WO2019111861A1

WO2019111861A1 - Iridoid-compound-derived red pigment composition and method for producing same

Info

Publication number: WO2019111861A1
Application number: PCT/JP2018/044449
Authority: WO
Inventors: 敬子泉田; 浜崎　孝治; 貴正横山
Original assignee: 三栄源エフ・エフ・アイ株式会社
Priority date: 2017-12-05
Filing date: 2018-12-04
Publication date: 2019-06-13
Also published as: JPWO2019111861A1

Abstract

The present invention addresses the problem of providing a technique which relates to the production of an iridoid-compound-derived red pigment composition, and is advantageous from the viewpoint of the safety of the produced pigment composition, and can produce a red pigment composition that is not only improved in color lightness but also can have a hue having both of brilliant redness and clearness acceptable in various fields including a milky product, a beverage and the like. The present invention relates to a method for producing an iridoid-compound-derived red pigment composition, the method being characterized by including a step of subjecting a solution, which contains an organic acid comprising ascorbic acid, a compound analogous to ascorbic acid or at least two compounds selected from ascorbic acid and the compound in a total amount of 4 molar equivalent or more relative to the total molar equivalent of an iridoid compound, to the red color development associated with the reaction between an iridoid aglycon having a carboxyl group at position-4 in an iridoid skeleton with a compound containing an amino group, thereby producing a red pigment compound having a property of developing a color having both of brilliant redness and clearness.

Description

Iridoid compound-derived red pigment composition and method for producing the same

The present invention relates to an iridoid compound-derived red pigment composition and a method for producing the same. More specifically, the present invention relates to a technology for producing a red-pigment composition derived from an iridoid compound having a color tone and a combination of light-redness, which can be used in various fields.

Gardenia red pigment is a pigment exhibiting a red color tone produced from a gardenia fruit extract, and is a natural pigment having relatively high stability to light and 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 an amino group-containing compound. In the development of the gardenia red pigment, the pigment having a red color tone has been developed by improving a part of the process of producing the blue pigment which is a pigment compound having a structure derived from an iridoid compound (patented) Literature 1).
In addition, gardenia red pigment also overlaps with the consumer's safety intention in recent years because it is derived from plant raw materials, and instead of insect-derived cochineal pigment and other synthetic red pigment etc., food, drink, cosmetics, quasi-drugs and medicine Demand in many fields such as is expanding. In particular, the gardenia red pigment is used as an excellent pigment material which can also be used in the food and beverage field.

While such excellent advantages are recognized in many cases in the gardenia red pigment, there is also a problem of narrowing the range of application and practical use thereof in terms of its coloring characteristics.
Specifically, the conventional gardenia red pigment generally tends to exhibit a bluish dark purple red tone, but is not suitable for coloring a food material to be bright red. There is. The characteristic regarding the said color is a place which does not raise a problem in particular if the color assumed the dark red or muddy purple system or the target material itself is originally dark color, etc., while milk white food materials such as dairy products and paste products Also, its use is difficult in applications where the beverage etc. is colored bright red etc.

Here, as a prior art related to lightening of a gardenia red pigment, a technology related to Patent Document 2 is disclosed. In the document, specifically, there is disclosed a method of using a specific amino acid or a salt thereof as a primary amino group-containing substance and adding an excessive amount of a specific organic acid at the time of red color development in the production process (( Patent Document 2).
In this technology, excessive addition of citric acid or the like is one of the solution means (Patent Document 2 left column, lines 3 to 8 and lines 30 to 32; Example 1, Tables 1 and 2 and the like) However, when the present inventors performed the reproduction, it was not possible to say that the color was near bluish purple and that a sufficiently vivid red tone gardenia red pigment was prepared (this specification). Examples 1 and 2).

In addition, as a technique for lightening of a gardenia red pigment, a method of adding a sulfite ion such as sodium pyrosulfite or potassium pyrosulfite in the formation reaction of the pigment composition (Patent Document 3), a method of adding a taurine-containing substance ( The method of adding the substance of patent document 4), etc. at the time of reaction can be mentioned.
However, the lightening effects of these compounds in Patent Document 3 and Patent Document 4 are high in L value but low in b value and strong in bluish color (Patent Document 3 paragraph 0027 and Example, Patent Document 4 paragraph 0035) And, it can not be recognized as a color tone that can achieve the vivid red color tone which is the subject of the present application.
In addition, sulfite ions such as sodium metabisulfite and potassium pyrosulfite used in the technology according to Patent Document 3 are compounds that are concerned about the effects when used in food and drink applications, and removal processing was performed in the subsequent steps. It is also recognized as a technology that can be avoided for the current consumer who is highly security oriented. In addition, since the taurine-containing substance used in the technology according to Patent Document 4 is a substance whose price per unit weight is so expensive that it can not be compared with ordinary organic acids etc., there is a problem in the point of raw material acquisition. It is also recognized.

Thus, there is a need for a technique for overcoming the problems related to the color development characteristics of the prior art gardenia red pigment, in order to expand the range of application and practical use of the gardenia red pigment, in the prior art in this technical field. No technology has been reported that can realize a bright reddish gardenia red pigment that can be used in various fields.

Japanese Patent Publication No. 55-5778 Patent No. 2802451 Patent No. 5753733 Patent No. 4605824

The present invention has been made in view of the circumstances of the prior art described above, and the subject of the present invention is a technique relating to the production of an iridoid compound-derived red pigment composition, and in terms of the safety of the produced pigment composition. Provided is a suitable technology, and a technology for producing a red pigment composition having a combination of redness and lightness that can be used in various fields including milky white products, beverages, etc., not simply improvement in lightness. The purpose is

The inventors of the present invention conducted intensive studies in the state of the above-mentioned prior art, and found that ascorbic acid was used in the step of performing red color development accompanied by the action of iridoid aglycone having a carboxyl group at position 4 of iridoid skeleton and an amino group containing compound. I conceived the method of adding excess. The inventors of the present invention developed a red color by the method based on the above idea, and thus a beautiful red iridoid compound-derived red pigment composition having both bright redness and bright redness whose color tone was shifted to the yellow side was prepared. I found that.
Furthermore, when the present inventors intensively researched, when the ascorbic acid addition amount in the organic acid added in red color development is more than fixed, the above-mentioned "color tone excellent in reddishness" is achieved. I found it to be done. And when the total amount of all the organic acids containing ascorbic acid in the said red color development is more than fixed, it discovered that it became a color tone to which lightness and chroma were fully provided. In addition, the present inventors can prepare a red pigment composition with variations in color tone by changing the ratio of ascorbic acid and other organic acids to be added together with the above conditions. Found out.

Here, “the color tone excellent in reddish color” in the present invention is that “a value, b value, and CHROMA value in the Hunter Lab color system show high values due to“ action of ascorbic acid ”in red color development. When lightening is performed by simply increasing the amount of organic acid of citric acid, although it is achieved, the lightness (L value) is bluish even though the lightness (L value) is improved compared to before the increase. As a result, it exhibits a dark color tone, and a gardenia red pigment having both bright redness and lightness is not realized (Examples 1 and 2 of the present specification).
In this respect, in Patent Document 2 which is the prior art as described above, ascorbic acid is described as one of them in the paragraph of the list of examples of organic acids (Patent Document 2 p2 right column, lines 2-3), However, the said description of patent document 2 is only parallel writing of the citric acid etc. which do not show the reddishness which concerns on this invention. Further, in Patent Document 2, an example using ascorbic acid is only described as a comparative example as one of usage examples in the case where lightness is not sufficient (Patent Document 2 p3 right side Table 1 and No. 1 Lines 19-21).
Similarly, although ascorbic acid is listed and listed as an example of an organic acid also in patent documents 3 and 4 (patent document 3 paragraph 0036, patent document 4 paragraph 0030), also in these descriptions, the bright redness concerning the present invention is mentioned. In the examples of Patent Documents 3 and 4, only the example in which citric acid is added as an organic acid is disclosed.
As is apparent from these points, Patent Documents 2 to 4 are only documents disclosing inventions based on technical ideas different from the present invention, and even when the descriptions of these documents are taken into consideration, It can not be understood that the excellent bright red tone which can not be achieved by other organic acids such as citric acid can be realized when the acid is added at the time of red color development.

The present inventors have completed the present invention based on the above findings. The present invention relates specifically to the invention described below.
[Item 1]
In a method of producing an iridoid compound-derived red pigment composition,
(Step 1) 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,
The organic acid containing ascorbic acid, its analogous compound, or two or more compounds selected from these is carried out in a solution containing 4 molar equivalents or more in total of organic acids relative to the total molar equivalents of iridoid compounds,
Producing a red pigment compound having a color forming property having bright redness and lightness,
A method for producing an iridoid compound-derived red pigment composition, comprising:
[Section 2]
The step of performing the red coloration described in the above (Step 1) is
In addition to ascorbic acid, its analogous compounds, or two or more compounds selected therefrom as the organic acid, a solution containing an organic acid other than these is used.
Item 2. A method for producing the iridoid compound-derived red pigment composition according to Item 1.
[Section 3]
The step of performing the red coloration described in the above (Step 1) is
It is carried out in a solution containing one molar equivalent or more of ascorbic acid, an analogue thereof, or two or more compounds selected therefrom with respect to the total molar equivalent of the iridoid compound.
The manufacturing method of the iridoid compound origin red pigment composition as described in claim 1 or 2.
[Section 4]
The step of performing the red coloration described in the above (Step 1) is
As a molar ratio with respect to the total amount of organic acids, it is carried out in a solution containing 12.5% or more of ascorbic acid, its analogous compounds, or two or more compounds selected therefrom.
Item 4. A method for producing an iridoid compound-derived red dye composition according to any one of Items 1 to 3.
[Section 5]
The step of performing the red coloration described in the above (Step 1) is
The organic acid may be selected from citric acid, succinic acid, malic acid, lactic acid, tartaric acid, fumaric acid, or similar compounds thereof, in addition to ascorbic acid, its analogous compounds, or two or more compounds selected therefrom. In a solution containing two or more compounds,
5. A method for producing a red pigment composition derived from the iridoid compound according to any one of items 1 to 4.
[Section 6]
The method for producing an iridoid compound-derived red pigment composition according to any one of Items 1 to 5, wherein the iridoid compound-derived red pigment composition is a gardenia red pigment composition.
[Section 7]
The method according to any one of items 1 to 4, wherein the step described in the above (Step 1) is carried out prior to and / or in parallel with the formation of a red color, from the formation of iridoid aglycone from iridoid glucoside by β-glycosidic bond hydrolysis. The manufacturing method of the iridoid compound origin red pigment composition in any one of 6.
[Section 8]
A process for producing an iridoid compound-derived red pigment composition according to any one of items 1 to 7, which comprises performing the above-mentioned (step 1), to a produced iridoid compound-derived red pigment composition. A method for imparting color development characteristics having lightness.
[Section 9]
Iridoid compound-derived red pigment composition having the characteristics described below:
When the aqueous solution of pH 5.0 is prepared with the McIlvaine buffer so as to have a color value E ^10% _{1 cm} value 0.05 and the above-mentioned red dye composition is obtained, the following (formula 1) is satisfied:
(Expression 1): Δa + Δb ≧ 2
Δa = a ₁ -a ₀
Δ b = b _1- b ₀
(Wherein, a ₁ and b ₁ represent the a value and b value respectively in the Hunter Lab color system in the aqueous solution containing the iridoid compound-derived red pigment composition, and a ₀ and b ₀ represent the iridoid, respectively) The a value and the b value in an aqueous solution prepared in the same manner as described above except that a standard dye is blended instead of the compound-derived red dye composition are shown, where the standard dye is the sample described in Example 1. 1 shows a pigment composition prepared in the same manner as 1-1).
[Section 10]
Item 8. An iridoid compound-derived red pigment composition obtained by the method according to any one of Items 1 to 7.
[Item 11]
Item 11. A dye preparation comprising the iridoid compound-derived red dye composition according to item 9 or 10.
[Section 12]
Item 11. A food or drink product containing the iridoid compound-derived red pigment composition according to item 9 or 10, or the pigment preparation according to item 11, a cosmetic, a medicine, a quasi-drug, a hygiene daily product, or a feed.
[Section 13]
Item 8. A pigment preparation, a food or drink, a cosmetic, a medicine, a quasi-drug comprising a step of containing the iridoid compound-derived red pigment composition obtained by the method according to any one of items 1 to 7 , Sanitation daily necessities, or methods of producing feed.

