KR20170035839A - Brown to Dark Brown Dye - Google Patents

Abstract

One of the objects of the present invention is to provide a coloring agent for brown to brown pigments having excellent acid resistance and / or salt resistance and capable of inhibiting the occurrence of precipitation, spots and staining even when used under conditions of low pH or high salt concentration . When brownish or brownish coloring matter is dissolved in water so as to have a color value E of ^{10% (500 nm)} = 0.1, citric acid is added in an amount of 1% by weight to give a brownish to brownish coloring matter Of the present invention have characteristics of excellent acid resistance and / or salt resistance, and even when used under conditions of low pH or high salt concentration, the coloring matter, The occurrence of coloring unevenness and the like can be suppressed.

Description

{Brown to Dark Brown Dye}

The present invention relates to a pigment of brown to brown type having excellent acid resistance and / or salt resistance and also having excellent foamability and foam stability. The present invention also relates to a method for producing such a pigment from brown to brown.

Conventionally, as a natural coloring for coloring a food or drink in a color system ranging from brown to brown, a brown to brown coloring matter such as a cacao coloring matter, a high coloring matter pigment, an onion coloring matter and a tamarind coloring matter is widely used. These brown to brown pigments are prepared by extracting pigment components from plant raw materials. For example, in the case of a cacao pigment, it is produced by extracting a pigment component from a cacao seed (sheath and soybean) as a raw material. Further, botanical raw materials of brown to brown pigments such as cacao seeds (sheath and soybean) contain impurities such as polysaccharides, gum, protein, etc. in addition to coloring components, Discoloration, formation of precipitates, and the like. Therefore, in the production of pigments ranging from brown to brown, it is important to reduce these impurities. Various methods are being studied.

Conventionally, various methods have been reported for reducing the amount of impurities and obtaining pigments ranging from brown to brown in the preparation of color tones from brown to dark brown. For example, Patent Document 1 discloses a process of extracting a cacao husk from neutral to slightly alkaline, a process of removing the gum by adding acetone after adjusting the pH of the obtained extract to 1 to 2, It has been reported that a dye which is soluble in water and stable at a wide range of pH can be obtained by carrying out a treatment of making alkaline and precipitating a pigment by salting out. Further, in Patent Document 2, it is reported that a dye in which the incorporation of contaminants is reduced is obtained by subjecting the cacao husk to an acid treatment in advance and then performing an extraction treatment. Further, in Patent Document 3, it has been reported that a dye having no odor has already been obtained by removing impurities using an ultrafiltration membrane having a cut-off molecular weight of 2,000 to 100,000 after the cacao husk is subjected to a weakly alkaline extraction treatment.

However, since the components of the brown to brown pigments obtained by the conventional production method are inevitably mixed under low pH or high salt concentration conditions, they can be satisfactory in terms of stability under low pH conditions or high salt concentration conditions If it is added to acidic beverages such as carbonated beverages, juice drinks, jelly and yogurt, and salt-containing foodstuffs such as seasonings, sauces, soups and carrules, precipitation, spots and staining may occur .

On the other hand, in order to improve a cooling sensation and a good taste in drinking alcoholic beverages, beverages, non-alcoholic beverages, carbonated beverages, foamable juice drinks and the like, there is a demand for properties capable of generating bubbles and maintaining stable bubbles. Conventionally, it is known that caramel dyes effectively retain bubbles generated in caramel dyes even among dyes of brown to brown type, so that they can be used as foam stabilizers for foamable beverages (see Patent Document 4). However, there has been no report on a technique of providing excellent foamability and foam stability using pigments other than caramel dyes.

With the background of such prior arts, it is desired to develop a pigment from brown to brown, which can be stained stably even under conditions of low pH or high salt, or a brown to brown type pigment having excellent foamability and foam stability have.

Patent Document 1: JP-A-48-17825 Patent Document 2: JP-A-53-109529 Patent Document 3: JP-A-60-43355 Patent Document 4: JP-A-2014-82940

One of the objects of the present invention is to provide a process for producing a polyurethane or brown-based polyurethane resin having excellent acid resistance and / or salt resistance and capable of inhibiting the occurrence of precipitation, spots, coloring unevenness and the like even under a condition of low pH or high salt concentration Thereby providing a pigment. Another object of the present invention is to provide a brown to brown pigment having excellent foamability and foam stability. Further, another object of the present invention is to provide a method for producing a pigment from brown to brown which has the above characteristics.

Means for Solving the Problems The present inventors have intensively studied to solve the above problems and found that a brown to brown pigment having at least one of the following characteristics (i) to (iii) has excellent acid resistance and / It is possible to suppress the occurrence of precipitation, spots, staining and the like even when used under low pH or high salt concentration conditions. Further, the inventor of the present invention has found that a brown to brown pigment having at least one of the following characteristics (i) to (iii) has strong bubble strength and excellent foamability, and can stably maintain the bubble generated for a long time And found that it was excellent in terms of foam stability.

(i) citric acid is added to the dye solution obtained by dissolving a pigment of a brown to brown color system in water such that the color value E is ^{10% (500 nm)} = 0.1, so that 60% Or more.

(ii) citric acid is added to the dye solution obtained by dissolving the pigment of the brown to brown type in water such that the color value E is ^{10% (500 nm)} = 0.1, so that 40% Of sodium chloride is added so as to be 10% by weight to the coloring matter solution in which the pigment is dissolved in water so as to maintain the state in which the pigment is dissolved in water to obtain a color value E of ^{10% (500 nm)} = 0.1. More than 80% of the brown pigment remains dissolved.

