoid compound is high. As an example of preparation of the extract from a plant, the raw material is crushed, crushed, ground, crushed, pulverized, dried, etc., and then with water, hydrous alcohol, alcohol, or the like. Extracts that have been subjected to treatments such as filtration and purification can be used as plant raw material extracts.
Further, when the plant body is used as a raw material as it is without undergoing the extraction step, it is also possible to use the squeezed product, fruit juice, puree, dried product thereof and the like of the plant body as a raw material.

Hydrolysis treatment of precursor The red color development according to the present invention is carried out by using an iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton as a reaction substrate.
In the present invention, an iridoid aglycon having a carboxyl group at the 4-position of the iridoid skeleton can be directly used as a raw material, but i) when an iridoid compound having an alkyl ester group at the 4-position of the iridoid skeleton is used as a precursor. Can be used by decomposing the 4-position of the iridoid skeleton into a carboxyl group by ester hydrolysis treatment. Here, as a specific embodiment of the alkyl ester group at the 4-position, a methyl ester group is preferable. In addition, ii) when an iridoid glycoside is used as a precursor, it is possible to hydrolyze the β-glycosidic bond to generate aglycone and use it.

When an iridoid compound having an alkyl ester group at the 4-position of the iridoid skeleton as a precursor is used as a raw material in the method for producing a red pigment composition according to the present invention, i) the 4-position of the iridoid skeleton is subjected to ester hydrolysis treatment. It is preferable to carry out a reaction that decomposes into a carboxyl group.
The ester hydrolysis treatment according to the present invention may be any means as long as it involves a reaction of hydrolyzing an alkyl ester group to a carboxyl group at the 4-position of the iridoid skeleton, for example, a treatment using an alkaline solution, a treatment with an ion exchange resin, and the like. Means such as enzyme treatment having esterase activity can be adopted. As an example, an ester hydrolysis treatment can be performed by preparing an alkaline solution having a pH of about 10 to 13 with sodium hydroxide or the like and heating the solution at about 40 to 70 ° C.

When an iridoid glycoside as a precursor is used as a raw material in the method for producing a red pigment composition according to the present invention, ii) iridoid aglycone is produced by hydrolyzing the β-glycosidic bond at the 1-position of the iridoid skeleton. It is preferable to carry out a reaction to cause the reaction.
The β-glycosidic bond hydrolysis treatment may be any means involving a reaction for hydrolyzing the β-glycosidic bond at the 1-position of the iridoid skeleton, for example, an enzyme treatment having β-glucosidase activity or a microorganism having β-glucosidase activity. Means such as treatment and treatment using an acidic solution can be adopted. As an example, an aglycone-forming reaction can be carried out by preparing an enzyme solution having β-glucosidase activity having a pH of about 3 to 6 and treating the enzyme solution in the solution. Here, the enzyme having β-glucosidase activity can be used without particular limitation, and for example, cellulase or the like can be used. Examples of commercially available cellulase preparations include cellulase T "Amano", cellulase A "Amano" (manufactured by Amano Enzyme Co., Ltd.), cellulase KSM, Multifect A40, cellulase GC220 (manufactured by Genencore Kyowa Co., Ltd.), and cellulase GODO-TCL. , Cellulase GODO TCD-H, Besselex, Cellulase GODO-ACD (manufactured by Joint Sake Seisha), Cellulase (manufactured by Toyo Spinning Co., Ltd.), Cellulase, Cellulase XL-522 (manufactured by Nagase Chemtex), Cellulase, Deni Max (above Novozymes), Cellulase AC40, Cellulase AL, Cellulase T2 (above HBI), Cellulase "Onozuka" 3S, Cellulase Y-NC (above Yakult Pharmaceutical Co., Ltd.), Sumiteam AC, Sumiteam C (above new) (Manufactured by Nippon Kagaku Kogyo Co., Ltd.), Entilon CM, Entilon MCH, Biohit (manufactured by Rakuto Kasei Kogyo Co., Ltd.) and the like.

The precursor treatment described in i) and ii) above is preferably performed by a treatment method suitable for the substance or composition, depending on the type of the raw material compound or raw material composition used as the precursor.
For example, when an iridoid glycoside having an alkyl ester group at the 4-position of the iridoid skeleton is used as a precursor, it is necessary to perform both treatments i) and ii) above. Specific examples of the compound include geniposide and gardenoside, which are iridoid glycosides having a methyl ester group at the 4-position of the iridoid skeleton. Preferably, geniposide, which is abundant in gardenia fruits, is preferable.

In addition, when an iridoid glycoside having a carboxyl group at the 4-position of the iridoid skeleton is used as a precursor, the treatment of ii) above is required. Specific examples of the compound include geniposidic acid and the like. Preferably, geniposidic acid, which is abundant in gardenia fruits, is preferable. Here, geniposidic acid is a compound obtained by hydrolyzing the methyl ester group at the 4-position of the iridoid skeleton of geniposide, which is abundantly contained in gardenia fruits, into a carboxyl group.

Further, when iridoid aglycone having an alkyl ester group at the 4-position of the iridoid skeleton is used as a precursor, the treatment of i) above is required. Specific examples of the compound include genipin, which is an iridoid aglycone having a methyl ester group at the 4-position of the iridoid skeleton.

In the production method according to the present invention, when a plant or a plant extract is used as a raw material, the content ratio of the iridoid glycoside having a methyl ester group at the 4-position of the iridoid skeleton corresponding to the precursor is large. It is preferable to perform both the treatments of)) and ii) to produce iridoid aglycone, which is a substrate for red color development.
Here, the relationship between the structure of the iridoid compound and the treatment step in the production method according to the present invention is shown in a table using geniposide, geniposidic acid, and the like, which are iridoid compounds abundantly contained in gardenia fruits, as examples.

[Red color]
The method for producing a red pigment composition according to the present invention is a method for producing a red color with an action with an amino group-containing compound on an iridoid aglycone having a carboxyl group at the 4-position of the above-mentioned iridoid skeleton.
As used herein, the term "red coloration" refers to a series of reactions that proceed with the action of the above-mentioned iridoid aglycone and an amino group-containing compound. Here, "the action of the iridoid aglycon and the amino group-containing compound" means that the oxygen atom at the 2-position of the iridoid skeleton is replaced with the nitrogen atom derived from the amino group-containing compound, and the amino group-containing compound is bonded to the iridoid compound. Refers to a complex reaction consisting of an oxidative polymerization reaction between iridoid compounds and an oxidative polymerization reaction (see Japanese Patent Publication No. 55-5778).

Solvent, etc. Water is preferably used as the solvent for the solution that develops a red color according to the present invention. More preferably, purified water, distilled water, ultrapure water, or the like is preferably used, but any grade water used for food and drink production, dye preparation, and the like can be used as the solvent without any problem. Further, as the solvent, an aqueous solution containing various salts, organic acids, pH adjusters, pH buffers, lower alcohols and the like can be used as long as it does not substantially inhibit red color development.

Dicarboxylic acid having a specific structure The red color development according to the present invention is carried out under the condition that a dicarboxylic acid having a specific structure and / or a similar compound thereof is present in the reaction solution. In the present invention, by performing red color development under the condition that the compound is present, the structure of the produced red pigment compound and / or the composition of the red pigment composition is changed, and the red pigment composition is changed depending on the compositional characteristics. Will exhibit light resistance. In particular, it exhibits excellent light resistance under long-term light irradiation conditions. Further, in the present invention, by performing red color development under the condition that the compound is present, the obtained red dye composition exhibits light color resistance in addition to exhibiting light color resistance.

The red color development according to the present invention is carried out in a solution containing a dicarboxylic acid having a specific structure, a similar compound thereof, or two or more compounds selected from these as a reaction solution. Here, as the dicarboxylic acid having a specific structure, a compound represented by the following structural formula (i) can be specifically mentioned. Note that R ₁₁ in the formula indicates a hydrogen atom or a hydroxyl group. Further, the compound represented by the structural formula (i) is described as including a compound in an ionic state at the time of dissolution.

In the present invention, it is optimal to use the dicarboxylic acid according to the above structural formula (i), but it is also possible to use a similar compound thereof.
In the present specification, the "similar compound" is a compound similar to the above dicarboxylic acid and exhibiting a light resistance-imparting action comparable to or equal to or higher than that of the dicarboxylic acid when used in this step. Point to. Examples of the compound similar to the dicarboxylic acid include isomers of the dicarboxylic acid.
Further, the compound similar to the dicarboxylic acid includes a derivative of the dicarboxylic acid or a derivative thereof. The derivative refers to a compound or the like that has undergone functional group substitution or the like while maintaining the basic skeletal structure of the dicarboxylic acid or its isomer, but is compared with the dicarboxylic acid when used in this step. It is possible to use any compound that exhibits a light resistance-imparting action that is comparable to or equal to or higher than that of the compound.
In addition, the compound similar to the above-mentioned dicarboxylic acid includes a compound such as a salt of the above-mentioned dicarboxylic acid, a compound such as a salt of the above-exemplified compound, and the like. Further, examples of the compound similar to the above-mentioned dicarboxylic acid include those in an ionic state at the time of dissolution of the above-exemplified compound.

_{When R 11} is a hydrogen atom (−H) in the above structural formula (i), the compound is succinic acid. Here, "succinic acid" in the present specification is _{a kind of organic acid represented by the chemical formula of HOOC- (CH 2} ) _2- COOH, and is a compound constituting the citric acid cycle in oxygen respiration in the living body. Functions as one of. Since succinic acid is a compound widely used as an umami component, an acidulant, a food and drink additive for pH adjustment, and an excipient for pharmaceutical products, it is recognized as a compound having high safety to the human body. Further, succinic acid is inexpensive as a raw material. In addition, it is a substance that is highly soluble in water and easy to handle in the manufacturing process such as addition.
In the present invention, it is preferable to use succinic acid as the organic acid having the specific structure, but it is also possible to use a compound similar to succinic acid. In the present specification, "these analog compounds" include compounds similar to succinic acid and which exhibit the same light resistance-imparting action as succinic acid when used in this step. Here, the succinic acid analog includes a succinic acid analog that has undergone functional group substitution or the like while maintaining the basic skeletal structure of succinic acid. Further, the succinic acid analog includes a derivative having undergone functional group substitution. For example, the succinic acid analog compound according to the present invention can include oxysuccinic acid in which one of the hydrogen atoms at the 2-position of the skeleton carbon is a hydroxyl group. Here, oxysuccinic acid is another name for malic acid.
The succinic acid analog compound in the present invention also includes a compound such as a salt of succinic acid or a salt of the above-mentioned analog compound. Further, the succinic acid analog compound includes an ionic state of succinic acid or an ionic state of the above compound.