The present invention is a technique relating to the production of an iridoid compound-derived red pigment composition, which is a suitable technique from the viewpoint of the safety of the pigment composition produced, and includes various products including milky white products, beverages, etc. It is possible to provide a red pigment composition having a combination of redness and lightness that can be used in various fields.
According to the present invention, it becomes possible to provide, for example, a gardenia red pigment having a bright redness and a light colorability that can be used also for bright red coloring of milky white products, beverages etc., and it is difficult with conventional gardenia red pigment It can be widely used for various applications and products.

In the manufacturing process of the iridoid compound origin red pigment composition in a present Example, it is the flowchart which showed the outline of the main processes.

FIG. 6 is a diagram showing the plotting results on the a-axis and b-axis orthogonal coordinates of the Hunter Lab color system in the evaluation of coloring properties of the gardenia red pigment composition according to Example 1.

It is the photographic image which image | photographed the sample bottle filled with the gardenia red pigment composition manufactured in Example 1. FIG.

In color development characteristic evaluation of the gardenia red pigment composition which concerns on Example 2, it is the figure which showed the plotting result on the a-axis of the Hunter Lab color system, and the b-axis orthogonal coordinate.

It is the photographic image which image | photographed the sample bottle filled with the gardenia red pigment composition manufactured in Example 2. FIG.

In color development characteristic evaluation of the gardenia red pigment composition which concerns on Example 3, it is the figure which showed the plotting result on the a-axis of the Hunter Lab color system, and the b-axis orthogonal coordinate.

It is the photographic image which image | photographed the sample bottle filled with the gardenia red pigment composition manufactured in Example 3. FIG.

In color development characteristic evaluation of the gardenia red pigment composition which concerns on Example 4, it is the figure which showed the plotting result on the a-axis of the Hunter Lab color system, and the b-axis orthogonal coordinate.

It is the photographic image which image | photographed the sample bottle filled with the gardenia red pigment composition manufactured in Example 4.

The present invention relates to a red pigment composition derived from an iridoid compound having both bright redness and lightness, a method for producing the same, and use thereof. Hereinafter, embodiments of the present invention will be described in detail.
This application is an application accompanied by a priority claim based on Japanese Patent Application No. 2017-233021 filed by the present applicant in Japan, the entire contents of which are incorporated by reference into the present application.

1. Preparation of Iridoid Compound Derived Red Pigment Composition The iridoid compound derived red pigment composition according to the present invention can be prepared and manufactured according to the process described below. In addition, in the manufacturing method according to the present invention, unless it substantially interferes with the function and effect exerted by the technical feature according to the present invention, excluding including other steps other than the steps described below. Absent. Moreover, the technical scope concerning this invention is not limited to the aspect including all the following processes except an essential process.

The process for producing the iridoid compound-derived red pigment composition according to the present invention comprises: (Step 1) ascorbic acid, red color development accompanied by the action of iridoid aglycone having a carboxyl group at the 4-position of iridoid skeleton and an amino group containing compound; The reddish color is obtained by a solution containing an organic acid containing the similar compound or two or more compounds selected from these, in a total amount of the organic acid of 4 molar equivalents or more to the total molar equivalent of the iridoid compound. And a step of producing a red dye compound having a color forming property having lightness.

[Iridoid compound]
In the present specification, the "iridoid compound" refers to a compound having an iridoid skeleton. Here, a compound having an iridoid skeleton refers to a compound including a structure comprising a 5-membered ring fused to a hetero 6-membered ring containing oxygen, and more specifically, a basic skeleton represented by the structural formula (I) It refers to a compound having a structure. Here, in structural formula (I), the ring structure is given to the iridoid skeleton constituent atoms by numbering.
The iridoid compound in the present specification is used as a term including not only iridoid glycosides but also the aglycone iridoid aglycone. Moreover, as an iridoid compound in this specification, the thing of the ionic state at the time of melt | dissolution is also included.
Here, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ in the structural formulas refer to any functional groups, but in the reaction substrate for red color development according to the present invention, R ₁ is a carboxyl group It becomes. 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 to a carboxyl group via ester hydrolysis.

The iridoid compounds contained in plants and fruits usually have an inactive and stable glycoside structure in many cases. In this case, R ₂ is a sugar molecule linked via a β-glycosidic bond. In the case of aglycone which is a reaction substrate for red color development according to the present invention, it has a structure in which a hydroxyl group (—OH) is added to the 1 position of the iridoid skeleton. Specifically, the structure is represented by Structural Formula (II).
In addition, examples of compounds in which R ₃ , R ₄ , and R ₅ have many compounds containing a hydrogen atom (—H) as a functional group but have a hydroxyl group, an alkyl group, or a functional compound containing a phenyl compound are also reported. ing. Also, although there are many examples where R ₃ and R ₄ are a hydrogen atom (—H), examples of compounds such as an alkyl group or an alkyl alcohol group are also reported for R ₃ and R ₅ .
Here, at the carbons at the 6 and 7 positions of the iridoid skeleton and / or at the carbons at the 7 and 8 positions of the iridoid skeleton, a structure having a double bond shown in structural formula (III) or structural formula (IV) Also included. The carbons at positions 6 and 7 of the iridoid skeleton and / or the carbons at positions 7 and 8 of the iridoid skeleton may be bonded via a common atom or molecular structure. For example, structures such as structural formula (V), structural formula (VI) and the like bonded via oxygen can be mentioned.
Furthermore, as the iridoid compound in the present invention, an embodiment in which the compound is provided with various functional groups is acceptable as long as the stability and coloring properties 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 performing red color development 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. Here, "an 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 carboxyl group at the fourth position in the iridoid skeleton.
Specific examples of the compound include genipinic acid and the like. Genipinic acid is an aglycone of geniposidic acid which is abundantly contained in gardenia fruits. It is also a compound obtained by hydrolyzing the 4-position methyl ester group of the iridoid skeleton of genipin to a carboxyl group.

Raw material plant As a manufacturing method of the red pigment composition concerning the present invention, it is suitable to use a plant containing an iridoid compound as a raw material as a raw material. As raw materials according to the present invention, for example, gardenia, wit (genipa americana), catalpa, silkworm, and the like can be mentioned. Moreover, as a raw material site | part of a plant body, although it is also possible to use any site | part of the above-ground part which comprises a plant body, and an underground part, it is suitable to use a fruit. It is preferable to use a gardenia fruit in terms of the production of a pigment composition excellent in red color development characteristics.
Here, the term "gardenia fruit" as used herein can refer to the fruit of a plant belonging to the genus Rubiaceae Gardenia, but more specifically refers to the fruit of a species belonging to gardenia. As a plant belonging to gardenia, Gardenia jasminoides, Gardenia augusta etc. can be mentioned in detail. Further, plants belonging to gardenia also include hybrids with these close relatives and close relatives. As plants belonging to gardenia, mention may be made in particular of Gardenia jasminoides.
In terms of the production of a pigment composition excellent in red color development characteristics, it is preferable to preferably use the fruit of Gardenia jasminoides.

When using a plant raw material in the manufacturing method of the red pigment composition which concerns on this invention, the iridoid compound containing extract from a plant body can be used as a raw material. The extraction method of the iridoid compound from the plant can be performed by 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 increased. As an example of preparation of an extract from a plant body, for example, the raw material is crushed, crushed, ground, crushed, crushed, powdered, dried and the like, and then treated with water, water-containing alcohol, alcohol or the like. What was extracted and processed, such as filtration and refinement | purification, can be used as a plant raw material extract.
Moreover, when using a plant body as a raw material as it is as a raw material, without passing through an extraction process about a plant body, it is also possible to use the squeeze thing of a plant body, fruit juice, puree, these dried materials etc. as a raw material.

Hydrolysis Treatment of Precursor The red coloration 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, it is possible to directly use iridoid aglycone having a carboxyl group at position 4 of the iridoid skeleton as a raw material, but i) when using an iridoid compound having an alkyl ester group at position 4 of the iridoid skeleton as a precursor. Can be used by decomposing the 4-position of the iridoid skeleton to 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, in the case of using iridoid glucoside as a precursor ii), it is possible to hydrolyze the β-glycosidic bond to generate aglycone for use.

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

When the precursor iridoid glucoside is used as a raw material in the method for producing a red pigment composition according to the present invention, ii) the iridoid aglycone is formed by hydrolyzing the β-glycosidic bond at position 1 of the iridoid skeleton It is preferable to carry out the reaction.
The hydrolysis treatment of the β-glycosidic bond may be any means involving a reaction to hydrolyze the β-glycosidic bond at position 1 of the iridoid skeleton, for example, an enzyme treatment having β-glucosidase activity, a microorganism having β-glucosidase activity Means such as treatment or treatment using an acidic solution can be employed. As one example, an aglycone production reaction can be carried out by preparing an enzyme solution having β-glucosidase activity of about pH 3 to 6 and treating it in the solution.
Here, the enzyme having β-glucosidase activity can be used without particular limitation, and for example, cellulase can be used. As commercially available cellulase preparations, for example, cellulase T "Amano", cellulase A "Amano" (above Amano Enzyme Co., Ltd.), Driselase KSM, Multifect A40, cellulase GC220 (above Genene Core Kyowa Co., Ltd.), cellulase GODO-TCL Cellulase GODO TCD-H, Besselex, Cellulase GODO-ACD (manufactured by Kyodo Shuseki Co., Ltd.), Cellulase (manufactured by Toyobo Co., Ltd.), Cellulase, Cellulase XL-522 (manufactured by Nagase ChemteX Co., Ltd.), Cell soft, Deni Max (more than Novozymes), cellulosin AC40, cellulosin AL, more cellulosin T2 (more than H), cellulase "Onozuka" 3S, cellulase Y-NC (all above Yakult Pharmaceutical Co., Ltd.), Sumi Team AC, Sumi Team C ( As described above, Shin Nippon Chemical Industry Co., Ltd., Enchilon CM, Enchilon MCH, Bio-Hit (above, Shoto Kasei Kogyo Co., Ltd.) and the like can be mentioned.

The precursor treatment described in the above i) and ii) is preferably carried out by a treatment method suitable for the substance and composition depending on the kind of the raw material compound and the 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 carry out 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 that is abundantly contained in gardenia fruit is suitable.
When an iridoid glycoside having a carboxyl group at the 4-position of the iridoid skeleton is used as a precursor, the treatment of the above ii) is necessary. Specific examples of the compound include genipocidic acid and the like. Preferably, geniposidic acid, which is abundant in gardenia fruit, is suitable. 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 fruit, to a carboxyl group.
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 necessary. 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 of iridoid glucoside having a methyl ester group at position 4 of the iridoid skeleton corresponding to the precursor is large. It is preferred to carry out both treatments of) and ii) to form 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 the table with an example of an iridoid compound, i.

[Red color]
The method for producing a red dye composition according to the present invention is a method of performing red color development accompanied by the action of an amino group-containing compound on iridoid aglycone having a carboxyl group at the 4-position of the above-described iridoid skeleton.
As used herein, “red color development” refers to a series of reactions that proceed with the action of the iridoid aglycone and the amino group-containing compound. Here, "the action of iridoid aglycone and an amino group-containing compound" means that the oxygen atom at position 2 of the iridoid skeleton is substituted by the nitrogen atom derived from the amino group-containing compound, and the amino group-containing compound is bound to the iridoid compound Refers to a complex reaction consisting of a reaction to be conducted and an oxidation polymerization reaction of iridoid compounds (see Japanese Patent Publication No. 55-5778).