(iii) When 1 wt% of citric acid and 10 wt% of sodium chloride are added to a coloring solution obtained by dissolving a coloring agent of a brown to brown color system in water such that the color value E is ^{10% (500 nm)} = 0.1, 20% or more of the dye in the system remains dissolved.

Further, the brown to brown pigments having the above characteristics may be supplied with an oxygen gas under an alkaline condition against a pigment of a brown to brown type (or a plant raw material including a pigment of a brown to brown type) . ≪ / RTI > Further, the brown to brown pigments having the above characteristics can be obtained by providing a solution containing a pigment of a brown to brown color system to an adsorption resin treatment, a cation exchange resin treatment, an anion exchange resin treatment, or an activated carbon treatment, And recovering a specific portion. The present invention has been completed by further examination based on this knowledge.

That is, the present invention provides the invention of the following embodiment.

Item 1. A brownish or brownish coloring matter having at least one of the following characteristics (i) to (iii):

(i) citric acid is added to the dye solution obtained by dissolving a pigment of a brown to brown color system in water such that the color value E is ^{10% (500 nm)} = 0.1, so that 60% Or more.

(ii) citric acid is added to the dye solution obtained by dissolving the pigment of the brown to brown type in water such that the color value E is ^{10% (500 nm)} = 0.1, so that 40% Of sodium chloride is added so as to be 10% by weight to the coloring matter solution in which the pigment is dissolved in water so as to maintain the state in which the pigment is dissolved in water to obtain a color value E of ^{10% (500 nm)} = 0.1. More than 80% of the brown pigment remains dissolved.

(iii) When 1 wt% of citric acid and 10 wt% of sodium chloride are added to a coloring solution obtained by dissolving a coloring agent of a brown to brown color system in water such that the color value E is ^{10% (500 nm)} = 0.1, 20% or more of the dye in the system remains dissolved.

Item 2. The multicolor brown to brown colorant according to Item 1, having at least two of the above characteristics (i) to (iii).

Item 3. The multicolor brown or brown colorant according to item 1 or 2, which is at least one selected from the group consisting of cacao colorant, high colorant colorant, onion colorant and tamarind colorant.

Item 4. The brownish or brownish coloring matter according to any one of Items 1 to 3, which is used for coloring a food or drink having a pH of 2 to 6 and / or a salt concentration of 1 to 30% by weight.

Item 5. A coloring agent for seasoning ornamental plants containing the pigment from brown to brown as described in any one of Items 1 to 4.

Item 6. A seasoning product containing the brown-based or brown-based coloring matter according to any one of Items 1 to 4.

Item 7. A foaming agent or foam stabilizer for a foamable beverage containing the pigment from brown to brown as described in any one of Items 1 to 4.

Item 8. The effervescent drink containing the pigment from brown to brown as described in any one of Items 1 to 4.

Item 9. The use of the brown to brown pigment described in any one of Items 1 to 4 for coloring seasoning products.

Item 10. The foaming agent for foamable beverages according to any one of items 1 to 4, wherein the foam is of a brownish to brownish color, or foam stabilizer.

Item 11. The use of the brown to brown pigment as described in any one of Items 1 to 4 for coloring a foamable beverage.

Item 12. A method for producing a pigment from brown to brown type, wherein a pigment solution of a brown to brown color system is obtained by supplying an oxygen gas under alkaline conditions to a pigment from brown to brown.

Item 13. A production method according to Item 12, wherein oxygen gas under alkaline conditions is supplied to a plant raw material containing a pigment of a brown to brown color system.

Item 14. The production method according to item 12 or 13, wherein air is supplied as the oxygen gas.

Item 15. The production method according to any one of Items 12 to 14, wherein the supply rate of the sample gas is 0.01 vvm or more.

Item 16. The production method according to any one of Items 12 to 15, wherein the pH at the time of supplying the oxygen gas is 8 or more.

Item 17. A production method according to any one of Items 12 to 16, which is applied to production of at least one kind selected from the group consisting of a cacao coloring matter, a high coloring matter pigment, an onion coloring matter, and a tamarind coloring matter.

Item 18. A method for treating a non-adsorbed portion by treatment with an adsorbent resin, a cation exchange resin treatment by treatment with an adsorbent resin treatment, a cation exchange resin treatment, an anion exchange resin treatment, or an activated carbon treatment, And recovering a non-adsorbed portion by anion exchange resin treatment, or a non-adsorbed portion by an activated carbon treatment.

The brown to brown pigments of the present invention have excellent acid resistance and / or salt resistance and can inhibit the occurrence of precipitation, spots, staining and the like even under low pH conditions or high salt concentrations, Uniform and good coloring can be achieved with respect to various food and beverage products, including food and beverage products of high salt concentration.

Further, the pigments of brown to dark brown type according to the present invention are excellent in foamability and foam stability, so that when added to a carbonated foamable beverage, bubbles can efficiently be formed and the foam produced can be stably maintained for a long time.

Further, according to the method for producing a pigment from brown to yellow of the present invention, it is possible to easily produce a brown to brown pigment having excellent acid resistance and / or salt resistance, excellent foamability and foam stability.

Further, the brown to brown pigments of the present invention have excellent acid resistance and / or salt resistance, and are also good in hygroscopicity. Therefore, they are suitable as coloring agents used in foods and beverages having a low pH and / or a high salt concentration. Moreover, the pigment of the present invention from brown to brown is excellent in colorability as well as excellent foamability and foam stability, and is therefore also suitable as a coloring agent for use in carbonated foamable beverages.