_{When R 11} is a hydroxyl group (−OH) in the above structural formula (i), the compound is malic acid. Here, "malic acid" in the present specification is _{a kind of organic acid represented by the chemical formula of HOOC-CH (OH) -CH 2-} COOH, and is L-malic acid (L- (-)-Malic). It is used as a term to refer to acid). In the living body, it functions as one of the compounds constituting the citric acid cycle in oxygen respiration. Further, also functions as a CO ₂ source of the Calvin cycle in the chloroplast of the plant. Since malic acid is a compound widely used as a food and drink additive such as an acidulant, a pH adjuster, and an emulsifier, it is recognized as a compound having high safety to the human body. Furthermore, malic acid is also inexpensive as a raw material. In addition, it is a substance that is highly soluble in water and easy to handle in the manufacturing process such as addition.
In the present invention, it is preferable to use malic acid as the organic acid having the above-mentioned specific structure, but it is also possible to use a compound similar to malic acid.
In the present specification, the "similar compound thereof" includes a compound which is similar to malic acid and exhibits a light resistance-imparting action equivalent to that of malic acid when used in this step. Malic acid analogs include optical isomers of L-malic acid. Examples of the optical isomer include D-malic acid (D- (+)-Malic acid). It may also be racemic.
Here, the malic acid-like compound includes a malic acid-like compound that has undergone functional group substitution or the like while maintaining the basic skeletal structure of malic acid or an isomer thereof. In addition, malic acid analogs include derivatives that have undergone functional group substitution. For example, the malic acid-like compound according to the present invention can include succinic acid in which the hydroxyl group at the 2-position of the skeleton carbon is a hydrogen atom.
The apple-like compound in the present invention also includes a compound such as a salt of malic acid or a salt of the above-mentioned analog. Further, the malic acid analog includes an ionic state of malic acid or an ionic state of the above compound.

The amount of the dicarboxylic acid or the like having the above-mentioned specific structure contained in the reaction solution in the red color development according to the present invention needs to be present in a large amount with respect to the iridoid compound contained in the reaction solution. That is, it is necessary to carry out the red color development according to the present invention in a solution containing a high concentration that cannot be imagined from the usual amount of succinic acid, malic acid or the like.
Specifically, the blending amount of the dicarboxylic acid or the like having the specific structure contained in the reaction solution is preferably 5 molar equivalents or more with respect to the total molar equivalents of the iridoid compound contained in the reaction solution. .. In particular, 6 molar equivalents or more, more preferably more than 6 molar equivalents, still more preferably 6.5 molar equivalents or more, still more preferably 7 molar equivalents or more, one more based on the total molar equivalents of the iridoid compound contained in the reaction solution. It is preferable in terms of imparting light resistance to the red dye composition produced to be preferably 8 molar equivalents or more. In terms of imparting particularly excellent light resistance, 6.5 molar equivalents or more, preferably 7 molar equivalents or more, and more preferably 8 molar equivalents or more are preferable with respect to the total molar equivalent of the iridoid compound contained in the reaction solution. be. Further, it is preferable that the molar equivalent is within the above range also in terms of imparting a bright red color.
The upper limit of the blending amount of the dicarboxylic acid having the specific structure is not particularly limited, but is, for example, 30 molar equivalents or less, preferably 25 molar equivalents or less, more preferably 25 molar equivalents or less, relative to the total molar equivalent of the iridoid compound contained in the reaction solution. Can be 20 molar equivalents or less.

Reaction conditions, etc. The red color development according to the present invention is carried out using iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton as a reaction substrate. As the iridoid aglycone, aglycones such as the geniposide ester hydrolyzate (for example, geniposidic acid) and the gardenoside ester hydrolyzate described above can be used.
It is preferable that the iridoid skeleton contains a geniposide ester hydrolyzate aglycone and / or a geniposide acid aglycone having a carboxyl group at the 4-position.

The amount of the iridoid compound contained in the solution for developing red color according to the present invention is not particularly limited as long as it is possible to develop red color. In a preferred embodiment, for example, the total amount of the iridoid compound contained in the solution is 0.1 to 75% by mass, preferably 0.5 to 50% by mass, based on the total mass of the solution in which the reaction is carried out. The amount can be raised. Further, the solution may contain a substance derived from a raw material other than the iridoid compound as long as it does not substantially inhibit red color development.

The red color development according to the present invention is a reaction involving a reaction in which an amino group-containing compound binds to an iridoid compound by substituting an oxygen atom at the 2-position of the iridoid skeleton with a nitrogen atom of the amino group of the amino group-containing compound.
As the amino group-containing compound suitable for the reaction, an amino acid which is a primary amino group-containing compound or a composition containing an amino acid can be used. For example, protein hydrolysates, peptides and the like can be used. As the protein hydrolyzate, for example, hydrolysates of various proteins such as wheat protein, soybean protein, milk protein, and collagen can be used. In addition, various amino acids such as glutamic acid, serine, arginine, lysine, aspartic acid, and glycine can be used. These sodium salts such as monosodium glutamate can also be preferably used. The amount of the amino group-containing compound contained in the reaction solution is not particularly limited, but in terms of preferable red color development characteristics, for example, a concentration of 0.7 equivalent or more as an amino acid is set with respect to the total molar equivalent of the iridoid compound. It is desirable to add it, and it is desirable to add a concentration of 1 molar equivalent or more. The upper limit of the amount of the amino group-containing compound with respect to the total molar equivalent of the iridoid compound is also not particularly limited, and examples thereof include 10 molar equivalents or less, more preferably 8 molar equivalents or less, and further preferably 6 molar equivalents or less.

For the red color development according to the present invention, it is preferable to carry out the reaction in an inert gas atmosphere with the reaction solution in terms of the red color development characteristics of the dye composition to be produced. The inert gas that can be used in this reaction is not particularly limited as long as it does not substantially hinder the progress of this reaction, but for example, nitrogen gas, argon gas, helium gas or the like can be used. can. It is preferable to use nitrogen gas or the like.

For the red color development according to the present invention, it is preferable to carry out the reaction under acidic conditions in terms of the red color development characteristics of the produced dye composition. The pH condition for red color development is preferably about pH 3 to 6, more preferably about pH 4 to 5. When the reaction is carried out under neutral or alkaline pH conditions, the resulting dye composition tends to be bluish and reddish, which is not suitable.
Here, as the pH adjusting means for acidic conditions, known means for blending an inorganic acid and / or an organic acid can be mentioned. It is preferable to acidify the reaction solution by blending a dicarboxylic acid or the like having the specific structure. If the reaction solution is over-acidified, it is not particularly limited as long as the pH adjusting means is adjusted to the usual alkaline conditions. As an example, means for blending sodium hydroxide, sodium carbonate, potassium hydroxide, trisodium phosphate and the like can be mentioned.

The red color development according to the present invention can be performed at room temperature of about 1 to 30 ° C. or room temperature of about 15 to 25 ° C., but it is possible to dramatically promote red color development by performing heat treatment. Suitable. The conditions for the heat treatment are 50 ° C. or higher, preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. The upper limit can be the boiling point of the aqueous solution, but it is preferably 100 ° C. or lower in the case of an aqueous solution under normal pressure and 150 ° C. or lower in the case of an aqueous solution under pressurized conditions. Specifically, it is 50 to 150 ° C, preferably 50 to 100 ° C.
The reaction time is a factor that is determined according to the temperature conditions and the like and may be appropriately determined, but it is desirable that the reaction time be carried out over a long period of several hours to several days at room temperature or room temperature. Further, under the heating conditions, for example, a range of about 1 minute to 96 hours, preferably about 10 minutes to 72 hours can be mentioned.
When the reaction conditions are insufficient due to the combination of the above temperature and / or time, the amount of the red dye compound produced is too small, which is not suitable. Further, if the reaction conditions are excessive due to the combination of the above temperature and / or time, there is a concern that unnecessary decomposition or the like may occur, which is not suitable.

In the red color development according to the present invention, it is possible to adopt an embodiment in which the reaction step is performed a plurality of times as desired. It is also possible to add various compounds and substances to be blended in the reaction solution in a plurality of times during the reaction.

[Refining, etc.]
In the method for producing a red pigment composition according to the present invention, the reaction solution obtained by the above operation can be used as an iridoid compound-derived red pigment composition, but solid-liquid separation, purification treatment, and concentration treatment are performed according to the intended use. , Dilution treatment, pH adjustment, drying treatment, sterilization treatment and the like to obtain an iridoid compound-derived red pigment composition having a desired quality and / or form.
These steps can be performed not only in the final stage after the red color is developed, but also in each of the above steps and after the treatment as appropriate. Further, it is possible to perform the desired treatments in combination, and it is also possible to perform the desired treatments a plurality of times.

The means for solid-liquid separation in the manufacturing process according to the present invention can be carried out by a conventional method. For example, it is possible to remove solid matter, aggregated insoluble matter and the like by performing filtration, suction filtration, coprecipitation, centrifugation and the like. Further, when performing filtration, it is also preferable to use a filtration aid (for example, diatomaceous earth). The solid-liquid separation treatment can be performed a plurality of times as desired.

The purification treatment in the production method according to the present invention can be carried out by using a conventional technique as long as the dye compound can be separated and purified. For example, it can be carried out by an adsorption treatment using silica gel, a porous ceramic, a styrene-based or aromatic synthetic resin or the like. It can also be carried out by an ion exchange treatment using a cationic resin or an anionic resin. Further, it can be carried out by a membrane separation treatment using a membrane filter membrane, an ultrafiltration membrane, a reverse osmosis membrane, an electrodialysis membrane, a functional polymer membrane or the like.
In the production method according to the present invention, it is preferable to carry out a purification means for removing unreacted small molecule compounds, decomposition products and the like from the produced red pigment composition. For example, it is preferable to carry out a purification treatment capable of removing small molecules having a molecular weight cut off of 3000 or less, preferably 2000 or less. In the present invention, it is preferable to remove the dicarboxylic acid having the specific structure, which is excessively added during the reaction, after the red reaction.