As a solvent of the solution such as a solvent for performing red color development according to the present invention, water is preferably used. More preferably, it is preferable to use purified water, distilled water, ultrapure water or the like, but if it is a grade of water used for food and drink manufacture, pigment preparation and the like, it can be used without problems as the solvent. Further, as the solvent, it is possible to use an aqueous solution containing various salts, organic acids, pH adjusters, pH buffers, lower alcohols and the like, as long as the red coloring is not substantially inhibited.

Ascorbic acid and / or its analogous compound The red color development according to the present invention is carried out under the condition that an organic acid containing ascorbic acid and / or its analogous compound is present as an organic acid in the reaction solution.
In the present invention, by performing red coloration in the presence of ascorbic acid and / or a similar compound thereof, the structure of the red pigment compound produced and / or the composition of the red pigment composition are changed, and the compositional A bright reddish yellowish tone is imparted to the color tone of the red pigment composition produced by the features. This achieves beautiful color development characteristics with "brightness" in the produced red pigment composition.

The red coloration according to the present invention is carried out in a solution containing ascorbic acid, its analogous compound, or two or more compounds selected therefrom as a reaction liquid.
Here, "ascorbic acid" is used as a term referring to L-ascorbic acid in the present specification. In the living body, it is a physiologically active substance that functions as vitamin C, and is a compound widely used as an antioxidant for food and drink etc., so it is recognized as a compound with high safety for the human body. Furthermore, ascorbic acid is inexpensive as a raw material. In addition, it is a substance that has high water solubility and is easy to handle with regard to handling in manufacturing processes such as addition. Moreover, as ascorbic acid in this specification, the thing of the ion state at the time of melt | dissolution is also included.

In the present invention, it is optimal to use L-ascorbic acid which is ascorbic acid, but it is also possible to use similar compounds.
In the present specification, “an analogue thereof” refers to an analogue of ascorbic acid and which exhibits a brightening property equal to or higher than that of ascorbic acid when used in this step. . Analogues of ascorbic acid include optical isomers and stereoisomers of L-ascorbic acid. For example, as an optical isomer, D-xyloascorbic acid can be mentioned. Further, as a stereoisomer, alaboisoascorbic acid can be mentioned, and erythorbic acid which is D-araboisoascorbic acid is also included in the stereoisomer.
Furthermore, as an analogous compound of ascorbic acid, a derivative of ascorbic acid or a derivative of an isomer thereof is also included. The derivative refers to a compound or the like in which a functional group is substituted while maintaining the basic skeleton structure of ascorbic acid or an isomer thereof, and among them, when used in this step, it is compared with ascorbic acid. It is possible to use any compound which exerts no reddening effect or an equal or more brightening effect.
Further, examples of compounds similar to ascorbic acid also include compounds such as salts of ascorbic acid, compounds such as salts of the compounds exemplified above, and the like. Moreover, as an ascorbic acid analogue compound, the thing of the ion state at the time of melt | dissolution of the compound illustrated above is also contained.

The amount of ascorbic acid and / or its analog compound to be contained in the reaction solution in the red color development according to the present invention needs to be larger than the amount usually expected to the iridoid compound contained in the reaction solution. is there. The presence of ascorbic acid and / or a similar compound thereof in a certain amount or more in the reaction solution realizes color development characteristics with "brightness" in the produced red pigment composition.
Specifically, it is preferable that the blending amount of ascorbic acid and / or its analog compound to be contained in the reaction liquid is 1 molar equivalent or more to the total molar equivalent of the iridoid compound contained in the reaction liquid. . In particular, it is at least 2 molar equivalents, preferably at least 3 molar equivalents, more preferably at least 4 molar equivalents, still more preferably at least 4.5 molar equivalents, particularly preferably 5 molar equivalents relative to the total molar equivalents of the iridoid compound contained in the reaction solution. A molar equivalent of at least 6, more preferably at least 6 molar equivalents, particularly preferably at least 6 molar equivalents is preferred from the viewpoint of imparting the reddishness of the resulting red pigment composition.
The upper limit of the blending amount of ascorbic acid and / or its analogous compound is not particularly limited, but, for example, 30 molar equivalents or less, preferably 25 molar equivalents or less, relative to the total molar equivalents of iridoid compounds contained in the reaction solution Preferably, 20 molar equivalents or less can be mentioned.
Here, in the present specification, the term "total molar equivalent of the iridoid compound" refers to the amount corresponding to the total moles (the total number of moles of all the compounds having an iridoid skeleton) of all the iridoid compounds contained in the reaction solution. Further, "molar equivalent to total molar equivalent of iridoid compound" indicates a molar ratio to an amount corresponding to the total moles of all iridoid compounds contained in the reaction solution.

Total Amount of Organic Acid In the present invention, the structure and / or red dye compound produced by performing red coloration under conditions where the organic acid containing ascorbic acid and / or its analogous compound is present in a large amount as the total amount Alternatively, the composition of the red pigment composition changes, and the compositional feature of the composition imparts to the color tone of the red pigment composition a bright and bright lighted red color tone. Thereby, in addition to the "brightness", in the produced red pigment composition, a color development characteristic having "brightness" is realized.

Specifically, the total amount of the organic acids contained in the reaction solution is preferably 4 molar equivalents or more with respect to the total molar equivalents of the iridoid compound contained in the reaction solution. In particular, it is at least 5 molar equivalents, more preferably at least 5.8 molar equivalents, still more preferably at least 6 molar equivalents, still more preferably at least 6 molar equivalents relative to the total molar equivalents of the iridoid compound contained in the reaction solution It is preferable from the viewpoint of imparting the bright redness and lightness of the red dye composition to be produced if it is preferably at least 6.5 molar equivalents, particularly preferably at least 7 molar equivalents.
The upper limit of the total amount of organic acids is not particularly limited, but for example, it is 30 molar equivalents or less, preferably 25 molar equivalents or less, more preferably 20 molar equivalents or less based on the total molar equivalents of the iridoid compound contained in the reaction solution. It can be mentioned.
Here, the "total amount of organic acid" is indicated in molar equivalents relative to the total molar equivalent of the iridoid compound contained in the reaction solution.

Other organic acids In the red color development according to the present invention, the organic compound to be contained in the reaction liquid in the range where i) the blending amount of ascorbic acid and / or its analogous compound and ii) the total amount of organic acids satisfy the above conditions As the acid, an embodiment in which an organic acid other than ascorbic acid and / or its analog compound is contained in the solution can be adopted.
That is, in the present invention, in the step of performing red color development described in the above (Step 1), as the organic acid, ascorbic acid, its analogous compounds, or two or more compounds selected therefrom It is possible to adopt an aspect of carrying out with a solution containing an acid.

In the present invention, by changing the ratio of ascorbic acid and / or other organic acid to be contained together with its similar compound within the range satisfying the above conditions, the red pigment composition according to the present invention can be obtained with variations in color tone. It becomes possible to prepare a product. That is, in the present invention, by changing the ratio of the organic acid in the range satisfying the above conditions i) and ii), it is possible to adjust the color tone of the obtained red pigment composition.

Here, as the "ratio" of ascorbic acid and / or a similar compound thereof to another organic acid, it is preferred that the content ratio of ascorbic acid and / or a similar compound to the total amount of organic acids is a certain value or more. Is preferable in terms of beautiful color development characteristics.
That is, in the present invention, ascorbic acid, as a molar ratio to the total amount of organic acids (total number of moles of all organic acids) contained in the reaction liquid, in the step of performing red color development described in (Step 1) above. 12.5% or more, preferably 25% or more, more preferably 35% or more, still more preferably 37.5% or more, particularly preferably 40% or more of the analogous compounds or two or more compounds selected therefrom It is preferable to carry out with a solution containing preferably 50% or more.
Here, “the molar ratio of ascorbic acid and the like to the total amount of organic acids contained in the reaction liquid” can be calculated using the molar equivalent to the total molar equivalent of the iridoid compound contained in the reaction liquid as an index. Specifically, the total molar equivalent of the iridoid compound contained in the reaction liquid is a molar equivalent of ascorbic acid, its analogous compound, or two or more compounds selected therefrom with respect to the total molar equivalent of the iridoid compound contained in the reaction liquid The total amount (unit: molar equivalent) of the organic acid to can be calculated as a denominator.

From the viewpoint of imparting a bright red color, as a molar ratio to the total amount of organic acids contained in the reaction solution, ascorbic acid, its analogous compounds, or two or more compounds selected therefrom are preferably 55% or more, more preferably 60 It is preferable to use a solution containing at least%, more preferably at least 62.5%, particularly preferably at least 70%, more preferably at least 75%.
In particular, in terms of coexistence of bright red color tone and color tone variation, ascorbic acid, a compound similar thereto, or two or more compounds selected from these as a molar ratio with respect to the total amount of organic acids contained in the reaction liquid. 5 to 95%, preferably 25 to 95%, more preferably 35 to 90%, still more preferably 37.5 to 90%, particularly preferably 40 to 90%, more preferably 50 to 87.5%. Solution can be mentioned suitably.

From the viewpoint of imparting color variation, in the step of performing red color development described in the above (Step 1), ascorbic acid, a compound similar thereto, or a compound selected from these as a molar ratio to the total amount of organic acids contained in the reaction liquid It is suitable to carry out with a solution containing 5% or more, preferably 10% or more, more preferably 12.5% or more of organic acids other than the above compounds.
In particular, in terms of achieving both bright red color tone and color tone variation, as a molar ratio to the total amount of organic acids contained in the reaction solution, ascorbic acid, its analogous compounds, or organic acids other than two or more compounds selected therefrom 5 to 90%, preferably 5 to 87.5%, more preferably 5 to 75%, still more preferably 10 to 65%, particularly preferably 10 to 62.5%, more preferably 12.5 to 50. The solution containing at% can be mentioned suitably.

Another kind of organic acid added together with ascorbic acid and / or its analog compound in the red color development of the present invention is an organic acid which realizes the color tone according to the present invention and can impart color variation. If it is, it is possible to use without particular limitation. In addition, it is possible to use an organic acid which achieves the colorability according to the present invention and has no or substantially no influence on the color tone without particular limitation.
Here, specifically, citric acid, succinic acid, malic acid, lactic acid and tartaric acid can be specifically mentioned as other organic acids which can realize the coloring characteristics of the bright red color tone and can impart color tone variation according to the present invention. , Fumaric acid, etc. can be mentioned.
It is also possible to adopt these similar compounds. Here, as these similar compounds, there can be mentioned compounds which exhibit a comparable function to those of these organic acids when used in this step. Examples of these similar compounds include derivatives of the above-described organic acids, isomers of the above-described organic acids, or derivatives of the above-mentioned isomers. In addition, compounds such as salts of these compounds and those in an ionic state at the time of dissolution are also included.
Moreover, in the red color development of the present invention, it is also possible to combine two or more compounds selected from these organic acids and their similar compounds, and include them in a solution.

That is, in the step of performing red color development as described in the above (Step 1), citric acid, succinic acid, malic acid, as the organic acid, in addition to ascorbic acid, its analogous compounds, or two or more compounds selected therefrom. It is possible to carry out in a solution containing lactic acid, tartaric acid, fumaric acid, their analogous compounds, or two or more compounds selected therefrom.
In addition, as an example of a preferred embodiment, when another acid is used as citric acid, succinic acid, their analogous compounds, or two or more compounds selected therefrom, it is particularly preferable in combination with ascorbic acid. It is preferable because the color development characteristics can be achieved.

In the red color development of the present invention, the color value of the red pigment composition produced may be improved with respect to the unit weight of the iridoid compound which is the raw material, depending on the kind of the above-mentioned other organic acids to be blended. For example, when citric acid, malic acid, succinic acid, lactic acid and the like are used in combination as another organic acid, the color value of the manufactured red pigment composition tends to be high, and the unit weight of the iridoid compound used as the raw material used The amount of color obtained around will improve.

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, an aglycone such as the geniposide ester hydrolyzate described above (eg, geniposidic acid, etc.), the Gardenoside ester hydrolyzate, etc. can be used. Preferably, it is preferable that the geniposide ester hydrolyzate aglycone having a carboxyl group at the 4-position of the iridoid skeleton is aglycone and / or geniposidic acid aglycone. In particular, it is preferable to contain genipinic acid.