Fig. 1 shows the result of observing the external appearance of the colored seasoning added with the conventional cacao pigment by centrifugal separation in Reference Test Example 1. Fig.
Fig. 2 shows the result of observing the appearance of pork cooked using the colored seasoning added with the conventional cacao pigment in Reference Test Example 1. Fig.
Fig. 3 is a graph showing the results of centrifugal separation of the coloring seasonings added with cacao dye in the measurement of the acid dissolution retention, the salt retention ratio, and the acid / As a result of observing the condition, the appearance of the pork cooked with the colored seasoning added with the cocoa pigment is observed.
4 shows the result of observing the state after centrifugation of the colored seasoning added with cacao dye in Test Example 5 and observing the appearance of the pork cooked with the colored seasoning added with cacao dye.
Fig. 5 shows the result of observing the state after centrifugal separation at the time of measurement of acid dissolution rate and dissolution rate of cacao pigment in Test Example 6. Fig.
Fig. 6 shows the result of observing the state after centrifugation in the measurement of the acid / salt dissolution rate of the cacao dye in Test Example 6. Fig.
Fig. 7 shows the result of observing the state after centrifugation of the colored seasoning added with cacao dye in Test Example 6. Fig.
Fig. 8 shows the results of examining the appearance of pork cooked with the colored seasoning added with the cocoa pigment of Example 13 and Comparative Examples 2 to 3 in Test Example 6. Fig.
Fig. 9 shows the results of observing the state before and after immersion of ion-exchanged water in the preparation of an egg prepared by using the colored seasoning added with the cacao dye or the commercial caramel coloring matter of Example 13 in Test Example 6. Fig.
10 shows the result of observing the state after centrifugation in the measurement of the acid dissolution rate retention, the salt retention ratio, and the acid / salt retention rate of cacao pigment in Test Example 7.
Fig. 11 shows the result of observing the state after centrifugation of the colored seasoning added with cacao dye in Test Example 7. Fig.
Fig. 12 shows the result of observing the state after centrifugation in the measurement of the acid dissolution retention and the salting-out retention ratios of the respective dyes of brown to brown type in Test Example 8. Fig.
Fig. 13 shows the results of observing the appearance of the acidic beverage before and after wide-width testing in Test Example 9. Fig.
Fig. 14 shows the result of observing the appearance immediately after the vibration of the buffer solution containing the cacao dye of Example 27 in Test Example 10. Fig.
Fig. 15 shows the result of observing the appearance after vibration of the buffer solution containing cacao dye of Example 27 in Test Example 11. Fig. The results of observing the appearance immediately after the vibration of the buffer solution containing the cacao pigment obtained in Examples 2, 12 and 27 to 30 and the commercial caramel color and after 5 minutes of vibration are shown.
16 shows the results of observing the appearance immediately after the vibration of the cacao dye obtained in Examples 2, 12, and 27 to 30 and the buffer containing the caramel coloring and the vibration after 5 to 60 minutes in Test Example 11 .
Fig. 17 is a graph showing the results of the evaluation of the results of Experimental Example 12, which were conducted immediately after the vibration including the caramel coloring matter, the cacao coloring matter (Example 31), the onion coloring matter (Example 32) and the high coloring matter (Example 33) And the appearance is observed.
18 shows the result of observing the appearance immediately after the vibration of the buffer solution containing various concentrations of cacao dye (Example 27) in Test Example 13;

One. Dark brown  To Brown  Pigment

In the present invention, the pigment from brown to brown is a pigment which can give a color tone of a brownish or brownish color to the object to be colored. More specifically, when a dye to be measured is diluted with a citric acid buffer solution (pH 7) (as described in the Food Additives Process Eighth Edition) so that the color value E is ^{10% (500 nm)} = 0.05, The L value measured by the spectral colorimeter is in the range of 5.00 to 95.00, the value of a is 1.00 to 16.00, and the value of b is 16.50 to 60.00.

In the present invention, there are no particular limitations on the kind of the brown to brown pigment, but specific examples thereof include cacao colorant, high colorant, onion colorant, tamarind colorant, persimmon colorant, caramel colorant, kooroo colorant , Shear nut coloring, papier coloring, pecan nuts coloring, logwood coloring, chicory coloring and the like. From the viewpoints of having more excellent acid resistance and / or salt resistance among these brown to yellow pigments, cacao colorant, high color pigment, onion colorant, tamarind colorant, more preferably cacao colorant, . Among these dyes of brown to brown type, cacao dye, onion dye, tamarind dye, and more preferably cacao dye are preferably used from the viewpoint of further providing excellent foamability and foam stability.

The brown to brown pigment of the present invention is characterized by having at least one of the following characteristics (i) to (iii). By having at least one of the following characteristics (i) to (iii), occurrence of precipitation, spots, coloring unevenness and the like can be suppressed even under a low pH condition or a high salt concentration condition, and uniform and good coloring becomes possible. Further, by having at least one of the following characteristics (i) to (iii), excellent foamability and foam stability can be provided.

(i) citric acid is added to the dye solution obtained by dissolving a pigment of a brown to brown color system in water such that the color value E is ^{10% (500 nm)} = 0.1, so that 60% Or more.

(ii) citric acid is added to the dye solution obtained by dissolving the pigment of the brown to brown type in water such that the color value E is ^{10% (500 nm)} = 0.1, so that 40% Of sodium chloride is added so as to be 10% by weight to the coloring matter solution in which the pigment is dissolved in water so as to maintain the state in which the pigment is dissolved in water to obtain a color value E of ^{10% (500 nm)} = 0.1. More than 80% of the brown pigment remains dissolved.