In the production method according to the present invention, operations such as concentration, dilution, and drying can be performed by a conventional method. Further, the purification process can be performed in the same manner as in the above paragraph. In addition, the pH adjustment operation can be performed by a conventional method.

In the manufacturing process according to the present invention, the sterilization treatment can also be performed by a conventional method. Examples of the sterilizing means include heat treatment, high pressure treatment, high pressure heat treatment, sterilization filter treatment, ultraviolet irradiation treatment, chemical treatment with a bactericidal agent, and the like. It is preferable to perform sterilization by heat treatment or high pressure heat treatment.
Examples of the temperature condition for sterilizing and heating include 60 ° C. or higher, preferably 70 ° C. or higher, and more preferably 80 ° C. or higher. The upper limit temperature is not particularly limited as long as it does not adversely affect the stability-imparting functional component, but may be 140 ° C. or lower under pressurized conditions, 100 ° C. or lower under normal pressure, and preferably 95 ° C. or lower.

[Method for imparting light resistance]
In the present invention, it is possible to impart light resistance to the produced iridoid compound-derived red pigment composition by performing the above-mentioned red color development in the production process of the iridoid compound-derived red pigment composition. That is, in the present invention, a method for imparting light resistance to the produced iridoid compound-derived red pigment composition, which comprises performing the above (step 1) in the process for producing the iridoid compound-derived red pigment composition. It will be possible to provide. In terms of the effect of imparting light resistance in the above (step 1), it is preferable to use succinic acid and / or malic acid among the compounds represented by the structural formula (i), and it is particularly preferable to use malic acid. be. The detailed properties of the light resistance imparted to the produced red pigment composition are described in paragraph 2 below. As described in.
Further, in the present invention, by performing the above-mentioned red color development in the production process of the iridoid compound-derived red pigment composition, the produced iridoid compound-derived red pigment composition is imparted with bright color in addition to light resistance. Is possible. In terms of the effect of imparting lightness in the above (step 1), it is preferable to use succinic acid and / malic acid among the compounds represented by the structural formula (i), and it is particularly preferable to use succinic acid. be. The detailed properties of the light color imparted to the produced red pigment composition are described in paragraph 2 below. As described in.

2. 2. Iridoid Compound-Derived Red Dye Composition The iridoid compound-derived red pigment composition according to the present invention is a dye composition having the following characteristics. The point to be emphasized as a characteristic of the red pigment composition according to the present invention is that it is excellent in light resistance, and in particular, it exhibits excellent color development stability even under light irradiation conditions, and is therefore derived from the iridoid compound according to the prior art. It can be widely used for applications and products that were difficult with the red pigment composition (gardenia red pigment composition).
The red pigment composition according to the present invention does not exclude features other than those described below, as long as it does not substantially interfere with the effects of the technical features according to the present invention. No. Further, the technical scope of the present invention is not limited to the embodiment including all of the following features except for the essential technical features.
In the present specification, among the numerical values representing the characteristics of the red dye composition according to the present invention, the measured values related to the Hunter Lab color system and the values calculated from the measured values are likely to fluctuate depending on the measuring device or the like. Since it is a value, it is desirable to evaluate each value by comparison with a comparative sample or the like using the same measuring device.

The red pigment composition derived from an iridoid compound according to the present invention is described in the above paragraph 1. It can be obtained by the production method described in 1. Here, regarding the red color development according to the present invention, the whole dye compound is produced by the comprehensive result of a plurality of reaction systems, but the mechanism of action thereof has not been completely elucidated and the compound structure that realizes the red color development. And the details of the composition are unknown. In the situation at the time of filing the application of the present application, in order to analyze the physical properties of the produced dye compound and identify the structural features that cause red color development, an expensive device such as a mass spectrometer is required, which is economical. The burden is heavy, and it is difficult to specify the compound structure even when these devices are used. In addition, it takes time to analyze in consideration of the speed of patent application.
Therefore, in the invention relating to the iridoid compound-derived red pigment composition according to the present invention, even if the wording in the claims includes a step of producing the product, the content of the invention is technically unclear only by the description. It is recognized that it does not correspond to the feature.

[Compositional characteristics]
The red pigment composition according to the present invention is a composition composed of a compound obtained by oxidatively polymerizing a reaction product of an iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton and an amino group-containing composition. It is not essential that the compound composition constituting the red dye composition according to the present invention contains the dicarboxylic acid or the like having the specific structure, and the dicarboxylic acid or the like having the specific structure added in the manufacturing process is produced. Even if it is removed from the composition of the above, it does not affect the light resistance and color development characteristics of the red dye composition according to the present invention.
The form of the red pigment composition according to the present invention includes, for example, a liquid form, a paste form, a gel form, a semi-solid form, a solid form, a powder form, and the like, but the form is not particularly limited.

Compound structure As the iridoid compound before the reaction, which is a constituent unit of the red pigment compound according to the present invention, the above paragraph 1. Aglycone, an iridoid compound having a carboxyl group at the 4-position of the iridoid skeleton described in the above, can be mentioned.
As the iridoid aglycone, preferably, a geniposide ester hydrolyzate aglycone and / or a geniposide acid aglycone can be mentioned.

[Stability to light]
The iridoid compound-derived red dye composition according to the present invention is a dye composition having high light resistance to light irradiation, and has a property that the color development characteristics are not easily lost under light irradiation conditions. The degree of stability is higher than that of the iridoid compound-derived red pigment composition produced by the prior art. The iridoid compound-derived red pigment composition according to the present invention can be suitably used for coloring distribution products, display products, etc., which are required to be resistant to long-term fluorescent lamp irradiation, etc., due to the characteristics related to the stability.

Dye Residuality The iridoid compound-derived red dye composition according to the present invention is a dye composition having color stability against light irradiation. Specifically, as described in (a-1) below, it is preferable that the value indicating the dye residual ratio after the light resistance test is in the range shown below.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following characteristics:
(A-1) The ^{red pigment composition derived from the iridoid compound is contained so as to have a color value E of 10% and a} _{1 cm} value of 50.5 in terms of 0.05% by mass, adjusted to Brix 10 ° with fructose-glucose liquid sugar, and When the acid sugar solution adjusted to pH 5.0 was stored at 10,000 lux irradiated with a white fluorescent lamp and at 10 ° C. for 5 days, the dye residual ratio was 62% or more, preferably 65% or more, more preferably 65% or more before storage. It is 68% or more, more preferably 70% or more, still more preferably 72% or more. Here, it can be evaluated that the higher the value of the dye residual ratio is, the higher the light stability with respect to light irradiation, and the more suitable the dye composition is.

Further, as described in (a-2) below, the iridoid compound-derived red pigment composition according to the present invention is subjected to a light resistance test depending on the presence or absence of addition of a dicarboxylic acid or the like having the above specific structure in the red color development step. It is preferable that the difference in the dye residual rate of the above is in the range shown below.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following characteristics:
(A-2) The ^{red pigment composition derived from the iridoid compound is contained so as to have a color value E of 10% and a} _{1 cm} value of 50.5 in terms of 0.05% by mass, adjusted to Brix 10 ° with fructose-glucose liquid sugar, and When the acid sugar solution adjusted to pH 5.0 is stored at 10000 lux of white fluorescent lamp irradiation and 10 ° C. for 5 days, the following formula (1) is satisfied:
Equation (1): LR _{1 −} LR ₀ ≧ 6
Here, "LR ₁ " indicates the residual dye ratio (%) of the acid sugar solution containing the iridoid compound-derived red pigment composition, which is the target, after being stored under the above-mentioned conditions by light irradiation. Further, "LR ₀ " is obtained after the acid sugar solution prepared in the same manner as above is subjected to light irradiation storage under the above conditions except that a commercially available product prepared by the conventional method is blended. The dye residual rate (%) is shown.
Here, the term "commercially available product" means the above paragraph 1. In the step of performing red color development in the production of the iridoid compound-derived red pigment composition described in the above, examples thereof include a red pigment composition prepared by performing a red color development step without blending a dicarboxylic acid or the like having the above-mentioned specific structure. .. Specifically, a dye preparation "Sunred [registered trademark] No. 2384" manufactured by Saneigen FFI Co., Ltd. can be mentioned.
In the present invention, the value on the right side in the formula (1) is a value indicating the degree of improvement in the dye residual rate in the light resistance test. The value may be 6 or more, but preferably 10 or more, more preferably 15 or more, and further preferably 18 or more.

Color difference ΔE
As described in (a-3) below, the iridoid compound-derived red pigment composition according to the present invention has a light resistance test before and after a light resistance test depending on the presence or absence of addition of a dicarboxylic acid or the like having the above specific structure in the red color development step. It is preferable that the ratio of the color difference ΔE value is in the range shown below.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following characteristics:
(A-3) The ^{red pigment composition derived from the iridoid compound is contained so as to have a color value E of 10% and a} _{1 cm} value of 50.5 in terms of 0.05% by mass, adjusted to Brix 10 ° with fructose-glucose liquid sugar, and When the acid sugar solution adjusted to pH 5.0 is stored at 10000 lux of white fluorescent lamp irradiation and 10 ° C. for 5 days, the following formula (2) is satisfied:
Equation (2): LE ₁ / LE ₀ ≤ 0.8
Here, "LE ₁ " indicates the ΔE value before and after the acid sugar solution containing the target iridoid compound-derived red pigment composition was stored under the above-mentioned conditions by light irradiation. In addition, "LE ₀ " is used before and after the acid sugar solution prepared in the same manner as above is subjected to light irradiation storage under the above conditions except that a commercially available product prepared by the conventional method is blended. Indicates the ΔE value of. Here, as the "commercial product", the same product as the commercially available product described in the above formula (1) can be used.
The value on the right side of the equation (2) in the present invention is a value indicating the degree of suppression of color tone change in the light resistance test. The value may be 0.8 or less, but preferably 0.7 or less, more preferably 0.65 or less, still more preferably 0.6 or less.