As a compounding quantity of the iridoid compound contained in the solution which performs red color development which concerns on this invention, if red coloring can be performed, it is possible to employ | adopt what kind of compounding quantity without a restriction | limiting in particular.
In a preferred embodiment, for example, the total amount of iridoid compounds 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 performed. The amount can be mentioned. In addition, 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 the reaction of the amino group-containing compound with the iridoid compound by substitution of the oxygen atom at position 2 of the iridoid skeleton with the nitrogen atom of the amino group of the amino group-containing compound.
As the amino group-containing compound suitable for the reaction, a composition containing an amino acid or an amino acid that is a primary amino group-containing compound 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, soy protein, milk protein, collagen and the like 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 sodium glutamate and the like can also be suitably used.
The amount of the amino group-containing compound to be contained in the reaction solution is not particularly limited, but in terms of the preferred red color development characteristics, for example, a concentration of 0.7 molar equivalent or more as the amino acid relative to the total molar equivalent of the iridoid compound Is desirable, and it is desirable to add a concentration that results in one or more molar equivalents. The upper limit of the amount of the amino group-containing compound to the total molar equivalent of the iridoid compound is also not particularly limited, but may be, for example, 10 molar equivalents or less, more preferably 8 molar equivalents or less, still more preferably 6 molar equivalents or less.

The red coloration according to the present invention is preferably carried out with the reaction solution under an inert gas atmosphere in view of the red coloration characteristics of the produced dye composition. As the inert gas which can be used in the present reaction, any inert gas which does not substantially inhibit the progress of the present reaction can be used without particular limitation. For example, nitrogen gas, argon gas, helium gas etc. may be used. it can. Preferably, nitrogen gas or the like is used.

The red color development according to the present invention is preferably carried out 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 at a pH of neutral or alkaline conditions, the resulting pigment composition tends to be bluish and reddish, which is not preferable.
Here, as a pH adjustment means to acidic conditions, the well-known means to mix | blend an inorganic acid and / or an organic acid can be mentioned. Preferably, the reaction solution is acidified by blending the above-mentioned organic acid. In addition, when the reaction solution is excessively acidified, pH adjustment means in the usual direction of alkalization may be performed, and it is not particularly limited. As an example, a means etc. which mix | blend sodium hydroxide, sodium carbonate, potassium hydroxide, trisodium phosphate etc. 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 at normal temperature of about 15 to 25 ° C. However, the heat treatment makes it possible to dramatically accelerate red color development. It is suitable. The heat treatment conditions are 50 ° C. or more, preferably 60 ° C. or more, and more preferably 70 ° C. or more. Although the upper limit can mention the boiling point of aqueous solution, in the case of the aqueous solution under normal pressure, 100 degrees C or less and 150 degrees C or less are suitable in the aqueous solution under pressure conditions. Specifically, the temperature is 50 to 150 ° C., preferably 50 to 100 ° C.
The reaction time may be an element which is determined according to the temperature conditions and the like, and may be appropriately determined. However, if the reaction temperature is room temperature or normal temperature, it is preferable to perform for several hours to several days. The heating conditions may be, for example, in the range of about 1 minute to 96 hours, preferably about 10 minutes to 72 hours.
If the reaction conditions are insufficient due to the combination of the above temperature and / or time, the amount of the red dye compound formed is too small to be suitable. In addition, in the case where the reaction conditions are too excessive due to the combination of the above temperature and / or time, unnecessary decomposition and the like may occur, which is not preferable.

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. In addition, an embodiment is also possible in which various compounds and substances to be added to the reaction solution are added in plural times during the reaction.

[Purification treatment etc]
In the method for producing a red pigment composition according to the present invention, the reaction liquid obtained by the above operation can be used as an iridoid compound-derived red pigment composition, but solid-liquid separation, purification treatment, concentration treatment depending on the application It is desirable to obtain an iridoid compound-derived red pigment composition which is subjected to dilution treatment, pH adjustment, drying treatment, sterilization treatment and the like to obtain a desired quality and / or form.
These steps can be appropriately performed not only at the final stage after red color development but also after the above-described respective steps and treatments. Further, it is also possible to perform desired processing in combination, and it is also possible to perform desired processing multiple times.

The means for solid-liquid separation in the production process according to the present invention can be performed by a conventional method. For example, filtration, suction filtration, coprecipitation, centrifugation and the like can be performed to remove solids, aggregated insolubles and the like. Moreover, when filtering, it is also suitable to use a filter aid (for example, diatomaceous earth etc.). In addition, it is also possible to perform the said solid-liquid separation process in multiple times as desired.

The purification treatment in the production method according to the present invention can be performed using conventional techniques as long as separation and purification of the dye compound are possible. For example, it can be carried out by adsorption treatment using silica gel, porous ceramic, styrenic or aromatic synthetic resin or the like. Moreover, it can also carry out by the ion exchange process using cationic resin or anionic resin. In addition, the membrane separation treatment can be performed 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 low molecular weight compounds or decomposition products from the produced red pigment composition. For example, it is preferable to carry out a purification treatment that enables removal of low molecular weight molecules having a molecular weight cut off of 3,000 or less, preferably 2,000 or less. In the present invention, it is preferable to remove ascorbic acid and the like excessively added at the time of the above reaction after the red reaction.

In the production method according to the present invention, the operation of processing such as concentration, dilution, drying and the like can be carried out by a conventional method. In addition, purification treatment can be performed in the same manner as the above paragraph. Moreover, it is possible to perform pH control operation by a conventional method.

In the production process according to the present invention, sterilization can also be performed by a conventional method. Examples of means for sterilization include heat treatment, high pressure treatment, high pressure heat treatment, sterilization filter treatment, ultraviolet irradiation treatment, chemical treatment with a sterilizing agent, and the like. Preferably, sterilization is preferably performed by heat treatment or high-pressure heat treatment.
As temperature conditions at the time of performing sterilization heating, 60 ° C or more, preferably 70 ° C or more, more preferably 80 ° C or more can be mentioned, for example. The upper limit temperature is not particularly limited as long as the stability imparting functional component is not adversely affected, but may be 140 ° C. or less under pressure conditions, 100 ° C. or less under normal pressure, preferably 95 ° C. or less.

Ascorbic acid or the like added at the time of red color development in the present invention does not substantially affect the equilibrium state of the reaction and the like. That is, it is recognized that the method for producing the red pigment composition according to the present invention is a technique comparable to the prior art in terms of the production yield with respect to the raw materials.

[Method for imparting color development characteristics having bright redness and lightness]
In the present invention, the iridoid compound-derived red pigment composition produced in the production process of the iridoid compound-derived red pigment composition according to the present invention has a beautiful color forming property having both bright redness and lightness. It becomes possible to grant.
That is, in the present invention, the iridoid compound-derived red pigment composition produced in the production process of the iridoid compound-derived red pigment composition is characterized in that the iridoid compound-derived red pigment composition produced is brighter and brighter A method is provided to impart chromogenic properties.

Further, in the present invention, the ratio of ascorbic acid and / or its similar compound to the total amount of organic acids in the red colored solution, the ratio of other organic acids to the total amount of organic acids, the type and combination of other organic acids By doing this, it is also possible to impart a coloration variation to the produced iridoid compound-derived red pigment composition while having both reddishness and lightness.
That is, in the present invention, the iridoid compound-derived red pigment composition produced in the production process of the iridoid compound-derived red pigment composition is characterized in that the iridoid compound-derived red pigment composition produced is brighter and brighter And a method of applying a color tone change.

Here, about the detailed characteristic of the coloring property provided to the red pigment composition manufactured, the following paragraph 2. As described in

2. Iridoid Compound-Derived Red Pigment Composition The iridoid compound-derived red pigment composition according to the present invention is a pigment composition provided with the features described below. The point to be emphasized as the characteristics of the red pigment composition according to the present invention is the point of being excellent in bright redness and lightness and bright different from the bluish dark tone of ordinary gardenia red pigment etc. A color development characteristic of bright red tone is realized.
As the red pigment composition according to the present invention, unless it substantially interferes with the function and effect exerted by the technical features according to the present invention, it is excluded that the other features other than the features described below are included. Absent. Further, the technical scope of the present invention is not limited to the embodiment including all the following features except the essential technical features.

The iridoid compound-derived red pigment composition according to the present invention comprises the above-mentioned paragraph 1. It is possible to obtain by the manufacturing method as described in. Here, with regard to red color development according to the present invention, a compound of a dye compound is formed by an overall result of a plurality of reaction systems, but its action mechanism is not completely elucidated, and a compound which realizes red color development The details of the structure and composition are unknown. In the situation at the time of filing the present application, in order to analyze the physical properties of the produced dye compound to specify the structural features and the like that cause red coloration, expensive equipment such as a mass spectrometer is required, which is economical It is difficult to identify the compound structure even if these devices are used. In addition, analysis takes time in consideration of the quickness 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 a product, it is technically unclear the contents of the invention only by the description. It is recognized that the feature is not applicable.

[Compositional feature]
The red pigment composition according to the present invention is a composition comprising a compound obtained by oxidation polymerization of 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. That is, the color forming property of the red dye composition according to the present invention is exhibited by a compound obtained by oxidation polymerization of 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. .
The compound composition constituting the red pigment composition according to the present invention does not necessarily include ascorbic acid and / or a similar compound thereof or another organic acid. That is, the color forming properties of the red pigment composition according to the present invention are not exhibited by the inclusion of the organic acid in the composition produced after red color development, but after the production of the organic acid added in the production process. Even if it is removed from the composition, it does not affect the color development characteristics of the red pigment composition according to the present invention.
Further, as the form of the red pigment composition according to the present invention, for example, liquid form, paste form, gel form, semi-solid form, solid form or powder form may be mentioned, but the form is not particularly limited.

Compound Structure As the iridoid compound before the reaction to be a constituent unit of the red pigment compound according to the present invention, the above-mentioned paragraph 1. Mention may be made of the aglycone of the iridoid compounds having a carboxyl group at the 4-position of the iridoid skeleton described in 1. As the iridoid aglycone, preferably, geniposide ester hydrolyzate aglycone and / or geniposidic acid aglycone can be mentioned. In particular, genipinic acid can be mentioned.

[Coloring characteristics]
As color development characteristics of the iridoid compound-derived red pigment composition according to the present invention, the composition characteristic of the composition constitutes a pigment composition exhibiting bright redness and lightness. Specifically, while the iridoid compound-derived red pigment according to the prior art tends to be bluish to exhibit purple or dark red tone, the iridoid compound-derived red pigment composition according to the present invention exhibits a bright and bright red tone. .

a Value and b Value The iridoid compound-derived red pigment composition according to the present invention is a pigment composition exhibiting a unique bright red tone. In the iridoid compound-derived red pigment composition according to the present invention, it is preferable that the a value and the b value in the Hunter Lab color system be in the following ranges when measured according to the method described below.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following features:
When the aqueous solution of pH 5.0 is prepared with the McIlvaine buffer so as to have a color value E ^10% _{1 cm} value 0.05 and the above-mentioned red dye composition is obtained, the following (formula 1) is satisfied:
(Expression 1): Δa + Δb ≧ 2
Δa = a ₁ -a ₀
Δ b = b _1- b ₀
Here, a ₁ and b ₁ in the formula respectively indicate the a value and the b value in the Hunter Lab color system in the aqueous solution containing the iridoid compound-derived red pigment composition. Further, a ₀ and b ₀ respectively indicate the a value and the b value in the aqueous solution prepared in the same manner as described above except that a standard dye is blended instead of the iridoid compound-derived red dye composition.
Here, the standard dye is the above-mentioned paragraph 1. In the step of performing red color formation in the preparation of the red pigment composition derived from iridoid compound as described in the above, using the conventional red dye composition prepared by combining only citric acid which is the prior art and performing the red color development step it can. Specifically, a red pigment composition prepared by blending 4.3 molar equivalents of citric acid with respect to the total molar equivalent of the iridoid compound contained in the reaction solution and performing a red color development step can be used as a standard pigment. . In one aspect, a dye prepared in the same manner as Sample 1-1 described in Example 1 herein can be used as a standard dye.