(iii) When 1 wt% of citric acid and 10 wt% of sodium chloride are added to a coloring solution obtained by dissolving a coloring agent of a brown to brown color system in water such that the color value E is ^{10% (500 nm)} = 0.1, 20% or more of the dye in the system remains dissolved.

In the present invention, the term "color value E ^{10% (500 nm)} " means the measurement of absorbance (measuring cell width: 1 cm) at an absorption wavelength of 500 nm of a brown to brown dye, v% absorbance of the dye solution.

Hereinafter, when the citric acid is added so as to be 1% by weight to the coloring solution obtained by dissolving the pigment of the brown to brown type in water such that the color value E is ^{10% (500 nm)} = 0.1, the proportion of the coloring matter which remains in the dissolved state is There is also a case where it is marked as 'the maintenance rate of the use of acid.' When ^10% by weight of sodium chloride is added to a coloring solution obtained by dissolving a colorant of a brown to brown color system in water such that the color value E is ^{10% (500 nm)} = 0.1, The ratio of the pigment of the brown system is sometimes referred to as "salt retention rate". Furthermore, when 1 wt% of citric acid and 10 wt% of sodium chloride were added to a coloring solution obtained by dissolving a colorant of brown to brown type in water to have a color value E of ^{10% (500 nm)} = 0.1, the dissolved state The ratio of the colorants of the brownish brown to the brownish color that is maintained may be expressed as 'acid / salt retention ratio'.

The characteristic of the above (i) is effective in suppressing the occurrence of precipitation, spotting, coloring unevenness and the like in a low pH condition, and enabling stable coloring in an acidic food or drink. In addition, the characteristics of the above (i) are effective for providing excellent foamability and foam stability. As the characteristic of the above-mentioned (i), it is required that the acid dissolution retention ratio satisfies 60% or more. From the viewpoint of further excellent acid resistance, further excellent foamability and foam stability, the acid retention ratio is preferably 65 Or more, more preferably 70% or more, and particularly preferably 80% or more.

The characteristic of (ii) above is effective in suppressing the occurrence of precipitation, spots, staining and the like in a low pH and high salt concentration condition and enabling stable coloring in an acidic food or drink having a high salt concentration do. Further, the property (ii) above is also effective for providing excellent foamability and foam stability. As the characteristics of the above-mentioned (ii), it is necessary that the acid dissolution retention ratio is 40% or more and the salt dissolution retention ratio is 80% or more. However, it is required to have further excellent acid resistance and / or salt resistance, more excellent foamability and foam stability It is preferable that the acid retention ratio is 50% or more and the salt retention ratio is 85% or more, more preferably the acid retention percentage is 60% or more and the salt retention ratio is 90% or more, Or more and a salt retention ratio of 90% or more, particularly preferably an acid solution retention rate of 80% or more and a salt retention ratio of 90% or more.

The characteristic of the above (iii) is effective in suppressing the occurrence of precipitation, spots, staining and the like in a low pH and high salt concentration condition and enabling stable coloring in an acidic food or drink having a high salt concentration do. In addition, the characteristics of (iii) above are also effective for providing excellent foamability and foam stability. As the characteristics of (iii), it is sufficient that the acid / salt solution retention ratio satisfies 20% or more. In view of providing more excellent acid resistance and / or salt resistance, more excellent foamability and foam stability, , Preferably 30% or more, and more preferably 40% or more.

The brown to brown pigment of the present invention is required to have at least one of the above characteristics (i) to (iii), and has excellent acid resistance and / or salt resistance and further excellent foamability and foam stability (I) to (iii), and more preferably all of the characteristics (i) to (iii) are satisfied.

On the other hand, in the present invention, the 'dissolution rate maintenance ratio' is obtained by the following method. First, a pigment of a brown to brown type is added to purified water so that the color value E is ^{10% (500 nm)} = 0.1 at room temperature, and a dye solution is prepared. Subsequently, citric acid was added to the dye solution so as to be 1 wt%, stirred sufficiently, and allowed to stand at a temperature of 5 캜 for 24 hours. After standing for 24 hours, the coloring matter solution is centrifuged to remove the insoluble matter, and the color value E ^{10% (500 nm)} of the obtained supernatant is measured. The ratio (%) of the color value E ^{10% (500 nm)} of the supernatant of the coloring matter solution after standing for 24 hours to the color value E ^{10% (500 nm)} of the coloring matter solution before addition of citric acid is obtained as the retention rate.

In the present invention, the 'salt retention ratio' is obtained by the same method as the acid dissolution retention ratio except that sodium chloride is added to the dye solution in an amount of 10 wt% instead of citric acid.

In the present invention, the "acid / salt solution retention ratio" is calculated by the same method as the acid dissolution retention ratio except that citric acid is added to the dye solution in an amount of 1% by weight of citric acid and 10% by weight of sodium chloride, It becomes.

Here, the color value E ^{10% (500 nm)} is a color value calculated by (dilution ratio of dye solution for absorbance measurement) x (absorbance of absorption wavelength 500 nm at an optical path length of 1 cm) x 0.1. On the other hand, in the measurement of the color value E ^{10% (500 nm)} , a citric acid buffer solution (pH 7) (the one described in the eighth edition of the Food Additives Process) is used as a dilute solvent for the colorimetric solution for absorbance measurement.

2. Dark brown  To Brown  Manufacturing method of pigment

The method for producing the brown to brown pigments of the present invention is not particularly limited as long as it is capable of obtaining at least one of the above-mentioned characteristics (i) to (iii).