Summary of light resistance The characteristics related to the above numerical range are the characteristics showing the color development stability of the iridoid compound-derived red pigment composition under light irradiation conditions, and the red pigment composition according to the present invention is resistant to long-term light irradiation. It is a feature showing that it has light resistance. Here, in the iridoid compound-derived red pigment composition produced by using an organic acid such as citric acid, which is a conventional technique, it is necessary to realize the characteristics shown in the above numerical range in which discoloration and discoloration under the above light irradiation conditions are severe. I can't. Further, even when compared with the red dye composition produced by the technique for imparting light resistance by adding taurine according to Patent Document 3, which is the prior art, it is possible to achieve excellent light resistance equal to or inferior to that of the red dye composition. It is accepted (Examples 1 and 3 of the present specification). Here, the method according to the prior art of Patent Document 3 is a technique in which a problem in cost is recognized and a problem in application to a wide range of applications including foods and drinks is recognized.

[Color development characteristics]
As the color-developing characteristics of the iridoid compound-derived red pigment composition according to the present invention, the dye composition exhibits excellent bright color due to the compositional characteristics constituting the composition. Specifically, the red pigment derived from an iridoid compound according to the prior art tends to exhibit a bluish dark purple color or a dark red color tone, whereas the red pigment composition derived from an iridoid compound according to the present invention has a bright and vivid reddish purple color. Presents a color tone.

CHROMA value (saturation)
Since the iridoid compound-derived red pigment composition according to the present invention has particularly excellent color-developing characteristics, it is a dye composition exhibiting a unique vivid color tone. From this point of view, the iridoid compound-derived red pigment composition according to the present invention has a CHROMA value in the range shown below in the Hunter Lab color system when measured according to the method described in (b-1) below. Suitable.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following characteristics:
(B-1) When ^{an aqueous solution containing the iridoid compound-derived red pigment composition so as to have a color value E of 10% and a} _{1 cm} value of 0.05 and having a pH of 5.0 prepared with a McIlvaine buffer solution, the following formula ( 3) is satisfied:
Equation (3): C ₁ −C ₀ ≧ 4
Here, "C ₁ " indicates the CHROMA value in the aqueous solution containing the target iridoid compound-derived red dye composition. Further, "C ₀ " indicates a CHROMA value in an aqueous solution prepared in the same manner as described above except that a standard dye is blended. Here, the term "standard dye" refers to paragraph 1. In the step of performing red color development in the production of the red pigment composition derived from the iridoid compound described in 1, the red pigment composition prepared by performing the red color development step by blending citric acid without blending the dicarboxylic acid having the above specific structure or the like. The substance can be a standard dye. Specifically, a red pigment composition prepared by blending 4.3 mol equivalents of citric acid with respect to the total molar equivalent of the iridoid compound contained in the reaction solution and performing a red coloring step can be used as a standard dye. can. For example, a dye prepared in the same manner as in Sample 5-1 described in Example 5 of the present specification can be used as a standard dye.
The value on the right side of the equation (3) in the present invention is a value indicating the degree of increase in the CHROMA value. The value may be 4 or more, but preferably 5 or more, more preferably 6 or more, and further preferably 6.5 or more. The upper limit of the value is not particularly limited, but may be, for example, 30 or less, preferably 20 or less.

a value (red tone)
Since the iridoid compound-derived red pigment composition according to the present invention has excellent red color-developing characteristics, it is a dye composition exhibiting a unique reddish-purple tone. From this point of view, the iridoid compound-derived red pigment composition according to the present invention has an a value in the Hunter Lab color system within the range shown below when measured according to the method described in (b-2) below. Suitable.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following characteristics:
(B-2) When ^{an aqueous solution containing the iridoid compound-derived red pigment composition so as to have a color value E of 10% and a} _{1 cm} value of 0.05 and having a pH of 5.0 prepared with a McIlvaine buffer solution, the following formula ( 4) is satisfied:
Equation (4): A ₁ −A ₀ ≧ 4
Here, "A ₁ " indicates an a value in the aqueous solution containing the target iridoid compound-derived red pigment composition. Further, "A ₀ " indicates an a value in an aqueous solution prepared in the same manner as described above except that a standard dye is blended. Here, as the "standard dye", the same as the standard dye described in the above formula (3) can be used.
The value on the right side of the equation (4) in the present invention is a value indicating the degree of increase of the a value. The value may be 4 or more, but preferably 5 or more, more preferably 6 or more, and further preferably 6.5 or more. The upper limit of the value is not particularly limited, but may be, for example, 30 or less, preferably 20 or less.

L value (brightness)
The red dye composition derived from an iridoid compound according to the present invention is a dye composition exhibiting light color because the entire color tone is bright in addition to the above-mentioned color development characteristics. As the L value indicating the lightness of the red dye composition according to the present invention, it is preferable that the L value shows a lightness equal to or higher than that of the gardenia dye according to the prior art.
From this point of view, the iridoid compound-derived red pigment composition according to the present invention has an L value in the Hunter Lab color system within the range shown below when measured according to the method described in (b-3) below. Suitable.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following characteristics:
(B-3) When ^{an aqueous solution containing the iridoid compound-derived red pigment composition so as to have a color value E of 10% and a} _{1 cm} value of 0.05 and having a pH of 5.0 prepared with a McIlvaine buffer solution, the following formula ( 5) is satisfied:
Equation (5): L _{1 −} L ₀ ≧ 0.8
Here, "L ₁ " indicates the L value in the aqueous solution containing the target iridoid compound-derived red pigment composition. Further, "L ₀ " indicates the L value in the aqueous solution prepared in the same manner as described above except that the standard dye is blended. Here, as the "standard dye", the same as the standard dye described in the above formula (3) can be used.
The value on the right side of the equation (5) in the present invention is a value indicating the degree of increase of the L value. The value may be 0.8 or more, but is preferably 1 or more, more preferably 1.2 or more, and even more preferably 1.4 or more. The upper limit of the value is not particularly limited, but may be, for example, 20 or less, preferably 15 or less.

Overall color tone As the red pigment composition according to the present invention, the higher the CHROMA value indicating the saturation as each value of the above-mentioned Hunter Lab color system, the more vivid the color tone is suitable. Further, the higher the a value indicating the red color development property, the more preferable the color tone is to exhibit purple with redness. Further, the lower the b value indicating the blue color development property, the more preferable the color tone is to exhibit purple with a bluish tint. Further, it is preferable that the L value indicating the lightness also shows a color tone equal to or equal to or higher than that of the gardenia dye according to the prior art.

The color tone of the iridoid compound-derived red pigment composition according to the present invention is reddish purple to yellowish red at pH 5. Specifically, it is a dye composition exhibiting a hue of 10P (reddish purple) to 5RP (reddish purple) to 10RP (purple red) when expressed by the HUE value (or JIS color name) in the Munsell color system. .. Preferably, it is a dye composition exhibiting a hue of 2RP to 8RP when expressed by the HUE value in the Munsell color system at pH 5.

The color development characteristics of the iridoid compound-derived red dye composition according to the present invention can also be shown as the ratio of the absorbance at the maximum absorption wavelength to the absorbance at another fixed wavelength.
Here, as the red dye composition according to the present invention, when the dye composition-containing aqueous solution is prepared so as to have a pH of 5.0 with McIlvaine buffer, the maximum absorption wavelength is 520 to 545 nm, preferably 530 to 542 nm. It is a dye composition having.

The feature regarding the numerical range regarding the color development characteristic is a feature showing that the iridoid compound-derived red pigment composition according to the present invention has a color development characteristic of exhibiting a bright and vivid reddish purple color. Here, the above-mentioned color development characteristics cannot be realized by the iridoid compound-derived red pigment composition produced by using an organic acid such as citric acid, which is a conventional technique. For example, the red pigment composition, which is a taurine-added reaction product obtained by the method according to the prior art of Patent Document 3, which has been reported to have light resistance, is significantly inferior in saturation to the red pigment composition according to the present invention. , The redness is light and the color development characteristics are greatly different.

[Stability against heat]
The red dye composition derived from an iridoid compound according to the present invention is a dye composition having high color development stability with respect to heat, and has a property that the color development characteristics are not easily lost by heat exposure or the like. The degree of stability is as high as or higher than that of the iridoid compound-derived red pigment composition produced by the addition of citric acid, which is another conventional technique.
The iridoid compound-derived red pigment composition according to the present invention can be suitably used for coloring distribution products that are required to be resistant to high temperature storage and the like due to its stability-related properties. In addition, it can be suitably used for modes assuming heat treatment such as retort sterilization, processing, and cooking.

Dye Residuality The iridoid compound-derived red dye composition according to the present invention is a dye composition having color stability with respect to heat. Specifically, when measured according to the method described in (c-1) below, it is preferable that the value indicating the dye residual ratio is in the following range.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following characteristics:
(C-1) The ^{red pigment composition derived from the iridoid compound is contained so as to have a color value E of 10% and a} _{1 cm} value of 50.5 in terms of 0.05% by mass, adjusted to Brix 10 ° with fructose-glucose liquid sugar, and When the acid sugar solution adjusted to pH 5.0 is stored in a dark place and at 50 ° C. for 5 days, the dye residual ratio is 60% or more, preferably 70% or more, more preferably 75% or more before storage. More preferably, it is 80% or more. Here, it can be evaluated that the higher the value of the dye residual ratio is, the higher the thermal stability is, and the more suitable the dye composition is.

Color difference ΔE
As described in (c-2) below, the red pigment composition derived from the iridoid compound according to the present invention has heat resistance depending on the presence or absence of addition of a dicarboxylic acid having a specific structure such as succinic acid or malic acid in the red color development step. It is preferable that the ratio of the color difference ΔE value before and after the test is in the range shown below.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following characteristics:
(C-2) The ^{red pigment composition derived from the iridoid compound was contained so as to have a color value E of 10% and a} _{1 cm} value of 50.5 in terms of 0.05% by mass, adjusted to Brix 10 ° with fructose-glucose liquid sugar, and When the acid sugar solution adjusted to pH 5.0 is stored in a dark place and at 50 ° C. for 5 days, the following formula (6) is satisfied:
Equation (6): HE ₁ / HE ₀ ≤ 1.2
Here, "HE ₁ " indicates the ΔE value before and after high-temperature storage of the acid sugar solution containing the iridoid compound-derived red pigment composition, which is the target, under the above conditions. Further, "HE ₀ " indicates a ΔE value before and after high-temperature storage of the acid sugar solution prepared in the same manner as described above except that a commercially available product was blended. Here, as the "commercial product", the same product as the commercially available product described in the above formula (1) can be used.
The value on the right side of the formula (6) in the present invention is a value indicating the degree of suppression of color tone change in the heat resistance test. The value may be 1.2 or less, but is preferably 1 or less, more preferably 0.8 or less, still more preferably 0.75 or less.