The value on the right side of the (formula 1) in the present invention is a value indicating that the color tone of the red pigment composition is on the red side and / or the yellow side as compared with the case where only citric acid is used as the prior art. It is. Here, the color tone of the red dye composition produced by the combination of ascorbic acid and / or its analog compound shows a value in which the b value is shifted to the yellow side. The a value indicates a value shifted to the red side.
Furthermore, with the increase of the blending amount of ascorbic acid and / or its analogue, the shift on the yellow side of the b value and / or the shift on the red side of the a value tends to be further intensified.
In addition, in the aspect which mix | blends other organic acids other than ascorbic acid and / or its analog compound, depending on the kind and quantity of the organic acid, b value becomes a bluish color development lower than the above-mentioned standard pigment | dye There is a case. However, even in this case, in the iridoid compound-derived red pigment composition according to the present invention, as shown in the above (formula 1), compared with the case where only citric acid which is the prior art is blended, Hunter A value indicating that the color tone is on the red side and / or the yellow side in the coordinates of the Lab color system (that is, the red side and / or the yellow side is higher than when only citric acid is blended). Show a reddish color tone.
The value of the right side of the (formula 1) in the present invention is preferably 2.5 or more, more preferably 3 or more, still more preferably 3.5 or more, particularly preferably 4 or more, the red color is more vivid It becomes a color tone and is further suitable as a coloring characteristic. The upper limit of the value may be, for example, 30 or less, preferably 20 or less, but the value is not particularly limited.

b Value In the red color development according to the present invention, the combination of ascorbic acid and / or a similar compound shows that the color tone of the red dye composition produced is shifted to the yellow side as compared with the case of using other organic acids. It becomes a thing.
In this respect, in the iridoid compound-derived red pigment composition according to the present invention, the b value in the Hunter Lab color system is preferably in the range shown below when measured according to the method described below.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following features:
When the aqueous solution of pH 5.0 is prepared with the McIlvaine buffer so as to have a color value E of ^10% _{1 cm} value 0.05, the following (formula 2) is satisfied:
(Formula 2): b ₁ −b _C 1.51.5
Here, b ₁ in the formula represents the b value in the Hunter Lab color system in the aqueous solution containing the iridoid compound-derived red pigment composition. In addition, b _c represents the b value in the aqueous solution prepared in the same manner as described above except that a comparative dye was blended instead of the iridoid compound-derived red dye composition.
Here, as a comparative dye, in the aspect which does not use another organic acid together in red color development, the thing similar to the standard dye as described in said (Formula 1) can be used.
In addition, as a comparative dye, in the embodiment in which another organic acid is used in combination in red color development, ascorbic acid and / or a similar compound thereof is mixed with the same molar equivalent of other organic acids in the total amount of organic acids. It is desirable to use a red pigment composition prepared by performing a red color development step as the comparative pigment. For example, in the aspect which mix | blends 8 molar equivalents of ascorbic acid and a succinic acid in the organic acid total amount, the red pigment composition produced | generated by mix | blending 8 molar equivalents only with a succinic acid can be made into the comparison pigment.

The value on the right side of the (formula 2) in the present invention is a yellow color of the red color tone of the red pigment composition as compared with the case where only citric acid which is the prior art is blended or an equivalent amount of other organic acids. It is a value indicating that the shift to the side is characteristic. Furthermore, in the red color development according to the present invention, the increase of ascorbic acid and / or its analogues tends to further improve the shift to the yellow side of the produced red pigment composition.
When the value of the right side of the (formula 2) in the present invention is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more, the yellowish color becomes bright red and the color tone is further suitable . The upper limit of the value may be, for example, 30 or less, preferably 20 or less, but the value is not particularly limited.

a Value and CHROMA Value The iridoid compound-derived red pigment composition according to the present invention is a pigment composition exhibiting a unique bright red tone. The iridoid compound-derived red pigment composition according to the present invention preferably has an a value and a CHROMA value in the Hunter Lab color system as described below, as measured according to the method described below.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following features:
When the aqueous solution of pH 5.0 is prepared with the McIlvaine buffer so as to have a color value E ^10% _{1 cm} value 0.05, the following (formula 3) is satisfied:
(Expression 3): Δa + ΔC ≧ 2
Δa = a ₁ -a ₀
ΔC = C ₁ -C ₀
Here, a ₁ and C ₁ in the formula respectively indicate the a value and the CHROMA value in the Hunter Lab color system in the aqueous solution containing the iridoid compound-derived red pigment composition. Further, a ₀ and C ₀ respectively indicate the a value and the CHROMA value in the aqueous solution prepared in the same manner as described above except that a standard dye is blended instead of the above-mentioned red dye composition derived from the iridoid compound.
Here, as the standard dye, one similar to the standard dye described in the above (formula 1) can be used. In one aspect, a dye prepared in the same manner as Sample 1-1 described in Example 1 herein can be used as a standard dye.

The value on the right side of the (formula 3) in the present invention indicates that the color tone of the red dye composition is on the red side and / or the bright side as compared with the case where only citric acid which is the prior art is blended. It is a value. Here, the color tone of the red dye composition produced by the combination of ascorbic acid and / or a similar compound thereof shows a value in which the CHROMA value is shifted to the bright side. The a value indicates a value shifted to the red side.
Furthermore, with the increase of the blending amount of ascorbic acid and / or its analog compound, the shift of the CHROMA value on the bright side and / or the shift of the red value on the a value tend to be further enhanced.
In addition, in the aspect which mix | blends other organic acids other than ascorbic acid and / or its analog compound, depending on the kind and quantity of the organic acid, b value becomes a bluish color development lower than said standard pigment | dye There is a case. However, even in this case, in the iridoid compound-derived red pigment composition according to the present invention, as shown in the above (formula 3), compared with the case where only citric acid which is the prior art is blended, Hunter A value indicating that the color tone is on the red side and / or the bright side in the coordinates of the Lab color system (that is, the red side and / or the bright side is higher than when only citric acid is blended) Show a bright red tone.
The value of the right side of the (formula 3) in the present invention is preferably 2.5 or more, more preferably 3 or more, still more preferably 3.5 or more, still more preferably 4 or more, particularly preferably 4.5 or more Particularly preferably, when it is 5 or more, red is a more vivid color tone, which is further preferable as a coloring property. The upper limit of the value may be, for example, 30 or less, preferably 20 or less, but the value is not particularly limited.

CHROMA Value The iridoid compound-derived red pigment composition according to the present invention is a pigment composition that exhibits excellent color saturation and excellent red coloration. In the red dye composition according to the present invention, in order to exhibit its bright redness and lightness color forming properties, Hunter, when the red dye composition to be produced is measured according to the method described below, It is preferable that each value in the Lab color system shows the following range.
That is, the iridoid compound-derived red pigment composition according to the present invention has the following features:
When the aqueous solution of pH 5.0 is prepared with the McIlvaine buffer so as to have a color value E of ^10% _{1 cm} value 0.05, the following (formula 4) is satisfied:
(Equation 4): C ₁ -C ₀ -1−1
Here, C ₁ in the formula represents a CHROMA value in the Hunter Lab color system in the aqueous solution containing the iridoid compound-derived red pigment composition. Further, C _0, except that the blending standard dye instead of the iridoid compounds derived from red dye composition exhibits a CHROMA value in aqueous solution prepared in the same manner as described above. Here, as the standard dye, one similar to the standard dye described in the above (formula 1) can be used. In one aspect, a dye prepared in the same manner as Sample 1-1 described in Example 1 herein can be used as a standard dye.

The value on the right side of the (formula 4) in the present invention indicates that the saturation of the red dye composition is equivalent or not inferior or greater than that in the case where only citric acid which is the prior art is blended. It is a value shown. Here, in the red color development according to the present invention, the increase in the total amount of the organic acid tends to improve the chroma of the red dye composition to be produced.
In the present invention, the value on the right side of the (formula 4) is preferably 0 or more, more preferably 1 or more, still more preferably 1.5 or more, particularly preferably 2 or more, particularly preferably 3 or more. The saturation is improved to obtain a bright color tone, which is further preferable as a coloring characteristic. The upper limit of the value may be, for example, 30 or less, preferably 25 or less, but the value is not particularly limited.

L value (brightness)
As the coloring characteristics of the red pigment composition according to the present invention, the contribution from the improvement of the above-mentioned value is large, but the L value, which indicates the lightness, is also involved as the overall color tone. That is, as the L value in the red pigment composition according to the present invention, an L equivalent to or equivalent to or more than that of the red pigment composition derived from an iridoid compound produced using an organic acid such as citric acid which is the prior art It is preferred that the value is indicated.
Here, as an iridoid compound origin red pigment composition manufactured using organic acids, such as a citric acid which is prior art, the thing similar to the standard pigment | dye as described in said (Formula 1) can be mentioned.

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

The coloring characteristics of the iridoid compound-derived red pigment composition according to the present invention can also be expressed as the ratio of the absorbance at the maximum absorption wavelength to the absorbance at another fixed wavelength.
Here, as the red pigment composition according to the present invention, when the pigment composition-containing aqueous solution is prepared to have a pH of 5 with McIlvaine buffer, 520 to 545 nm, preferably 530 to 542 nm, particularly preferably 534 to It is a dye composition having a maximum absorption wavelength at 538 nm.

Small Activity Regarding Coloring Characteristics The red dye composition according to the present invention exhibits coloring characteristics excellent in bright redness at each value of the above-mentioned Hunter Lab color specification system. Here, "bright redness" refers to a color tone exhibiting a bright and bright red color, and indicates high values of a value and / or b value. The higher the a value and / or b value, the brighter the color tone is, and the preferred red pigment composition in terms of bright red coloring characteristics. Preferably, those having high a and b values are preferable. In particular, when the b value indicating that it is a yellowish color tone is high, it exhibits a beautiful and bright red color, which is preferable. In addition, the higher the CHROMA value, the higher the color saturation and the brighter the color tone, which is preferable in terms of bright redness.
In addition, as the red pigment composition according to the present invention, a color developing property having brightness excellent in brightness and brightness is shown at each value of the above-mentioned Hunter Lab color system. Here, "brightness" refers to a bright and bright color tone, and the CHROMA value indicates a high value. The higher the CHROMA value, the brighter and brighter the color tone becomes, and the preferred red pigment composition in terms of light-colored color-forming characteristics. Further, the higher the L value, the higher the color tone, and the more preferable in lightness.
Here, the color forming properties indicated by the above-mentioned formulas for the above-mentioned Hunter Lab color system indicate that the iridoid compound-derived red pigment composition according to the present invention has a color forming property exhibiting bright and clear red color. It can not be realized with red color development in the presence of citric acid alone, which is a technology.

[Stability to light and heat]
The iridoid compound-derived red pigment composition according to the present invention is a pigment composition having high stability to light and heat, and has a characteristic that the color forming property is hardly lost upon light irradiation, heat exposure, and the like. The said degree of stability has high heat resistance and light resistance equivalent to or more than the iridoid compound origin red pigment composition manufactured by citric acid addition which is a prior art.
The iridoid compound-derived red pigment composition according to the present invention can be suitably used for coloring distribution products that require resistance to fluorescent lamp irradiation, high temperature storage and the like due to the characteristics relating to the stability. Moreover, it can be suitably used also in the aspect which assumes heat processing, such as retort sterilization, a process, and cooking.