[Method 1]

As a suitable example of the method for producing a pigment from brown to yellow in the present invention, there is a method of supplying oxygen gas to a pigment from brown to brown based on an alkaline condition (hereinafter sometimes referred to as "first method" ). By supplying oxygen under alkaline conditions as described above, insoluble components are removed under low pH conditions and / or high salt concentrations, so that a brown to brown pigment having the above characteristics can be obtained. Hereinafter, a specific embodiment of the first method will be described.

Raw materials of the first method

According to the first method, oxygen gas is supplied under alkaline conditions to colorants ranging from brown to brown.

In the first method, the raw material to be supplied with the oxygen gas under the alkaline condition is a brown to brown pigment extracted from a plant raw material containing a pigment of a brown to brown type, a brown to brown pigment obtained by culturing the microorganism A brown-based coloring matter, a synthesized brown-to-brown coloring matter, and the like. These pigments of the brown to brown type may be those which have been provided for the purification treatment by a conventional technique.

Further, in the first method, the plant raw material containing the pigment of the brown to brown type may be directly supplied as the oxygen gas under the alkaline condition. The method of using the plant raw material containing the pigment of the brown to brown system as the raw material of the first method and supplying the oxygen gas under the alkaline condition to the plant raw material is characterized in that the plant raw material is a multi- The extraction of the pigment can be performed at the same time, so that it can be said that it is suitable from the viewpoint of simplification of the manufacturing process.

(A plant raw material containing a pigment of a brown to brown type)

The plant raw materials containing the pigments of the brown to brown type are appropriately selected depending on the kinds of the brown to brown pigments to be produced. For example, in the case of the cacao pigments, the cacao husks and / or the cacao beans ; In the case of high pigment, high fruit and / or bark; In the case of an onion dye, the diameter and / or the sheath of the onion; Seeds of tamarind in the case of tamarind pigment; Persimmon fruit in the case of persimmon pigment; In the case of crepe pigment, maupuri; In the case of cyanat coloring, fir tree fruit and / or seed coat; In the case of a pecan nuts pigment, the pericarp and / or the ecchymosis of the pecan; In the case of logwood pigment, logwood core; In the case of chicory pigment, it can be said that it is the root of the government bond.

It is the seed coat of cacao husk, which is the raw material for extracting cacao pigment, and cacao (Theobroma cacao L. In addition, the cacao bean which is an extraction raw material of cacao pigment is a seed of cacao (Theobroma cacao L.). In the case of a cacao pigment, either of cacao husk or cacao bean may be used alone as an extraction raw material, or a combination thereof may be used. A suitable example of the raw material for extraction is cacao husks.

The high amount of the fruit which becomes the extraction raw material of the high pigment is seed of Sorghum nervosum BESS. In addition, the high amount of the husk which becomes the extraction raw material of the high pigment is the seed husk of the sorghum nervosum BESS. In the case of a high-color pigment, either of a high-content fruit or a shell may be used singly or in combination as a raw material for extraction.

The onion which is an extraction raw material of the onion coloring is the flower of the lily and the onion (Allium cepa LINNE). The envelope of the onion which becomes the extraction raw material of the onion pigment is the envelope of the lily and the onion (Allium cepa LINNE). In the case of an onion dye, either the phosphorus or the shell of the onion may be used singly or in combination as an extracting raw material.

The tamarind seed, which is the raw material for the tamarind pigment, is a seed of tamarindus indica LINNE.

The fruit of persimmon which becomes the extracting raw material of the persimmon pigment is the fruit of persimmon and persimmon (Diospyros kaki THUNB.).

The root of the horse that becomes the raw material of the crepe pigment is the root of the yam and hemp (Dioscorea matsudai HAYATA).

The fruit of the cedar tree which is the raw material of the cedar nut coloring is the fruit of the cedar tree (Butyrospermum parkii KOTSCHY.). In addition, the seed coat of the cinnabar tree (Butyrospermum parkii KOTSCHY.) Which is the raw material for the extraction of the cyanate pigment is the seed coat.

Pecan's perianth is an extract of walnut and pecan (Carya pecan ENGL. Et GRAEBN.), Which is an extraction source of pecan nuts pigment. Also, it is a subculture of pecan, walnut and pecan (Carya pecan ENGL. Et GRAEBN.) Which is an extraction raw material of pecan nuts pigment. In the case of the pecan nuts pigment, either of the peel or the pecan of the pecan may be used singly or as a mixture of the pecans as the extraction raw material.

The heartwood of logwood, which is the raw material for logwood pigment, is the core of soybean and logwood (Haematoxylon campechianum).

The root of the Kokongeji as the raw material of the chicory pigment is the root of the Cichorium intybus LINNE.

(Brown to brown pigments extracted from plant raw materials including pigments ranging from brown to brown)

The brown to brown pigments can be obtained from plant raw materials containing pigments ranging from brown to brown based on a known extraction process.

The plant material used as an extraction raw material for obtaining a pigment of a brown to brown type may be provided in a drying treatment, a degreasing treatment, a fermentation treatment, a power distribution treatment or the like, if necessary. It is preferable that the plant material used as the raw material for extraction is subjected to crushing treatment such as crushing and crushing in order to improve the extraction efficiency.

The extraction solvent used for extracting the brown to brown pigment from the plant material containing the pigment from brown to brown is suitably set in accordance with the kind of pigment to be used for the production of the brown to brown pigment.