The above-mentioned characteristics indicate that the red pigment composition according to the present invention has excellent heat resistance equal to or better than that of the conventional gardenia red pigment and the like. The stability is equivalent to that in the presence of an organic acid such as citric acid, which is a conventional technique, and it is shown that the dye composition can be used as a dye composition having excellent storage stability and processing characteristics.

[Gardenia red pigment composition]
Specific examples of the iridoid compound-derived red pigment composition according to the present invention include gardenia red pigment compositions produced by using gardenia fruit or an extract thereof as a raw material from which the iridoid compound is derived.
In the present specification, the term "gardenia red pigment composition" is used in the above paragraph 1. Refers to a pigment composition containing a red pigment compound produced by the action of an iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton derived from the gardenia fruit described in 1 and an amino group-containing composition.
Here, in the definition of "gardenia red pigment" in the 8th Edition Food Additives Official (Ministry of Health, Labor and Welfare), β-glucosidase is added to the mixture of ester hydrolysate and proteolytic product of iridoid glycosides obtained from gardenia fruits. As defined as the dye obtained by addition, the manufacturing process in the definition merely describes one aspect of the manufacturing process described in the present specification. Therefore, the gardenia red pigment composition according to the present invention is a pigment composition containing a wider range than the gardenia red pigment composition based on the general definition.
Further, the gardenia red pigment composition according to the present invention was produced by using geniposide and / or geniposidic acid separated or purified from gardenia fruit as a raw material without directly using gardenia fruit or an extract thereof as a raw material. A red pigment composition is also included. Further, a red pigment composition produced by using genipin and / or genipic acid derived from these as raw materials is also included.

[Terms related to pigments]
The main terms related to dyes used in the present specification are described below.
In the present specification, the "Hunter Lab color system (Lab system)" is a color system forming a color solid composed of Cartesian coordinates consisting of a-axis and b-axis indicating chromaticity and an L-axis perpendicular to the orthogonal coordinates. Is.
Here, the "L value" is a value expressing the brightness numerically. When the L value = 100, it becomes white, and when the L value = 0, it becomes black. The "a value" is a value that numerically expresses the color tones of red and green. The larger the + value of the a value, the stronger the red color, and the larger the negative value of the a value, the stronger the green color. The "b value" is a value that numerically expresses the color tones of yellow and blue. The larger the + value of the b value, the stronger the yellow color, and the larger the negative value of the b value, the stronger the blue color.

In the present specification, the "CHROMA value" is a value obtained by numerically expressing the distance from the origin in the Hunter Lab color system by the following equation (11). It is used as a value indicating saturation. The larger the value, the more vivid the color.

In the present specification, "color difference (ΔE)" is a point between (a ₁ , b ₁ , L ₁ ) and (a ₂ , b ₂ , L ₂ ) in which two colors are plotted in the Hunter Lab color system. It is a value expressed numerically by calculating the distance between the two by the following formula (12).

In the present specification, the "HUE value" refers to the formation angle of a straight line connecting the origin and the plot (a value, b value) on the orthogonal coordinates of the a-axis and the b-axis in the Munsell color system. It is a value representing the hue expressed by converting it into the hue notation in. It is a value representing the hue with a symbol and a numerical value.

In the present specification, the “maximum absorption wavelength” (λmax) indicates a light wavelength (nm) at which the absorption degree in the visible light region of the dye or the dye composition is maximum. Further, in the present specification, the "absorbance" is a value indicating the degree to which a substance absorbs light. For example, the absorbance (A _λ ) of the maximum absorption wavelength (λmax) can be obtained by the following equation (13). In the formula, A means the absorbance, λ means the maximum absorption wavelength, A _λ means the absorbance at the maximum absorption wavelength, I means the incident light intensity, and I ₀ means the transmitted light intensity.

In the present specification, the "dye residual ratio" is a value calculated by the following formula (14) based on the absorbance of the maximum absorption wavelength of each dye measured before and after the test such as stability. In the present specification, the residual ratio of the dye compound in which the maximum absorption wavelength is maintained is calculated as the dye residual ratio, and is used as a value for evaluating the ratio of the dye compound in which the color development characteristics are stably maintained.

In the present specification, the "color values" means "color value ^E _{10% 1 cm",} the "color value ^E _{10% 1 cm",} when the preparation of the 10 weight% of the dye composition-containing solution, It is a value calculated based on the absorbance (A: Absorbance) of the maximum absorption wavelength (λmax) in the visible light region using a measuring cell having an optical path length of 1 cm.
In the present specification, "color value conversion" means converting a dye (dye composition) into a numerical value per color value. For example, 0.05% by mass in terms of color value 60 means an amount in which the dye content contained in the solution becomes 0.05% by mass when the dye (dye composition) is adjusted to have a color value of 60. means.

In the present specification, the "McIlvaine buffer" is _{a buffer prepared using citric acid and phosphate (Na 2} HPO ₄ ), and is also known as a citric acid buffer.

3. 3. Use The iridoid compound-derived red pigment composition according to the present invention is described in paragraph 2 above. It is a dye composition having the characteristics described in the above, and is a red dye composition having excellent light stability, which exhibits excellent light resistance under long-term light irradiation conditions. Therefore, the red pigment composition according to the present invention can be widely used for applications and products that were difficult with the iridoid compound-derived red pigment composition (gardenia red pigment composition) according to the prior art.

[Dye preparation]
The iridoid compound-derived red pigment composition according to the present invention can be used as a dye preparation. In particular, when the red pigment composition according to the present invention is a gardenia red pigment composition, it is preferable to use it as a gardenia red pigment preparation.
Examples of the form of the dye preparation according to the present invention include liquid form, paste form, gel form, semi-solid form, solid form, powder form and the like, and are not particularly limited. In addition, processed solid shapes such as granules and tablets can be mentioned.
Further, since the iridoid compound-derived red pigment composition according to the present invention is water-soluble, it can be used as it is as a water-soluble dye preparation, but it is an oil-soluble dye preparation (W / O type) or double emulsification. It can also be processed into a dye preparation (W / O / W type) or the like and used.

In the dye preparation according to the present invention, the blending ratio of the iridoid compound-derived red dye composition can be appropriately adjusted according to the type and purpose of the dye preparation, and is not particularly limited, but for example, the color value E. ^{It is preferable to mix the mixture so that the 10%} _{1 cm} value is 20 or more, preferably 30 or more, and more preferably 40 or more. The upper limit of the color value of the dye preparation according to the present invention is not particularly limited, and examples thereof include a color value E of ^{10% and a} _{1 cm} value of 800.
The blending ratio of the iridoid compound-derived red pigment composition in the dye preparation may be calculated based on the above color value, but the mass base is, for example, 0.1 to 99% by mass, preferably 1 to 90% by mass, more preferably. Can be mentioned as 5 to 75% by mass.

In the dye preparation according to the present invention, other functional ingredients may be blended as long as the light resistance and color development characteristics of the red dye composition according to the present invention are not substantially impaired. .. Specifically, the dye preparation according to the present invention can be blended with an additive having a function of stabilizing or improving color development characteristics and the like. For example, antioxidants, pH adjusters, thickening polysaccharides, other food materials and the like can be blended, but the present invention is not particularly limited thereto.
Further, as the dye preparation according to the present invention, it is possible to add other dyes in addition to the red dye composition according to the present invention. The dye preparation according to the present invention can be a dye preparation adjusted to a desired color tone by blending the other dye. As the other dye that can be blended here, it is preferable that the dye is a natural dye having stable color development characteristics as in the red dye composition in the present invention. Examples include natural pigments such as gardenia jasmine, gardenia blue pigment, safflower pigment, anthocyanin pigment, monascus pigment, turmeric pigment, tamarind pigment, oyster pigment, caramel pigment, spirulina pigment, kouryan pigment, cochineal pigment, and tomato pigment. It can, but is not particularly limited to these.

[product]
In addition to being able to be suitably used as a colorant using the iridoid compound-derived red pigment composition (gardenia red pigment composition) according to the present invention. The iridoid compound-derived red pigment composition (gardenia red pigment composition), which is a conventional technique, can be used in a wide range of fields even for applications where the method and timing of addition are limited or the product itself cannot be used.

The red pigment composition or pigment preparation according to the present invention can be suitably used as a natural colorant used in products such as foods and drinks, cosmetics, pharmaceuticals, quasi-drugs, daily necessities for hygiene, and feeds. Is. That is, in the present invention, it is possible to provide foods and drinks, cosmetics, pharmaceuticals, quasi-drugs, daily necessities for hygiene, or feeds containing the red pigment composition or the pigment preparation according to the present invention.
Here, an example of a product example that can be colored with the red pigment composition or the dye preparation according to the present invention is shown below, but the colorable product according to the present invention is not limited thereto.
Examples of "food and drink" include beverages, chilled confectionery, desserts, sugar confectionery (eg, candy, gummies, marshmallows), gum, chocolate, confectionery (eg, cookies), bread making, processed agricultural products (eg, pickles, etc.). ), Processed livestock products, processed marine products, dairy products, noodles, seasonings, jellies, syrups, jams, sauces, liquors and the like.
Examples of "cosmetics" include skin lotions, lipsticks, sunscreen cosmetics, make-up cosmetics, and the like.
Examples of the "pharmaceutical product" include various tablets, capsules, drinks, troches, mouthwashes and the like.
Examples of "quasi-drugs" include nutritional supplements, various supplements, dentifrices, mouth refreshers, odor preventives, hair restorers, hair restorers, skin moisturizers, and the like.
Examples of "hygienic daily necessities" include soaps, detergents, shampoos, conditioners, hair treatments, dentifrices, bath salts, and the like.
Examples of the "feed" include various pet foods such as cat food and dog food; feed for ornamental fish and farmed fish; and the like.