Gardenia red pigment composition
Specific examples of the iridoid compound-derived red pigment composition according to the present invention include a gardenia red pigment composition produced using a gardenia fruit or an extract thereof as a source material of the iridoid compound.
In the present specification, the term "gardenia red pigment composition" refers to the above paragraph 1. And a pigment composition comprising a red pigment compound produced with the action of an iridoid aglycone having a carboxyl group at the 4-position of the iridoid skeleton derived from a gardenia fruit described in and a composition containing an amino group.
Here, in the definition of "gardenia red pigment" in the 8th edition food additive official document (Ministry of Health, Labor and Welfare), a mixture of ester hydrolyzate and proteolysis product of iridoid glucoside obtained from gardenia fruit is β-glucosidase Defined as a dye obtained by the addition, the production process in the definition only describes one aspect of the production process described in the specification. Therefore, the gardenia red pigment composition according to the present invention is a pigment composition including a wider range than the gardenia red pigment composition based on the general definition.
In addition, the gardenia red pigment composition according to the present invention is manufactured 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 etc. Also included are red pigment compositions. Further included are red pigment compositions prepared using genipin and / or genipinic acid derived therefrom as a raw material.

[Term related to pigment]
The major terms relating to dyes used in the present specification are described below.
In the present specification, "Hunter Lab color system (Lab system)" is a color system that forms a color solid composed of orthogonal coordinates including a-axis and b-axis indicating chromaticity and an L-axis perpendicular thereto. It is.
Here, the “L value” is a value representing the lightness numerically. It becomes white when L value = 100 and becomes black when L value = 0. The “a value” is a value representing the red and green color tones numerically. The larger the value of a, the stronger the red, and the smaller the value of a, the stronger the green. The “b value” is a value representing the yellow and blue tones numerically. The larger the b value, the stronger the yellow color, and the smaller the b value, the stronger the blue color.

In the present specification, the "CHROMA value" is a value representing the distance from the origin in the Hunter Lab color system numerically by the following formula (11). Used as a value indicating saturation. The larger the value is, the brighter the color is.

In the present specification, “color difference (ΔE)” is a point at which two colors are plotted in the Hunter Lab color system ((a ₁ , b ₁ , L ₁ ) and (a ₂ , b ₂ , L ₂ ). The distance of the distance between the two is calculated by the following equation (12) and is represented by a numerical value.

In the present specification, “HUE value” refers to a forming angle of a straight line connecting a plot (a value, b value) on the a-axis and b-axis orthogonal coordinates in the Hunter Lab color system and the origin. It is a value representing the hue expressed by converting to the hue notation in. It is a value representing the hue as a symbol and a numerical value.

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

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 measurement cell with an optical path length of 1 cm.
In the present specification, "color value conversion" refers to conversion of a dye (dye composition) into a value per color value. For example, when the pigment (pigment composition) is adjusted to have a color value of 60, 0.05 mass% in terms of the color value of 60 means an amount such that the pigment content in the solution is 0.05 mass%. means.

As used herein, “McIlvaine (McMilvaine) buffer” is a buffer prepared using citric acid and phosphate (Na ₂ HPO ₄ ), also known as citrate buffer.

3. The iridoid compound-derived red pigment composition according to the present invention differs from the conventional bluish dark color iridoid compound-derived red pigment composition according to the above paragraph 2. It is a pigment composition having the characteristics described in the above, and a red pigment composition excellent in bright redness. In particular, it is a red pigment composition which exhibits beautiful color development characteristics combining reddishness and lightness.
Therefore, the red pigment composition according to the present invention can be widely used for applications and products that were difficult to use with the iridoid compound-derived red pigment composition according to the prior art (in particular, the gardenia red pigment). .

[Pigment preparation]
The iridoid compound-derived red pigment composition according to the present invention can be used as a pigment preparation. In particular, when the red pigment composition according to the present invention is a gardenia red pigment composition, it is suitable to use it as a gardenia red pigment preparation.
The form of the pigment preparation according to the present invention may be, for example, liquid, paste, gel, semi-solid, solid, powder and the like, and is not particularly limited. Moreover, processed solid shapes, such as granular form and a tablet, can be mentioned.
In addition, 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 pigment formulation, but it can be used as an oil-soluble pigment formulation (W / O type) or double emulsion It is also possible to process it into a pigment preparation (W / O / W type) or the like and use it.

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

In the dye preparation according to the present invention, other functional components can be blended as long as the color development characteristics of the red dye composition according to the present invention are not substantially impaired. For example, the dye preparation according to the present invention can be blended with an additive having a function to stabilize or improve the color development property and the like. In addition, antioxidants, pH adjusters, polysaccharide thickeners, and other food materials can be blended.

In addition to the red pigment composition according to the present invention, other pigments can be blended as the pigment preparation according to the present invention. The dye preparation according to the present invention can be made into a dye preparation adjusted to a desired color tone by blending the other dyes.
As other dyes that can be added here, natural dyes having a stable coloring characteristic like the red dye composition in the present invention are suitable. As an example, natural pigments such as gardenia yellow pigment, gardenia blue pigment, safflower pigment, anthocyanin pigment, bilberry pigment, turmeric pigment, tamarind pigment, oyster pigment, caramel pigment, spirulina pigment, kolyan pigment, cochineal pigment, tomato pigment etc. Although it can mention, it is not restricted in particular in these.

[Product]
The red pigment composition or the pigment preparation according to the present invention can be suitably used for a use as a coloring agent using an iridoid compound-derived red pigment composition according to the prior art, in addition to the prior art iridoid compound Products which were difficult to use in terms of color tone with the derived red pigment composition (especially gardenia red pigment) can be used in a wide range of fields.

The red pigment composition or pigment preparation according to the present invention can be suitably used as a natural coloring agent for products such as food and drink, cosmetics, medicines, quasi drugs, daily goods for hygiene, or feeds. It is. That is, in the present invention, it is possible to provide a food or drink, a cosmetic, a medicine, a quasi-drug, a daily product for hygiene, or a feed containing the red pigment composition or pigment preparation according to the present invention.
Here, although an example of a product example which can be colored with the red pigment composition or pigment preparation concerning the present invention is shown below, it is not limited as these as a colorable product concerning the present invention.
Examples of “food and drink” include beverages, frozen desserts, desserts, sugar confectionery (eg, candy, gummy, marshmallow), gum, chocolate, confectionery (eg, cookies etc.), bread making, agricultural products (eg, pickles etc.) Processed meat products, processed fish products, dairy products, noodles, seasonings, jellies, syrups, jams, sauces, liquors and the like.
"Cosmetics" may include skin lotions, lipsticks, sunscreen cosmetics, makeup cosmetics, and the like.
"Pharmaceutical" can include various tablets, capsules, drinks, troches, and mouthwashes.
Examples of "quasi-drugs" include nutritional aids, various supplements, dentifrices, mouth fresheners, odor preventives, hair nourishing agents, hair restorers, skin moisturizers, and the like.
Examples of "daily hygiene products" include soaps, detergents, shampoos, rinses, hair treatments, toothpastes, bath agents, and the like.
Examples of the "feed" include various pet foods such as cat food and dog food; food for ornamental fish and cultured fish; and the like.

The dye composition or dye preparation according to the present invention has a color forming property excellent in red and bright color tone, and in particular, it is based on milky white which tends to be a dull color which is difficult to use with conventional gardenia red pigment etc. It is possible to color the material to be a color tone with a bright red color tone. For example, it is possible to use suitably also for coloring of a milk beverage, a dairy product, a fish meat processed product etc.
Similarly, it is possible to color bright red tones even for beverage products that are difficult to use with conventional gardenia red pigments. For example, it is possible to use suitably also to a soft drink which has transparency, liquor, etc.

The pigment composition or pigment preparation according to the present invention is a technique characterized by the addition of an organic acid such as ascorbic acid, and thus is a suitable technique from the viewpoint of safety, and it can be taken into the human body. It is suitable for use in coloring applications for target products. In particular, it is suitable for use in coloring applications such as food and drink.
In addition, the dye composition or the dye preparation according to the present invention has excellent light resistance and heat resistance which are the features of the iridoid compound-derived red dye composition. Therefore, it is possible to use suitably also to coloring of a product etc. which assumed exposure to light in storage, a display, etc. It can also be used for products that are expected to be exposed to high temperature storage.

The dye composition or dye preparation according to the present invention can be suitably used for coloring use in the production process of the above-mentioned product.
As a process of coloring the above-mentioned product, it is possible to carry out according to the means of the usual method in each product except blending the pigment composition or pigment preparation concerning the present invention as a natural pigment. Moreover, as a compounding ratio of the red pigment composition or pigment formulation which concerns on this invention with respect to these products, it is possible to adjust suitably according to the kind and objective of products. For example, the content of the dye composition in the product is 0.001 to 1% by mass, preferably 0.005 to 0.5% by mass, more preferably 0.01 to 0.2% by mass, in terms of color value 80. More preferably, it is possible to blend so as to be 0.02 to 0.1% by mass.

[Various manufacturing methods]
In the present invention, methods for producing a pigment preparation, various products and the like are included. That is, the present invention includes a step of containing or compounding the iridoid compound-derived red pigment composition obtained by the production method described in the above paragraph, pigment preparation, food and drink, cosmetics, and pharmaceuticals The present invention includes a method for producing quasi-drugs, daily products for hygiene, or feed.
As a manufacturing process in each of these manufacturing methods, the feature, the process, etc. which were described in the said paragraph can be referred or referred and used. For example, as the content or blending amount of the above-mentioned iridoid compound-derived red pigment composition, it is possible to refer to or cite the description of the above paragraph regarding the pigment preparation and each product. Moreover, as a manufacturing process in each manufacturing method, it is possible to employ | adopt the usual method in pigment | dye formulation or each product except mix | blending the said iridoid compound origin red pigment composition.

[Individual effects of each product]
The red pigment composition or the pigment preparation according to the present invention can be colored in a bright and bright red color tone in a product manufactured by blending the same, yet another excellent effect and effect depending on the product to be colored May be played. The effects include various effects such as secondary effects of the above-mentioned effects and effects of foreign substances.

In the case where the raw material, which is the product to be colored in pink tone , is a product having a white color, when an ordinary gardenia red pigment is used, it tends to be dark blue due to the color tone when it is mixed with the raw material It was difficult to express the shade in bright pink etc. On the other hand, when coloring is performed using the red pigment composition or pigment preparation according to the present invention, the bright "pink" is obtained even when the raw material etc. becomes a mixed color tone with a product having a white color system. Color development is possible. In addition, it is also possible to develop a color tone that impresses strawberry, which is difficult with ordinary gardenia red pigment.
As products suitable for coloring in a pinkish color tone in the present invention, for example, bread, gum, pudding, bavaroa, strawberry milk, various dairy products, candy, flower paste, cream, cookie, donut, cake, biscuit, syrup , Jam etc. can be mentioned. Moreover, even if it is products other than these, if it can generally be recognized equivalent to these products, it will be recognized as what is contained in the said products. In the present invention, since dark blue coloration caused by mixing with a white-based material is suppressed, it is possible to color a product having a white-based material in a bright pink color with respect to a product having a white-based material.

Hereinafter, the present invention will be described by way of examples, but the scope of the present invention is not limited by these.
The main steps in the process for producing the iridoid compound-derived red pigment composition according to this example are shown as a flow chart in FIG. In this example, the description "GP to molar equivalent" is a value indicating the addition amount or content of the compound used in the production process of the gardenia red pigment composition in terms of the molar ratio to the raw material, geniposide. . In this specification, it may be described as "eq".
In the examples, “*” indicates that the product is a product of San-Ei Gen F.F.I., and “*” indicates a registered trademark of San-Ei Gen F.F.

[Example 1] "Evaluation of color development characteristics by addition of ascorbic acid"
When ascorbic acid was added as an organic acid to be added in the production process of the gardenia red pigment composition, the influence on the coloring characteristics of the produced gardenia red pigment composition was examined.

(1) "Preparation of gardenia red pigment composition"
A solution of pH 12 was prepared by adding 2.25 g of a 48% sodium hydroxide solution to 11 g of an aqueous solution containing 32% of purified geniposide (hereinafter sometimes abbreviated as GP) to prepare a solution of pH 12, and the solution was hydrolyzed to 30 mL. The ester hydrolysis treatment was carried out by stirring at 50 ° C. for 2 hours to form geniposidic acid.
After hydrolysis treatment, 6.6 g (GP to 4.3 molar equivalent) of sodium glutamate was added, and various organic acids shown in Table 2 were added as organic acids to adjust the pH value to about 4.4 to 4.6. Then, water was added to prepare a solution of 50 g in weight, and heat treatment was performed at 80 ° C. for 10 minutes.
Here, as a comparative sample, citric acid was added and used so as to be 4.3 molar equivalents with respect to GP according to the formulation described in the example of Patent Document 2 which is the prior art.