For example, in the case of a cacao pigment, an alkaline aqueous solution may be used as an extraction solvent. In the case of high coloring matter, water, hydrous ethanol, acidic ethanol, or alkaline aqueous solution may be used. In the case of an onion pigment, water, hydrous ethanol or an alkaline aqueous solution may be used as an extraction solvent. In the case of a tamarind pigment, an alkaline aqueous solution may be used as an extraction solvent. In the case of the sensitizing dye, an alkaline aqueous solution may be used as the extraction solvent. In the case of a crepe pigment, water, an alkaline aqueous solution, propylene glycol, or hydrous ethanol may be used as an extraction solvent for the roots of a horse. In the case of the cyanate pigment, an alkaline aqueous solution may be used as the extraction solvent for the fruit and / or seed coat of the cyanobacterium. In the case of the pecan nuts pigment, water, hydrous ethanol, or an acidic aqueous solution may be used as the extraction solvent for the pericarp and / or the ecchymosis of the pecan. In the case of log wood dye, water may be used as the extraction solvent for the logwood core. In the case of the chicory coloring matter, water may be used as the extraction solvent for the roots of the Japanese government bond.

In order to extract and treat the brown to brown pigment from a plant raw material containing a pigment of a brown to brown type, the plant raw material may be impregnated with an extraction solvent and stirred if necessary.

The amount of the extraction solvent used for the extraction treatment may be suitably set according to the kinds of the pigments of the brown to brown type for the purpose of production. For example, the weight ratio of the extraction raw materials to the plant raw materials 5 to 50 times, preferably 5 to 40 times, and more preferably 5 to 30 times.

The temperature during the extraction treatment may be suitably set in accordance with the kind of the pigment from brown to brown which is the object of production. For example, it may be 30 to 100 캜.

The extraction treatment time may be suitably set in consideration of the kind of the pigment from brown to brown which is to be produced, the amount of the extraction solvent to be used, the temperature at the extraction treatment, etc. For example, Preferably 1 to 20 hours, more preferably 1 to 10 hours.

(Brown to brown pigments obtained by culturing microorganisms)

The brown to brown pigment may be obtained by culturing a microorganism having an acidic activity of the pigment. For example, in the case of a Papia pigment, it can be obtained by recovering from a culture solution of yeast (Phaffia rhodozyma MILLER).

(Synthetic brown to brown pigments synthesized)

The brown to brown pigment may be obtained by synthesizing by a known method. For example, in the case of caramel coloring, it can be obtained by heat-treating edible carbohydrates such as sugar and glucose.

Treatment conditions of Method 1

In the first method, oxygen gas is supplied under alkaline conditions to a pigment of a brown to brown color system (which may be a state of a plant raw material including a pigment of a brown to brown color system). By supplying oxygen under the alkaline condition as described above, insoluble components are removed under the conditions of low pH and / or high salt concentration, so that a brown to brown pigment having the above characteristics can be obtained. Further, in the first method, when oxygen gas is supplied to a plant raw material containing a pigment from a brown to brown system under an alkaline condition, it is possible to obtain oxygen from the plant raw material, It is possible to selectively extract the coloring matter, which may contribute to the improvement of the production efficiency of the coloring from brown to brown coloring agents of the present invention.

When oxygen gas is supplied to a plant raw material containing a pigment of a brown to brown color system under an alkaline condition, the plant raw material may be provided in a drying process, a degreasing process, a fermentation process, a power distribution process or the like, if necessary. It is also preferable that the plant material is subjected to a crushing process such as crushing and crushing in order to efficiently obtain a brownish-brown pigment having the above-mentioned characteristics.

The liquid (alkali condition) at the time of oxygen supply is usually 8 or more, preferably 9 to 13, and more preferably 11 to 13. Such an alkaline condition can be produced by causing a pigment of a brown to brown color system (which may be a state of a plant raw material including a pigment of a brown to brown color system) in an alkaline aqueous solution.

There is no particular limitation on the concentration of the brown to brown pigment when the oxygen gas is supplied. For example, the concentration of the brown to brown pigment obtained by extracting the plant material, culturing the microorganism, If the case of providing the oxygen supply, an aqueous alkaline solution from the color value of ^{E 10% (500nm) = 0.1} ~ 70, preferably a color value of ^{E 10% (500nm) = 1} ~ 50, more preferably a color value of E ^{10% (500nm)} = The concentration is from 1 to 30. In the case of providing the plant raw material itself containing the pigments of the brown to brown type to the supply of the oxygen gas, the alkaline aqueous solution is added to the plant raw materials containing the pigments of the brown to brown type at a weight ratio of 5 to 50 times, Preferably 5 to 40 times, more preferably 5 to 30 times.

The alkali used in the preparation of the alkaline aqueous solution may be any alkali which can be used in the field of food and beverage, and examples thereof include sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, calcium hydroxide, Calcium carbonate, ammonium hydroxide, ammonia water, aluminum hydroxide, and iron hydroxide. These alkalis may be used singly or in combination of two or more kinds.

The alkaline aqueous solution may be one in which the alkali is added so as to satisfy a predetermined pH with respect to water. If necessary, additives such as an alcohol, an antiseptic, a solubilizing agent and a defoaming agent may be contained.

The temperature condition at the time of oxygen supply is usually 30 to 100 占 폚, preferably 50 to 100 占 폚, and more preferably 70 to 100 占 폚.

The oxygen gas to be supplied in the first method may be oxygen gas itself, but it may be a gas containing oxygen components other than oxygen, such as air, provided that oxygen gas is included . As the oxygen to be supplied during the extraction process from the viewpoint of reduction of production cost and the like, air is preferably used.