The dye composition or the dye preparation according to the present invention has a property of being resistant to fading and discoloration under light irradiation conditions due to having a property excellent in light resistance, and is a product or the like which is premised on light exposure in storage, display, etc. It can also be suitably used for coloring. For example, it can be suitably used for beverages, frozen desserts, desserts, sugar confectionery and the like.
Further, since the dye composition or the dye preparation according to the present invention has excellent color development characteristics such as a bright reddish purple tone and a bright color tone in addition to light resistance, the basic color tone is milky white, which tends to be a dull color tone. It is possible to color the material in a bright reddish-purple tone. For example, it can be suitably used for coloring milk beverages, dairy products, processed fish products and the like.
Further, since the dye composition or the dye preparation according to the present invention has heat resistance, it can be used for products that are expected to be exposed to high temperature storage.

Further, the dye composition or the dye preparation according to the present invention is suitable from the viewpoint of safety because it is a method technically characterized by adding a dicarboxylic acid having a specific structure such as succinic acid or malic acid. , Suitable for use in coloring products for the purpose of ingestion into the human body. It is particularly suitable for use in coloring applications such as food and drink.

The dye composition or the dye preparation according to the present invention can be suitably used for coloring in the manufacturing process of the above product. The step of coloring the above-mentioned product can be carried out according to a standard method for each product, except that the dye composition or the dye preparation according to the present invention is blended as a natural dye. In addition, the blending ratio of the red pigment composition or the dye preparation according to the present invention to these products can be appropriately adjusted according to the type and purpose of the product. For example, in terms of color value 80, the content of the dye composition in the product is 0.001 to 1% by mass, preferably 0.005 to 0.5% by mass, and more preferably 0.01 to 0.2% by mass. More preferably, it can be blended so as to be 0.02 to 0.1% by mass.

[Various manufacturing methods]
The present invention includes a method for producing a dye preparation, a product, or the like. Specifically, a method for producing a dye preparation, a food or drink, a cosmetic, a pharmaceutical product, a quasi-drug, a daily necessities, a feed, or the like, which comprises a step of containing the above-mentioned iridoid compound-derived red pigment composition. Is included in the present invention. Here, in the manufacturing method, the above paragraph 1. A step of containing a red pigment composition derived from an iridoid compound obtained by the production method described in 1.
As the blending amount and the like of the iridoid compound-derived red pigment composition in each of these production methods, it is possible to refer to the description in the above paragraph regarding the dye preparation and each product. Further, as the manufacturing process in each manufacturing method, it is possible to adopt a dye preparation or a conventional method for each product, except that the above-mentioned iridoid compound-derived red dye composition is blended.

Hereinafter, the present invention will be described with reference to examples, but the scope of the present invention is not limited thereto.
The main steps in the manufacturing process of the iridoid compound-derived red pigment composition according to this example are shown in FIG. 1 as a flow chart. In addition, in this Example, the description "GP vs. molar equivalent" is a value which shows the addition amount or content of the compound used in the manufacturing process of gardenia red pigment composition by the molar ratio with respect to geniposide which is a raw material. .. In the present specification, it may be referred to as "eq".
In this example, as the commercially available gardenia red pigment product used as a comparative sample, the dye preparation "Sunred [registered trademark] manufactured by San-Ei Gen FFI Co., Ltd. manufactured by performing the red coloring process by the conventional technique. ] No. 2384 ”was used.

[Example 1] "Production of gardenia red pigment composition and light resistance test"
When succinic acid was added in the production process of gardenia red pigment composition, the effect on the photostability of the produced gardenia red pigment composition was investigated.

(1) "Preparation of gardenia red pigment composition"
2.25 g of 48% sodium hydroxide solution was added to 11 g of an aqueous solution containing 32% of purified geniposide (hereinafter abbreviated as GP) to prepare a pH 12 solution, and the solution was hydrated to a volume of 30 mL. Ester hydrolysis treatment was carried out by stirring at 50 ° C. for 2 hours to generate geniposidic acid.
After the hydrolysis treatment, 6.6 g of sodium glutamate (GP vs. 4.3 molar equivalents) was added, and the amount of succinic acid shown in Tables 2 and 3 was added as an organic acid to adjust the pH value to about 4.4 to 4.6. A solution having a liquid weight of 50 g was prepared by adding water, and heat-treated at 80 ° C. for 10 minutes. With respect to the acid-adjusted solution, 0.6 g of cellulase was added under a nitrogen atmosphere and the mixture was gently stirred, and a β-glucosidase reaction was carried out at 50 ° C. for 24 hours to generate aglycone geniposidate. The pH was readjusted to about 4.5, and the heat treatment was carried out at 80 ° C. for 5 hours to promote the reaction with the amino group-containing compound and the oxidative polymerization reaction of the iridoid compound, and promoted red color development. The red color development in this example is a reaction that starts progressing using the produced aglycone as a substrate even during the β-glucosidase reaction, but rapidly progresses by the subsequent heat treatment.

After cooling to room temperature, 1 part by mass of diatomaceous earth, which is a filtration aid, is added to the liquid volume and mixed to form a layer of the diatomaceous earth in advance. Filter paper (NO.2 filter, φ150 mm, manufactured by Advantech Toyo Co., Ltd.) ) Was performed by suction filtration to collect the filtrate, and a solution of diatomaceous earth red pigment composition was obtained.

(2) "Light resistance test"
The dye composition prepared above has a color value of E ^{10%, a} _{1 cm} value of 0.05% by mass in terms of 50.5, Brix 10 ° (fructose-glucose liquid sugar Brix 75 °: 13.3% by mass), and pH 5.0 (anhydrous citric acid). And adjusted with trisodium citrate), an acid sugar solution was prepared. As the gardenia red pigment composition, the one prepared in (1) above was used. The prepared acid sugar solution was sterilized at 93 ° C. to prepare a PET bottle beverage obtained by filling a 200 mL PET bottle with a hot pack.
In addition, a commercially available gardenia red pigment product was added as a comparative sample to prepare a PET bottle beverage in the same manner as described above. The commercially available gardenia red pigment product used as the comparative sample here is a product manufactured by developing a red color without adding succinic acid. Further, as another comparative sample, a gardenia red pigment composition of a taurine-added reaction product, which has been reported to have a light resistance improving effect as a prior art, was separately prepared according to the method described in Japanese Patent No. 4605824. A PET bottled beverage to which the gardenia red pigment composition was added was prepared in the same manner.
Each PET bottle beverage was irradiated with a white fluorescent lamp 10000 Lux at 10 ° C. for 10 days using a fluorescent lamp irradiator to perform a stability test on light resistance. As a fluorescent lamp irradiator, a Cultivation chamber CLH-301 (manufactured by Tomy Seiko Co., Ltd.) was used.

(3) "Evaluation of pigment residual rate and color tone change"
For the beverage test solution (PET bottle beverage) before and after the stability test, transmission at a measurement wavelength of 380 to 780 nm using a spectrophotometer (V-560, manufactured by JASCO Corporation, optical path length of the measurement cell 1 cm). Photometric color measurement was performed, and the dye residual ratio when comparing before and after the stability test was calculated by the above formula (14). The results are shown in Table 2 and FIG.
Similarly, transmitted light color measurement at a measurement wavelength of 380 to 780 nm is performed, transmitted light color measurement is performed, and the three stimulus values (L value, a value, and b value) of the Hunter Lab color system are measured and stabilized. The color difference ΔE value indicating the change in color tone comparing before the test and after the stability test was calculated by the above formula (12). The results are shown in Table 3 and FIG. The results of visual observation of PET bottled beverages are shown in FIG.

As a result, when the beverage (Sample 1-1: succinic acid-free reaction product) to which a commercially available gardenia red pigment was added, which was a comparative product, was exposed to an irradiation environment of 10000 Lux, which corresponds to photoabuse, after 5 days. The dye residual rate decreased to about 54%, and after 10 days it decreased to about 37%. In addition, the ΔE value, which indicates the change in color tone after the test, also showed a high value, indicating that the color tone changes significantly due to light irradiation.
On the other hand, the beverages (Sample 1-3, Sample 1-4) to which the gardenia red pigment composition, which is a reaction product to which succinic acid was added, were exposed to a continuous irradiation environment of 10000 Lux fluorescent lamp, which corresponds to light abuse. Even if there was, about 70 to 80% of the dye was stably maintained even after 5 days, and about 60% of the dye was maintained even after 10 days (Fig. 2). Further, the ΔE value indicating the color tone change after the test is also reduced to about 65% as compared with the value of the comparative product (Sample 1-1) 10 days after the light irradiation, and the degree of the color tone change is significantly reduced. It was shown (Fig. 3). The gardenia red dye composition of the taurine-added reaction product, which has been reported to have a light resistance improving effect as a prior art, regarding the dye residual rate and the degree of suppression of color tone change according to these samples 1-3 and 1-4 (Sample 1-2). The value was higher than the effect of.
In addition, it was confirmed that there was little fading and discoloration after the light resistance test in the visual observation of the PET bottle beverage (Fig. 4).

From the above results, it was shown that the gardenia red pigment composition having excellent light resistance can be prepared by adding succinic acid in the production process of the gardenia red pigment composition and performing a series of reaction steps.

[Example 2] "Production of gardenia red pigment composition and light resistance test"
The light resistance imparted by the addition of succinic acid in the production process of the gardenia red pigment composition was retested by removing the reaction residual substances and the like.

(1) "Preparation of gardenia red pigment composition"
In the process of producing the gardenia red pigment composition, succinic acid is added in an amount of 10 molar equivalents to GP as an organic acid to be added at the time of red color development, and the gardenia red pigment composition solution (NO. 2 filter filtrate) was prepared. Here, the red color was developed by adjusting the pH to 4.5 after the addition of succinic acid. Further, the liquid volume scale at the time of red color development was adjusted to a liquid weight of 500 g.
The obtained dye composition solution was subjected to membrane treatment using a reverse osmosis membrane to remove low molecular weight fractions from Mv2500 to 3500 to remove low molecular weight compounds such as organic acids added. The added succinic acid was also removed by the membrane treatment. The recovered impermeable liquid is concentrated under reduced pressure with an evaporator, a ^{solution is prepared with water and ethanol so that the color value E is 10%,} _{1 cm} value = about 110, and heat sterilization is performed at 80 ° C. for 10 minutes to 150 mesh. After sieving in, the sample bottle was divided into small portions to obtain a concentrated solution of the red pigment composition of Kuchinashi.