The acid adjusted solution was mixed with 0.6 g of cellulase under a nitrogen atmosphere and gently stirred, and subjected to β-glucosidase reaction at 50 ° C. for 24 hours to generate genipic acid, which is a geniposidic aglycone. The pH was readjusted to about 4.5, and heat treatment was performed 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, thereby promoting red color development. The red coloration in the present example is a reaction which is initiated with the produced aglycone as a substrate even during the β-glucosidase reaction, but is a reaction which rapidly progresses due to the subsequent heat treatment.

After cooling to room temperature, 1 part by mass of diatomaceous earth, which is a filter aid, is added to and mixed with liquid volume, and the filter paper (NO. 2 filter, φ 150 mm, Advantech Toyo Co., Ltd.) The filtrate was collected by suction filtration with using the above solution to obtain a gardenia red pigment composition solution.
The comparative sample (sample 1-1) prepared in the same manner as the target sample in the above steps was also used as a standard sample in the present example and other examples.

(2) "Color development characteristics evaluation"
The coloring characteristics of the prepared dye composition solution were evaluated.
The value of color number E ^10% _{1 cm} was calculated by measuring the absorbance of the maximum absorption part at a wavelength of 520 to 545 nm using McIlvaine buffer pH 5.0 as a measurement solvent.
For each measurement value used for color evaluation, prepare a test solution with a color number E ^10% _{1 cm} = 0.05 using McIlvaine buffer pH 5.0 and measure it with a spectrophotometer (V-560, manufactured by JASCO, The transmitted light colorimetry at a measurement wavelength of 380 to 780 nm was performed using the optical path length of 1 cm of the cell, and the tristimulus values (L value, a value, and b value) of the Hunter Lab colorimetric system were measured.
The measured values were used to evaluate lightness, saturation, and hue. As "brightness", the value of the L value measured above was evaluated as it was. The "saturation" was evaluated by calculating the CHROMA value using the above equation (11). "Hue" was evaluated by calculating the HUE value. The “color difference” indicating the difference in color between each sample and the comparative sample (sample 1-1) according to the prior art was evaluated by calculating the ΔE value using the above equation (12). Further, the “Δa + Δb” value represented by the equation (1) is the difference between the a value of the target sample and the a value of the standard sample (sample 1-1), the b value of the target sample, and the standard sample (sample It calculated by adding the value of the difference with b value in 1-1).
The results are shown in Table 2 and FIG. Moreover, the result of visually observing the reagent bottle is shown in FIG.

As a result, in place of citric acid in a comparative sample (sample 1-1: GP to 4.3 molar equivalent) which is the prior art, ascorbic acid was added in approximately the same amount (GP to 4 molar equivalent) to perform red color development The gardenia red pigment composition (Sample 1-2) exhibited a bright red tone in which the b value was largely shifted to the yellow side as compared with the comparative sample. In addition, the HUE value also shows the value on the red side, and it was confirmed that a bright red color tone is exhibited also by visual observation of the filled reagent bottle.
On the other hand, in the case of a gardenia red pigment composition (Sample 1-1) colored in red by adding citric acid as a comparative sample (Sample 1-1), it exhibits a bluish purple tone in visual observation of each measured value and the filling reagent bottle Was confirmed.

Here, in the red pigment composition (Samples 1-3 to 1-5) in which red color was developed by increasing the addition amount of ascorbic acid from this, the a value becomes red as the addition amount of ascorbic acid increases. It showed a tendency to shift largely to the side, and a tendency to further intensify the red tone (see FIG. 2 showing the result of the two-dimensional plot). In addition, in these samples, the L value and the CHROMA value also tended to increase, and as the addition amount of ascorbic acid was increased, the reddishness and lightness were improved. In particular, the increase in the CHROMA value was remarkable.
The color tone of the red pigment composition achieved by the addition of ascorbic acid was a sufficiently bright red color even with GP to 4 molar equivalents, but in particular more than 5 molar equivalents of GP versus more particularly GP relative to 6 molar equivalents. When the above ascorbic acid was added, it was possible to realize a more vivid red color tone.
In addition, also in the visual observation of the HUE value and the filled reagent bottle, a bright and bright red color tone was confirmed in these red pigment compositions (Samples 1-3 to 1-5).
In addition, the maximum absorption wavelength (λmax) is 533 nm for the coloration red pigment composition (Sample 1-1) colored by adding citric acid to red color, and the color redia red pigmented by adding ascorbic acid The compositions (Samples 1-2 to 1-5) showed 534 to 536 nm.

(3) Summary From the above results, in the production process of the iridoid compound-derived red pigment composition, the red pigment composition obtained by adding ascorbic acid and performing a series of reaction steps has bright redness and bright color. It has been shown that a red pigment composition excellent in quality can be prepared. Here, in the prior art iridoid compound-derived red pigment composition using citric acid, a bluish purple color tone is obtained, and it is not possible to realize a color forming characteristic showing such a bright red color tone.
Furthermore, the above results show that it is possible to prepare a gardenia red pigment composition with further improved bright redness and lightness by increasing the amount of ascorbic acid added in this step.
In addition, in each sample in the present example, the pH at the time of reaction was almost the same as about 4.5, and therefore, the lightening action of the gardenia red pigment by increasing the amount of ascorbic acid is attributed to pH. It was shown that it was not an action.

[Example 2] "Evaluation on color development characteristics by combined use of ascorbic acid and citric acid"
When ascorbic acid and citric acid were added together in the production process of the gardenia red pigment composition, the influence on the coloring characteristics of the produced gardenia red pigment composition was examined.

(1) "Preparation of gardenia red pigment composition"
A solution of pH 12 was prepared by adding 2.25 g of a 48% sodium hydroxide solution to 11 g of an aqueous solution containing 32% of purified geniposide (hereinafter sometimes abbreviated as GP) to prepare a solution of pH 12, and the solution was hydrolyzed to 30 mL. The ester hydrolysis treatment was carried out by stirring at 50 ° C. for 2 hours to form geniposidic acid.
After hydrolysis treatment, 6.6 g (GP: 4.3 molar equivalents) of sodium glutamate was added, and various organic acids shown in Table 3 were added as organic acids to adjust the pH value to about 4.4 to 4.6. Then, water was added to prepare a solution of 50 g in weight, and heat treatment was performed at 80 ° C. for 10 minutes.
Here, as a comparative sample, citric acid was added and used so as to be 4.3 molar equivalents with respect to GP according to the formulation described in the example of Patent Document 2 which is the prior art.

With respect to the acid-adjusted liquid, 0.6 g of cellulase was added under nitrogen atmosphere and gently stirred to perform β-glucosidase reaction at 50 ° C. for 24 hours to generate genipinic acid, which is a geniposidic aglycone. The pH was readjusted to about 4.5, and heat treatment was performed 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, thereby promoting red color development. The red coloration in the present example is a reaction which is initiated with the produced aglycone as a substrate even during the β-glucosidase reaction, but is a reaction which rapidly progresses due to the subsequent heat treatment.

After cooling to room temperature, 1 part by mass of diatomaceous earth, which is a filter aid, is added to and mixed with liquid volume, and the filter paper (NO. 2 filter, φ 150 mm, Advantech Toyo Co., Ltd.) The filtrate was collected by suction filtration with using the above solution to obtain a gardenia red pigment composition solution.

(2) "Color development characteristics evaluation"
The coloring characteristics of the prepared dye composition solution were evaluated. The calculation of the values indicating lightness, saturation, and hue was performed by measuring the tristimulus values of the Hunter Lab colorimetric system in the same manner as the method described in Example 1. The “color difference” indicating the difference in color between each sample and the comparative sample according to the prior art (sample 2-1) was evaluated by calculating the ΔE value using the above equation (12). Further, the “Δa + Δb” value represented by the equation (1) is the difference between the a value of the target sample and the a value of the standard sample (sample 1-1), the b value of the target sample, and the standard sample (sample It calculated by adding the value of the difference with b value in 1-1).
The results are shown in Table 3 and FIG. Moreover, the result of visually observing the reagent bottle is shown in FIG.

As a result, in the production process of the gardenia red pigment composition, in the gardenia red pigment composition (sample 2-2 to sample 2-5) obtained by adding ascorbic acid and citric acid together and performing red coloration (sample 2-2 to sample 2-5) As compared with the red pigment composition (comparative sample: sample 2-1) obtained by adding only citric acid, which is a technology, each measured value and evaluation item resulted in a bright red color tone. In particular, the b value largely shifted to the yellow side and the CHROMA value showed a high value.
In these samples, the b value showed a tendency to shift to the yellow side as the addition amount of ascorbic acid increased, and the a value also showed a tendency to shift to the red side, and the red color tone tended to be further enhanced ( See Figure 4 which shows the results of a two dimensional plot). In addition, the CHROMA value showed a tendency to rise with the increase of the addition amount of ascorbic acid, and the result that the lightness was improved was shown.
In addition, also in the visual observation of the HUE value and the filling reagent bottle, the bright and bright red color tone exhibited by these red pigment compositions (Sample 2-2 to Sample 2-5) was confirmed.
On the other hand, with the gardenia red pigment composition (Sample 2-1) colored in red by the addition of citric acid as a comparative sample (Sample 2-1), it exhibits a bluish purple tone even in visual observation of each measured value and the filling reagent bottle That was confirmed.
The maximum absorption wavelength (λmax) was determined by adding ascorbic acid at 533 nm in the gardenia red pigment composition (Sample 2-1) colored with red by adding citric acid to perform red coloration The gardenia red pigment compositions (Sample 2-2 to Sample 2-5) exhibited 534 to 536 nm.

(3) Summary From the above results, in the production process of the iridoid compound-derived red pigment composition, the red pigment composition obtained by adding citric acid together with ascorbic acid to perform red coloration is a prior art. It was shown that a red pigment composition excellent in bright redness and lightness having a color tone shifted to the yellowish side can be prepared unlike the red pigment composition when only citric acid is used. That is, it was shown that the action which ascorbic acid gives to color tone in the said manufacturing process is an action exhibited also under the conditions which other organic acids coexist.

In consideration of the above results and the results of Example 1, at least the addition amount of ascorbic acid is at least 4.3 molar equivalents with respect to GP and the ascorbic acid relative to the total organic acid addition amount (at least 5.8 molar equivalents with GP). When the molar ratio was 74.1% or more, it was shown that a red pigment composition excellent in bright redness and lightness could be prepared. In particular, when the amount of ascorbic acid added is at least 6 molar equivalents of GP and the molar ratio of ascorbic acid to the total amount of added organic acids (GP at least 7.5 molar equivalents) is at least 80%, bright redness and bright It was shown that the colorability was further improved.

[Example 3] "Evaluation of chromogenic property by combination use of ascorbic acid and succinic acid"
When ascorbic acid and succinic acid were added together in the production process of the gardenia red pigment composition, the influence on the coloring characteristics of the produced gardenia red pigment composition was examined.

(1) "Preparation of gardenia red pigment composition"
In the production process of the gardenia red pigment composition, the organic acid added at the time of red color development is added as described in Tables 4 to 5 to prepare a gardenia red pigment composition solution in the same manner as described in Example 2. did.
As a comparative sample, one having undergone a series of preparation steps in the same manner was used except that succinic acid was added so as to be 8 molar equivalents with respect to GP.