The supply rate of the oxygen gas is suitably set in accordance with the pH at the time of supplying the oxygen gas, the amount of the liquid supplied with the oxygen gas, the presence or absence of the stirring in the supply of the oxygen gas, the stirring speed and the like. For example, 0.01 vvm or more, 0.01 to 2.0 vvm, and more preferably 0.05 to 1.0 vvm. More specifically, when the pH at the time of supplying oxygen gas is 12 or more and less than 13, the feeding rate of oxygen gas is 0.2 to 2 vvm, preferably 0.2 to 1 vvm, and the pH at the time of supplying oxygen gas is 13 or more In this case, the supply rate of the oxygen gas is 0.05 to 2 vvm, preferably 0.05 to 0.5 vvm. On the other hand, the supply rate of the oxygen gas exemplified here indicates the supply rate of the oxygen gas itself. That is, for example, when air is used as the oxygen gas, since air contains about 20% by volume of oxygen, air may be supplied at a rate five times the supply rate.

The supply time of the oxygen gas in the first method is suitably set in accordance with the pH at the time of supplying the oxygen gas, the amount of the liquid supplied with the oxygen gas, the presence or absence of the stirring in the supply of the oxygen gas, the stirring speed, Or more, preferably 1 to 10 hours, and more preferably 1 to 5 hours.

Further, when supplying oxygen gas, it is preferable to stir the oxygen gas to uniformly disperse the oxygen gas.

Since the liquid obtained after the supply of the oxygen gas in this way has dissolved the brown to brown pigments having the above characteristics, the liquid is provided to the solid-liquid separation treatment, and the liquid portion is recovered as a pigment solution of a brown to brown system . The pigment solution of the brown to brown system may be used as a colorant for food and beverage, and may be used as a coloring agent for a food or drink after neutralization, concentration, drying treatment or the like, if necessary.

The pigment solution of the brown to brown system obtained after the supply of the oxygen gas may be provided as it is or after the neutralization treatment or the concentration treatment and then to the purification treatment for removing or reducing the impurities such as the germination. By providing such a purification treatment, a more stable yellowish brown to brownish coloring matter can be obtained. Particularly, when oxygen gas is supplied to a plant raw material containing a pigment of a brown to brown type, it is preferable that the solution of a pigment of a brown to brown type obtained after oxygen gas supply is provided for the purification treatment.

The stagnant treatment performed on the dye solution is not particularly limited. For example, the adsorbent resin treatment, the cation exchange resin treatment or the anion exchange resin treatment similar to the second method described later may be performed, Method, and the like. As a preferable example, the following steps (i) to (iii) may be carried out sequentially.

(i) a step of adjusting the pH of the dye solution of the brown to brown system to 1 to 2,

(ii) a step of adding an organic solvent for coagulating the gums to the acidic brown to brown pigment solution obtained in the step (i) and recovering the water-soluble portion, and

(iii) a step of recovering a brownish to brownish coloring matter obtained by neutralizing or making the alkali-soluble part of the water-soluble part obtained in the step (ii).

In the step (i), in order to adjust the pH of the dye solution of the brown to brown range from 1 to 2, it is preferable to add the acid such as hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, . These acids may be used singly or in combination of two or more kinds.

The organic solvent used in the step (ii) is not particularly limited as long as it has a function of agglomerating gum, and for example, an organic solvent such as acetone and ethanol, preferably acetone . In addition, in the step (ii), the amount of the organic solvent added to the acidic brown to brown pigment solution obtained in the step (i) is included in the acidic brown to brown dye solution But it may be 0.4 to 9 times, preferably 0.6 to 4 times as much as the acidic brown to brown coloring matter solution at a dose ratio, for example. In the step (ii), the organic solvent is added to and mixed with the acidic brown to brown pigment solution to cause the gums contained in the acidic brown to brown pigment solution to flocculate, Therefore, by separating the agglomerates of the gum by filtration or the like, a water-soluble part in which the pigment of brown to brown type is dissolved is obtained.

In the step (iii), an alkali such as sodium hydroxide, potassium hydroxide, sodium phosphate, sodium carbonate, or potassium carbonate may be added to make the water-soluble portion obtained in the step (ii) neutral to weakly alkaline. These alkalis may be used singly or in combination of two or more kinds. The alkali may be added in the form of a solid as it is, or it may be added in the form of an aqueous alkali solution dissolved in water. In the step (iii), the pH of the water-soluble part may be adjusted to be neutral to slightly alkaline. More specifically, the pH after preparation may be 7-12, preferably 8-11. In the step (iii), by adjusting the water-soluble portion to be neutral to slightly alkaline, a brown to brown pigment is precipitated in the upper layer by salting out. By separating the upper layer portion by filtration or the like, the purplish brown to brown pigment of the present invention is obtained. The resulting brown to brown pigment may be subjected to other purification treatment, drying treatment or the like, if necessary.

[Second Method]

In addition to the first method described above, the coloring from brown to brown of the present invention can be performed by a method in which a solution containing a pigment of a brown to brown color system is subjected to an adsorption resin treatment, a cation exchange resin treatment, an anion exchange resin treatment, To thereby recover a non-adsorbed portion by adsorption resin treatment, a non-adsorbed portion by cation exchange resin treatment, an adsorbed portion by anion exchange resin treatment, or a non-adsorbed portion by activated carbon treatment (hereinafter, Law "in some cases). Hereinafter, a specific embodiment of the second method will be described.

Raw material of the second law

In the second method, a predetermined adsorption treatment is performed on a solution containing a pigment of a brown to brown color system.

In the second method, the solution to be subjected to the predetermined adsorption treatment may be an extract of a brown to brown pigment extracted from a plant raw material containing a pigment of a brown to brown color system, a brown color system obtained by culturing the microorganism A solution of a brown color system, a solution of a color system of a brown to brown system synthesized, and the like. Methods for obtaining pigments of brown to brown type by extracting from plant raw materials, culturing microorganisms, synthesizing, etc. are as described in the column of the first method.