(2) "Light resistance test"
The above-prepared dye composition was ^{blended at a color value of E 10% and a} _{1 cm} value of 50.5 in terms of 0.05% by mass to prepare a PET bottle beverage in the same manner as in Example 1. A PET bottle beverage to which a commercially available gardenia red pigment product, which is a comparative sample, was added was also prepared in the same manner as in Example 1.
Each PET bottle beverage was irradiated with a white fluorescent lamp 10000 Lux at 10 ° C. for 10 days using a fluorescent lamp irradiator to perform a stability test on light resistance. The procedure and operation of the stability test were carried out in the same manner as in the method described in Example 1.

(3) "Evaluation of pigment residual rate and color tone change"
For the beverage test solutions before and after the stability test, the dye residual rate when comparing before and after the stability test was calculated in the same manner as in the method described in Example 1. The results are shown in Table 4 and FIG.
Further, the color difference ΔE value indicating the color tone change comparing before and after the stability test was calculated and evaluated in the same manner as in the method described in Example 1. The results are shown in Table 5 and FIG. The results of visual observation of PET bottled beverages are shown in FIG.

As a result, in the beverage (Sample 2-2) to which the gardenia red pigment composition, which is a reaction product to which succinic acid was added, was exposed to the environment of continuous irradiation with a fluorescent lamp of 10000 Lux for 10 days, the gardenia on the market was commercially available. The dye residual ratio was significantly higher than that of the beverage to which the red pigment composition was added (Sample 2-1: Reaction product without addition of gardenia) (FIG. 5). It was also confirmed that the change in color tone was significantly reduced (FIGS. 6 and 7).
Here, the gardenia red pigment composition according to Sample 2-2 has the light resistance of Sample 2-2 because the residual succinic acid added during the reaction is removed by the film treatment performed in the process of producing the pigment composition. It was confirmed that the action is not a phenomenon exhibited by the coexistence of succinic acid in the dye composition. That is, it was confirmed that the light resistance of the gardenia red pigment composition according to the present invention is a phenomenon exhibited by the characteristics of the dye compound itself constituting the produced gardenia red pigment composition.
Further, the amount of succinic acid added during the production of the gardenia red pigment according to Sample 2-2 was a large amount of 10 molar equivalents with respect to the total molar equivalent of the iridoid compound as a raw material. It was confirmed that the gardenia red pigment composition produced was imparted with light resistance even when the red color was developed under the addition conditions.

From the above results, it was confirmed that the gardenia red pigment composition, which is the succinic acid-added reaction product according to the present invention, is a pigment composition having excellent light resistance. As a result, the gardenia red pigment composition according to the present invention is a gardenia red pigment composition having the property of being resistant to fading and discoloration even under long-term light irradiation conditions, which are easily deteriorated by the prior art gardenia red pigment. Was confirmed.

[Example 3] "Production of gardenia red pigment composition and light resistance test"
When malic acid was added in the production process of gardenia red pigment composition, the effect on the photostability of the produced gardenia red pigment composition was investigated.

(1) "Preparation of gardenia red pigment composition"
In the process of producing the gardenia red pigment composition, malic acid was added in an amount of 8 molar equivalents to GP as the organic acid to be added at the time of red color development, and the gardenia red pigment composition solution (NO. 2 filter filtrate) was prepared. Here, the red color was developed by adjusting the pH to 4.5 after the addition of malic acid. Further, the liquid volume scale at the time of red color development was adjusted to a liquid weight of 500 g.
The obtained dye composition solution was subjected to membrane treatment using a reverse osmosis membrane in the same manner as in Example 2, to remove fractions having lower molecules than Mv2500 to 3500, concentrated under reduced pressure, and adjusted in color value. After heat sterilization and dispensing into a reagent bottle, a concentrated solution of the red pigment composition of Kuchinashi was obtained.

(2) "Light resistance test"
The above-prepared dye composition was ^{blended at a color value of E 10% and a} _{1 cm} value of 50.5 in terms of 0.05% by mass to prepare a PET bottle beverage in the same manner as in Example 1. Here, as a comparative sample, a PET bottle beverage to which a commercially available gardenia red pigment product was added was prepared in the same manner as in Example 1. The commercially available gardenia red pigment product used as the comparative sample here is a product manufactured by developing a red color without adding malic acid. As another comparative sample, a gardenia red pigment composition of a taurine-added reaction product, which has been reported to have a light resistance improving effect as a prior art, was separately prepared according to the method described in Japanese Patent No. 4605824, and the gardenia was prepared separately. A PET bottled beverage to which the red pigment composition was added was prepared in the same manner.
Each PET bottle beverage was irradiated with a white fluorescent lamp 10000 Lux at 10 ° C. for 10 days using a fluorescent lamp irradiator to perform a stability test on light resistance. The procedure and operation of the stability test were carried out in the same manner as in the method described in Example 1.

(3) "Evaluation of pigment residual rate and color tone change"
For the beverage test solutions before and after the stability test, the dye residual rate when comparing before and after the stability test was calculated in the same manner as in the method described in Example 1. The results are shown in Table 6 and FIG.
Further, the color difference ΔE value indicating the color tone change comparing before and after the stability test was calculated and evaluated in the same manner as in the method described in Example 1. The results are shown in Table 7 and FIG. The results of visual observation of PET bottled beverages are shown in FIG.

As a result, in the beverage (Sample 3-3) to which the gardenia red pigment composition which is a malic acid-added reaction product was added, even when exposed to a continuous irradiation environment of a fluorescent lamp of 10000 Lux for 10 days, a commercially available gardenia Compared with the beverage to which the red pigment composition was added (Sample 3-1: the reaction product to which no malic acid was added), the residual pigment ratio was significantly higher (FIG. 8). It was also confirmed that the change in color tone was significantly reduced (FIGS. 9 and 10). The dye residual rate and the degree of suppression of color tone change according to the sample 3-3 are higher than the effect of the gardenia red dye composition (sample 3-2) of the taurine-added reactant, which has been reported to have a light resistance improving effect as a prior art. It showed a clearly high value.

From the above results, even when a series of reaction steps was carried out by adding malic acid, which is a kind of dicarboxylic acid having a structure similar to that of succinic acid, in the production process of gardenia red pigment composition, succinic acid was used. Similarly, it was confirmed that a gardenia red pigment composition having excellent light resistance can be prepared. In addition, it was confirmed that the effect was superior to the prior art of imparting light resistance by adding taurine.

[Example 4] "Evaluation of color development characteristics"
When succinic acid was added in the production process of the gardenia red pigment composition, the effect on the color development characteristics of the produced gardenia red pigment composition was investigated.

(1) "Preparation of gardenia red pigment composition"
In the process for producing the gardenia red pigment composition, succinic acid to be added at the time of red color development is added as shown in Table 8, and the gardenia red pigment composition solution (NO. 2) is carried out in the same manner as in the method described in Example 1. Filter filtrate) was prepared. Here, the red color was developed by adjusting the pH to 4.5 after the addition of succinic acid. Further, the liquid volume scale at the time of red color development was adjusted to a liquid weight of 50 g.

(2) "Evaluation of color development characteristics"
The color development characteristics of the above-prepared dye composition solution were evaluated. For the measured value used for color tone evaluation, ^{prepare a test solution having a color value of E 10%} _{1 cm} = 0.05 using McIlvaine buffer pH 5.0, and use a spectrophotometer (V-560, manufactured by Nippon Spectral Co., Ltd., measurement cell). The transmitted light color measurement was performed at a measurement wavelength of 380 to 780 nm using the optical path length of 1 cm), and the tristimulus values (L value, a value, and b value) of the Hunter Lab color system were measured. The measurements were then used to evaluate lightness, saturation, and hue. As the "brightness", the value of the L value measured above was used as it was for evaluation. The "saturation" was evaluated by calculating the CHROMA value using the above formula (11). The "hue" was evaluated by calculating the HUE value. The results are shown in Table 8, FIG. 11 and FIG. The results of visual observation of the reagent bottle are shown in FIG.

As a result, the L value indicating the lightness and the CHROMA value indicating the saturation showed high values in correlation with the amount of succinic acid added at the time of red color development in the dye production. In particular, the CHROMA value was confirmed to have a clear correlation with the amount of succinic acid added, indicating that the larger the amount of succinic acid added, the brighter the gardenia red pigment was prepared (Fig. 11). .. Specifically, regarding the correlation between the amount of succinic acid added and the rate of increase in the CHROMA value, a large CHROMA value was obtained between the GP vs. 2 molar equivalent (Sample 4-1) and the GP vs. 5 molar equivalent (Sample 4-2). An increase was confirmed. It was also confirmed that there was a gradual upward correlation between GP vs. 5 molar equivalents (Sample 4-2) and GP vs. 10 molar equivalents (Sample 4-4).
Further, the a value and the b value indicating the hue showed a correlation with the amount of succinic acid added, and showed a tendency to shift to the red and blue sides as the amount of succinic acid added increased (FIG. 12). In particular, the shift to the red side was remarkable. Specifically, a significant increase in a value (shift to the red side) was confirmed between the GP vs. 2 molar equivalent (Sample 4-1) and the GP vs. 5 molar equivalent (Sample 4-2). It was also confirmed that there was a gradual upward correlation between GP vs. 5 molar equivalents (Sample 4-2) and GP vs. 10 molar equivalents (Sample 4-4). A gradual decrease correlation was confirmed between the GP vs. 2 molar equivalent (Sample 4-1) and the GP vs. 10 molar equivalent (Sample 4-4) for the decrease in the b value (shift to the blue side).
The above-mentioned color development characteristics were also confirmed from the results of visual observation of the HUE value and the filling reagent bottle (FIG. 13).