(2) "Color development characteristics evaluation"
The coloring characteristics of the prepared dye composition solution were evaluated. The calculation of the values indicating lightness, saturation, and hue was performed by measuring the tristimulus values of the Hunter Lab colorimetric system in the same manner as the method described in Example 1. The “color difference” indicating the difference in color between each sample and the comparative sample (sample 3-1) according to the prior art was evaluated by calculating the ΔE value using the above equation (12). Further, the “Δa + Δb” value represented by the equation (1) is the difference between the a value of the target sample and the a value of the standard sample (sample 1-1), the b value of the target sample, and the standard sample (sample It calculated by adding the value of the difference with b value in 1-1).
The results are shown in Tables 4 to 5 and FIG. Further, the result of visual observation of the reagent bottle is shown in FIG.

As a result, in the production process of the gardenia red pigment composition, comparison was made between the gardenia red pigment compositions (samples 3-2 to 3-7) obtained by adding ascorbic acid and succinic acid together and performing red coloration. As compared with the red pigment composition (comparative sample: sample 3-1) obtained by adding only succinic acid which is a sample, each measured value and evaluation item resulted in showing a bright red color tone. In particular, the b value largely shifted to the yellow side, and the b value became a value showing a yellowish bright red tone.
In these samples, the b value tended to shift to the yellow side as the addition amount of ascorbic acid increased, and the bright red tone tended to be further enhanced as the addition amount of ascorbic acid increased (2 See Figure 6 which shows the results of the dimensional plot).
Further, also in the visual observation of the HUE value and the filled reagent bottle, a bright and bright red color tone was confirmed in these red pigment compositions (Sample 3-2 to Sample 3-7).
On the other hand, with the gardenia red pigment composition (Sample 3-1) colored in red by adding succinic acid, which is a comparison sample (Sample 3-1), the bluish red color tone is observed in each measured value and visual observation of the filling reagent bottle. It was confirmed to present.
In addition, the maximum absorption wavelength (λmax) for all the gardenia red pigment compositions (Sample 3-1 to Sample 3-7) was 536 to 537 nm.

(3) Summary From the above results, in the production process of the iridoid compound-derived red pigment composition, in the red pigment composition obtained by adding succinic acid together with ascorbic acid to perform red coloration, the succinic acid is used as the organic acid. It was shown that it was possible to prepare a red pigment composition excellent in bright redness and lightness, in which the color tone was shifted to the yellowish side, unlike the red pigment composition when only the acid was used. That is, it was shown that the action which ascorbic acid gives to color tone in the said manufacturing process is an action exhibited also under the conditions which other organic acids coexist.

From the above results, when at least the addition amount of ascorbic acid is at least 2 molar equivalents of GP and the molar ratio of ascorbic acid to the total addition amount of organic acid is 25% or more (sample 3-2), bright redness and bright color It has been shown that a red pigment composition excellent in quality can be prepared. In particular, when the amount of ascorbic acid added is at least 3 molar equivalents with respect to GP and the molar ratio of ascorbic acid to the total added amount of organic acid is 37.5% or more (Sample 3-3), bright redness and lightness Was shown to be even better.

In this example, the test is conducted by making the total amount of the organic acid to be added constant at 8 molar equivalents with respect to GP, so the phenomenon of redness of the color tone of the red pigment composition obtained after the reaction It was confirmed that the action was not due to the use of ascorbic acid. On the other hand, when the result and the result of Example 1 were taken into consideration together, it was suggested that the increase of the CHROMA value showing the saturation was a value which increased in correlation with the total amount of the organic acid added at the time of the reaction.
That is, the color development characteristics of the red pigment composition according to the present invention with respect to the reddishness and lightness are i) imparting of a vivid red tone with a yellowish color by the presence of a certain amount or more of ascorbic acid in the reaction solution It has been suggested that it is realized that the provision of a bright and clear color tone is realized by the fact that the total amount of the organic acid is more than a certain amount.
In addition, the color tone adjustment of the red pigment composition obtained is possible by changing the ratio with the other organic acid added with ascorbic acid in the range which satisfy | fills the conditions of said i) and ii) as said result It was also recognized as a result indicating that

[Example 4] "Evaluation on color development characteristics by combined use of ascorbic acid and citric acid"
When ascorbic acid and citric acid were added together in the production process of the gardenia red pigment composition, the influence on the coloring characteristics of the produced gardenia red pigment composition was examined.

(1) "Preparation of gardenia red pigment composition"
In the production process of the gardenia red pigment composition, an organic acid to be added during red color development is added as described in Tables 6 to 7 to prepare a gardenia red pigment composition solution in the same manner as described in Example 2. did.
As a comparative sample, one subjected to a series of preparation steps in the same manner was used except that citric acid was added so as to be 8 molar equivalents with respect to GP.

(2) "Color development characteristics evaluation"
The coloring characteristics of the prepared dye composition solution were evaluated. The calculation of the values indicating lightness, saturation, and hue was performed by measuring the tristimulus values of the Hunter Lab colorimetric system in the same manner as the method described in Example 1. The “color difference” indicating the difference in color between each sample and the comparative sample (sample 4-1) according to the prior art was evaluated by calculating the ΔE value using the above equation (12). Further, the “Δa + Δb” value represented by the equation (1) is the difference between the a value of the target sample and the a value of the standard sample (sample 1-1), the b value of the target sample, and the standard sample (sample It calculated by adding the value of the difference with b value in 1-1).
The results are shown in Tables 6 to 7 and FIG. Moreover, the result of visually observing the reagent bottle is shown in FIG.

As a result, in the production process of the gardenia red pigment composition, comparison was made between the gardenia red pigment compositions (samples 4-2 to 4-8) obtained by adding ascorbic acid and citric acid together and performing red coloration. As compared with the red pigment composition (comparative sample: sample 4-1) obtained by adding only citric acid which is a sample, each measurement value and evaluation item resulted in showing a bright red color tone. In particular, the b value largely shifted to the yellow side, and the b value became a value showing a yellowish bright red tone.
In these samples, the b value tended to shift to the yellow side as the addition amount of ascorbic acid increased, and the bright red tone tended to be further enhanced as the addition amount of ascorbic acid increased (2 See Figure 8 which shows the results of the dimensional plot).
Further, also in the visual observation of the HUE value and the filling reagent bottle, a bright and bright red color tone was confirmed in these red pigment compositions (Sample 4-2 to Sample 4-8).
On the other hand, in the case of a gardenia red pigment composition (Sample 4-1) in which red color was developed by adding only citric acid as a comparative sample (Sample 4-1), a bluish red color tone was observed in each measured value and visual observation of the filling reagent bottle It was confirmed that the
In addition, the maximum absorption wavelength (λmax) for all the gardenia red pigment compositions (samples 4-1 to 4-8) was 536 to 537 nm.

(3) Summary As the above results show, even when the ratio of citric acid and ascorbic acid is changed while keeping the total amount of the organic acid added constant at GP molar ratio of 8 molar equivalents, the citric acid is combined with ascorbic acid. It was shown that the red pigment composition obtained by adding an acid and performing red color development can be used to prepare a red pigment composition excellent in bright redness and lightness.
From the results, it was found that the red coloration phenomenon of the color of the red pigment composition obtained after the reaction in the coexistence of another organic acid and ascorbic acid used ascorbic acid instead of increasing the total amount of the organic acid added. It was also confirmed under coexistence conditions with citric acid that it is an action attributable. That is, it was shown that the reddish phenomenon of the color tone of the red pigment composition according to the present invention is an action which is widely exhibited by the combination use with ascorbic acid regardless of the type of other organic acids.

Also, from the above results, bright red at least when the addition amount of ascorbic acid is at least 1 molar equivalent of GP and the molar ratio of ascorbic acid to the total addition amount of organic acid is 12.5% or more (sample 4-2) It was shown that a red pigment composition excellent in color and lightness can be prepared.

1-1: Sample 1-1
1-2: Sample 1-2
1-3: Sample 1-3
1-4: Sample 1-4
1-5: Sample 1-5

2-1: Sample 2-1
2-2: Sample 2-2
2-3: Sample 2-3
2-4: Sample 2-4
2-5: Sample 2-5

3-1: Sample 3-1
3-2: Sample 3-2
3-3: Sample 3-3
3-4: Sample 3-4
3-5: Sample 3-5
3-6: Sample 3-6
3-7: Sample 3-7

4-1: Sample 4-1
4-2: Sample 4-2
4-3: Sample 4-3
4-4: Sample 4-4
4-5: Sample 4-5
4-6: Sample 4-6
4-7: Sample 4-7
4-8: Sample 4-8

Claims

In a method of producing an iridoid compound-derived red pigment composition,
(Step 1) 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,
The organic acid containing ascorbic acid, its analogous compound, or two or more compounds selected from these is carried out in a solution containing 4 molar equivalents or more in total of organic acids relative to the total molar equivalents of iridoid compounds,
Producing a red pigment compound having a color forming property having bright redness and lightness,
A method for producing an iridoid compound-derived red pigment composition, comprising:
The step of performing the red coloration described in the above (Step 1) is
In addition to ascorbic acid, its analogous compounds, or two or more compounds selected therefrom as the organic acid, a solution containing an organic acid other than these is used.
The manufacturing method of the iridoid compound origin red pigment composition of Claim 1.
The step of performing the red coloration described in the above (Step 1) is
It is carried out in a solution containing one molar equivalent or more of ascorbic acid, an analogue thereof, or two or more compounds selected therefrom with respect to the total molar equivalent of the iridoid compound.
The manufacturing method of the iridoid compound origin red pigment composition of Claim 1 or 2.
The step of performing the red coloration described in the above (Step 1) is
As a molar ratio with respect to the total amount of organic acids, it is carried out in a solution containing 12.5% or more of ascorbic acid, its analogous compounds, or two or more compounds selected therefrom.
The method for producing the iridoid compound-derived red pigment composition according to any one of claims 1 to 3.
The step of performing the red coloration described in the above (Step 1) is
The organic acid may be selected from citric acid, succinic acid, malic acid, lactic acid, tartaric acid, fumaric acid, or similar compounds thereof, in addition to ascorbic acid, its analogous compounds, or two or more compounds selected therefrom. In a solution containing two or more compounds,
A method of producing the red pigment composition derived from the iridoid compound according to any one of claims 1 to 4.
The method for producing an iridoid compound-derived red pigment composition according to any one of claims 1 to 5, wherein the iridoid compound-derived red pigment composition is a gardenia red pigment composition.
The process according to (Step 1) above, wherein the reaction for producing iridoid aglycone from iridoid glucoside by β-glycosidic bond hydrolysis is carried out prior to and / or in parallel with red color development. 6. A method for producing the iridoid compound-derived red pigment composition according to any one of the above 6.
A process for producing an iridoid compound-derived red pigment composition according to any one of claims 1 to 7, characterized in that the iridoid compound-derived red pigment composition produced is bright red. And a method of imparting a coloring property having lightness.
Iridoid compound-derived red pigment composition having the characteristics described below:
When the aqueous solution of pH 5.0 is prepared with the McIlvaine buffer so as to have a color value E 10% 1 cm value 0.05 and the above-mentioned red dye composition is obtained, the following (formula 1) is satisfied:
(Expression 1): Δa + Δb ≧ 2
Δa = a 1 -a 0
Δ b = b 1- b 0
(Wherein, a 1 and b 1 represent the a value and b value respectively in the Hunter Lab color system in the aqueous solution containing the iridoid compound-derived red pigment composition, and a 0 and b 0 represent the iridoid, respectively) The a value and the b value in an aqueous solution prepared in the same manner as described above except that a standard dye is blended instead of the compound-derived red dye composition are shown, where the standard dye is the sample described in Example 1. 1 shows a pigment composition prepared in the same manner as 1-1).
An iridoid compound-derived red pigment composition obtained by the method according to any one of claims 1 to 7.
A pigment preparation comprising the iridoid compound-derived red pigment composition according to claim 9 or 10.
A food or drink product containing the iridoid compound-derived red pigment composition according to claim 9 or 10, or the pigment preparation according to claim 11, a cosmetic, a medicine, a quasi-drug, a hygiene daily product, or a feed.
A pigment preparation, a food / beverage product, a cosmetic, a medicine, an extra-drug part comprising the step of containing the iridoid compound-derived red pigment composition obtained by the method according to any one of claims 1 to 7. Products, hygiene items, or methods of producing feed.