From the above results, it was shown that the gardenia red pigment composition having a bright reddish purple color can be produced by increasing the amount of succinic acid added in the process of producing the gardenia red pigment composition. In particular, it was shown that by increasing the amount of succinic acid added, a gardenia red pigment composition having a bright reddish-purple tone with improved saturation can be produced.
Here, the color tone of the Kuchinashi red pigment composition achieved by adding succinic acid equal to or more than 5 molar equivalents to GP is a vivid purplish red tone, and in particular, the color tone achieved by adding succinic acid equal to or more than 7 molar equivalents to GP is extremely vivid. It showed a reddish purple tone.
In the manufacturing process of this example, the pH of the solution before the heat treatment that promotes red color development was readjusted to about 4.5 as in Example 1, so that the gardenia red pigment due to the addition of succinic acid was used. It was confirmed that the lightening action was not caused by pH.

[Example 5] "Comparison of color development characteristics with citric acid-added reactant"
The color development characteristics of the gardenia red pigment composition, which is a succinic acid-added reaction product, were compared with the gardenia red pigment composition, which is a citric acid-added reaction product, which is a prior art.

(1) "Preparation of gardenia red pigment composition"
In the process of producing the gardenia red pigment composition, succinic acid is added in an amount of 10 molar equivalents to GP as the organic acid to be added at the time of red color development, and the gardenia red pigment composition solution (NO) is the same as the method described in Example 1. .2 Filter filtrate) was prepared. As a comparative sample, a gardenia red pigment composition solution (NO.2 filter filtrate) was prepared in the same manner by adding an organic acid to be added at the time of red color development in an amount equivalent to 4.3 molar equivalents (pH about 4.5). bottom. Here, the red color was developed by readjusting the pH to 4.5 after the addition of the organic acid. Further, the liquid volume scale at the time of red color development was adjusted to a liquid weight of 500 g.
The obtained dye composition solution was subjected to membrane treatment using a reverse osmosis membrane in the same manner as in Example 2, to remove fractions having lower molecules than Mv2500 to 3500, concentrated under reduced pressure, and adjusted in color value. After heat sterilization and dispensing into a reagent bottle, a concentrated solution of the red pigment composition of Kuchinashi was obtained.

(2) "Evaluation of color development characteristics"
The color development characteristics of the above-prepared dye composition solution were evaluated. The values indicating the lightness, the saturation, and the hue were calculated by measuring the three stimulus values of the Hunter Lab color system in the same manner as in the method described in Example 4. The color difference ΔE value indicating the difference in color tone between the prepared samples was calculated using the formula (12) in the same manner as in the method described in Example 1 except that the values between the samples were compared. The results are shown in Table 9, FIG. 14, and FIG.

As a result, the gardenia red pigment composition (Sample 5-2), which is a succinic acid-added reaction product, is compared with the gardenia red pigment composition (Sample 5-1), which is a citric acid-added reaction product, which is a prior art. The L value indicating lightness and the CHROMA value indicating saturation showed high values. In particular, the CHROMA value indicating saturation was a significantly high value (FIG. 14). Further, the a value and the b value indicating the hue tended to shift to the red and blue sides, and the shift to the red side was particularly remarkable (FIG. 15).
Here, the gardenia red pigment composition according to the present embodiment has the residual succinic acid added during the reaction removed by the film treatment performed in the process of producing the pigment composition, so that the color development characteristics of the sample 5-2 are the same. It was confirmed that this is not a phenomenon exhibited by the coexistence of succinic acid in the dye composition. That is, it was confirmed that the color-developing characteristic of the gardenia red pigment composition according to the present invention is a phenomenon exhibited by the characteristics of the dye compound itself constituting the produced gardenia red pigment composition.

From the above results, by adding succinic acid in the red color development in the gardenia red pigment composition manufacturing process, a vivid reddish purple tone completely different from the red pigment composition obtained by adding citric acid, which is a prior art. It has been shown that a dye composition exhibiting the above is prepared.

[Example 6] "Evaluation of heat resistance"
The thermal stability of the gardenia red pigment composition prepared in the above example was evaluated.

(1) "Preparation of gardenia red pigment composition"
The gardenia red pigment composition, which is the concentrated solution after the film treatment prepared in Examples 2 and 3, was subjected to the following test.

(2) "Heat resistance test"
The above-prepared dye composition was ^{blended at a color value of E 10% and a} _{1 cm} value of 50.5 in terms of 0.05% by mass to prepare a PET bottle beverage in the same manner as in Example 1. Further, as a comparative sample, a PET bottle beverage to which a commercially available product or a dye composition according to the prior art was added was prepared in the same manner as in the method described in Example 3. Each PET bottled beverage was stored in a dark place at a high temperature of 50 ° C. for 10 days to perform a stability test on heat resistance.

(3) "Evaluation of pigment residual rate and color tone change"
For the beverage test solutions before and after the stability test, the dye residual rate when comparing before and after the stability test was calculated in the same manner as in the method described in Example 1. The results are shown in Table 10.
Further, the color difference ΔE value indicating the color tone change comparing before and after the stability test was calculated and evaluated in the same manner as in the method described in Example 1. The results are shown in Table 11.

As a result, in the beverage to which the gardenia red pigment composition which is a succinic acid addition reaction product was added (Sample 6-3) and the beverage to which the gardenia red pigment composition which is an apple acid addition reaction product was added (Sample 6-4), Even when exposed to a storage environment of 50 ° C, which corresponds to heat abuse, for 5 days, about 82 to 86% of the pigment is stably maintained, and a beverage containing a commercially available gardenia red pigment composition (Sample 6-). It showed a higher value than 1) and the gardenia red pigment composition (Sample 6-2) of the taurine-added reaction product which is a prior art. Furthermore, about 78 to 84% of these gardenia red pigment compositions were stably maintained even after 10 days. In addition, the ΔE value indicating the change in color tone after the test was lower than that of the comparative samples 6-1 and 6-2.

From the above results, it was confirmed that the gardenia red pigment compound prepared by adding succinic acid or malic acid during the reaction is a pigment compound having thermal stability equal to or higher than that of the commercially available gardenia red pigment.

4-1: Sample 4-1
4-2: Sample 4-2
4-3: Sample 4-3
4-4: Sample 4-4

5-1: Sample 5-1
5-2: Sample 5-2

Claims (11)

In the method for producing a red pigment composition derived from an iridoid compound,
(Step 1) A compound represented by the following structural formula (i) with respect to the total molar equivalent of the iridoid compound, which produces a red color with the action of the iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton and the amino group-containing compound. , The similar compound, or two or more compounds selected from these, in a solution containing 5 mol equivalents or more to produce a light-resistant red pigment compound.
A method for producing a red pigment composition derived from an iridoid compound, which comprises:

(In the formula, R ₁₁ represents a hydrogen atom or a hydroxyl group.). The step of performing the red color development according to the above (step 1) is performed with a solution containing a larger amount of succinic acid and / or malic acid than 6 molar equivalents with respect to the total molar equivalent of the iridoid compound, claim 1. The method for producing a red pigment composition derived from an iridoid compound according to. The method for producing an iridoid compound-derived red pigment composition according to claim 1 or 2, wherein the iridoid compound-derived red pigment composition is a gardenia red pigment composition. The step according to the above (step 1) is to carry out a reaction for producing iridoid aglycone from an iridoid glycoside by β-glycosidic bond hydrolysis prior to and / or in parallel with red color development. The method for producing an iridoid compound-derived red pigment composition according to any one of 3 to 3. In the method for producing a red pigment composition derived from an iridoid compound,
(Step 1') The red coloration associated with the action of the geniposide ester hydrolyzate aglycon and / or the geniposidate aglycon having a carboxyl group at the 4-position of the iridoid skeleton and the amino group-containing compound was added to the total molar equivalent of the iridoid compound. On the other hand, it was carried out under acidic conditions with a solution containing a larger amount of succinic acid and / or iridoid than 6 mol equivalents.
The process of producing a red pigment compound with light resistance,
Including
The step according to the above (step 1') is to carry out a reaction for producing iridoid aglycone from an iridoid glycoside by β-glycosidic bond hydrolysis prior to and / or in parallel with red color development.
The iridoid compound-derived red pigment composition is a gardenia red pigment composition.
A method for producing a red pigment composition derived from an iridoid compound, which comprises the above. The production of the iridoid compound-derived red pigment composition, which comprises performing the above-mentioned (step 1) according to any one of claims 1 to 4 or the above-mentioned (step 1') according to claim 5. A method for imparting light resistance to a red pigment composition derived from an iridoid compound. The iridoid compound-derived red pigment composition obtained by the production method according to any one of claims 1 to 5. Iridoid compound-derived red pigment composition having the characteristics described in the following (A) and (B):
(A) The ^{red pigment composition derived from the iridoid compound was contained so as to have a color value E of 10% and a} _{1 cm} value of 50.5 in terms of 0.05% by mass, adjusted to Brix 10 ° with fructose-glucose liquid sugar, and pH 5. When the acid sugar solution adjusted to 0 was stored at 10000 lux irradiated with a white fluorescent lamp and at 10 ° C. for 5 days, the residual dye ratio was 62% or more before storage.
(B) When ^{an aqueous solution containing the iridoid compound-derived red pigment composition so as to have a color value E of 10% and a} _{1 cm} value of 0.05 and having a pH of 5.0 prepared with a McIlvaine buffer solution, the following formula is satisfied:
Equation: C _{1 −} C ₀ ≧ 4
(In the formula, C ₁ indicates the CHROMA value in the aqueous solution containing the iridoid compound-derived red dye composition, and C ₀ indicates the CHROMA value in the aqueous solution prepared in the same manner as described above except that the standard dye is blended. Here, the standard dye indicates a dye composition prepared in the same manner as in Sample 5-1 described in Example 5). A dye preparation containing the iridoid compound-derived red pigment composition according to claim 7 or 8. A food or drink, a cosmetic, a pharmaceutical product, a quasi-drug, a daily necessities for hygiene, or a feed containing the iridoid compound-derived red pigment composition according to claim 7 or 8 or the dye preparation according to claim 9. A dye preparation, a food or drink, a cosmetic, a pharmaceutical product, or a quasi-drug, which comprises a step of containing the iridoid compound-derived red pigment composition obtained by the production method according to any one of claims 1 to 5. A method for manufacturing a product, sanitary daily necessities, or feed.

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