In the second method, it is preferable that the solution provided for the predetermined adsorption treatment contains water as a solvent. In addition, in the second method, the solution to be subjected to the predetermined adsorption treatment is preferably a state in which the solid content is removed, and may be provided for treatment such as neutralization treatment, concentration treatment, .

Treatment conditions of the second method

In the second method, a solution containing a pigment of a brown to brown color system is subjected to an adsorption resin treatment, a cation exchange resin treatment, an anion exchange resin treatment, or an activated carbon treatment to form a nonadsorption portion by adsorption resin treatment, a cation exchange The non-adsorbed portion by the resin treatment, the adsorbed portion by the anion exchange resin treatment, or the non-adsorbed portion by the activated carbon treatment is recovered.

The adsorbent resin treatment in the second method is a treatment for passing a solution containing a pigment of a brown to brown color system to the adsorbent resin, and the portion (non-adsorbed portion) through which the adsorbent resin is not adsorbed (That is, the brown to brown pigment of the present invention).

The adsorption resin is a nonpolar or medium polarity porous resin also called a synthetic adsorbent. Specific examples of such adsorbent resins include styrene resins such as styrene-divinylbenzene copolymer, acrylic resins such as (meth) acrylic acid ester-ethylene glycol dimethacrylate copolymer, methacrylic resins, polyvinyl resins , And dextran-based resins. Among these adsorbent resins, a styrene resin is preferably used from the viewpoint of obtaining a brownish to brownish pigment having more excellent acid resistance and / or salt resistance. Specific examples of commercially available adsorbent resins include styrene resins such as Diaion HP10, Diaion HP20, Diaion HP21, Diaion HP40, Diaion HP50, Sephapie SP207, Sephapie SP70, Amberlite XAD2000, Amberlite XAD4, Amberlite FPX66 (manufactured by Rohm & Haas), etc.); Examples of the acrylic resin include Diaion HP2MG (manufactured by Mitsubishi Kagaku) and Amberlite HXAD-7HP (manufactured by Rohm and Haas).

The temperature condition of the adsorption resin treatment in the second method is not particularly limited and can be performed at room temperature, for example. Further, in the adsorbent resin treatment, there is no particular limitation on the passing speed of the solution containing the pigment of the brown to brown type and the washing liquid passing through as required. However, for example, as the space velocity (SV) To 10 / h, preferably 0.5 to 5 / h.

The cation exchange resin treatment in the second method is a treatment for passing a solution containing a pigment of a brown to brown color system to a cation exchange resin and is a treatment of passing through a part (non-adsorption Part) is recovered as a brown to brown pigment (that is, a brown to brown pigment of the present invention) satisfying the above characteristics.

The type of the functional group in the cation exchange resin used in the second method is not particularly limited as long as cation exchange is possible. For example, -SO ₃ M (M is an alkali metal or a hydrogen atom) have. Specific examples of commercially available cation exchange resins include UBARLITE 200CT, UBALITE IR120B, UBALITE IR124, UBALITE 252, UBALITE FPC3500, UBALITE IRC76 (manufactured by Rohm and Haas) Diaion SK1B, Diaion SK102, Diaion SK116, Diaion PK208, Diaion WK10, Diaion WK20 (hereinafter referred to as Mitsubishi Kagaku Co., Ltd.), and the like.

In the cation exchange resin treatment, there are no particular limitations on the temperature condition, the liquid passing rate of the solution containing the pigment from brown to brown, and the like. For example, if it is set in the same range as the case of the adsorption resin treatment do.

The anion exchange resin treatment in the second method is a treatment for passing a solution containing a pigment of a brown to brown type to an anion exchange resin, and a portion (adsorption portion) adsorbed to the anion exchange resin is treated (I.e., a brown to brown pigment of the present invention) satisfying the characteristics of the present invention.

The kind of the functional group in the anion exchange resin used in the second method is not particularly limited as long as anion exchange can be performed. For example, -N≡ (CH ₃ ) ₃ X (X represents a chlorine atom or the like Halogen atom), -N (-C ₂ H ₄ OH) = (CH ₃ ) ₂ X (X is a halogen atom such as a chlorine atom). Specific examples of commercially available anion exchange resins include UBALITE IRA958, UBALITE IRA400J, UBALITE IRA402BL, UBBARITE IRA404J, UBBARITE IRA900J, UBBARITE IRA904, UBBARITE IRA458RF, UBBARITE IRA410J, (Commercially available from Mitsubishi Kagaku Co., Ltd.), and the like can be given as examples of the curable resin composition of the present invention. Examples of the curable resin include IRA411, IRA910CT, IRA910CT (manufactured by Rohm and Haas), Daiion PA306, Daiion WA10 and Daiion WA20.

In the anion exchange resin treatment in the second method, the passage of the solution containing the pigment of the brown to brown type and the passage of the desorption liquid are sequentially carried out for the anion exchange resin, and from the passive desorption liquid, To recover the brown pigment. In addition, a washing liquid may be passed between the passing liquid of the extract and the passing liquid of the desorbing liquid, if necessary.

The composition of the desalination liquid is not particularly limited as long as it is a solution capable of desorbing the brown to brown pigment adsorbed on the anion exchange resin, and examples thereof include an aqueous alcohol solution. The kind of alcohol used in the alcohol aqueous solution is not particularly limited, and examples thereof include ethanol, propanol, butanol, and preferably ethanol. The alcohol concentration to be used in the alcohol aqueous solution is not particularly limited, but is, for example, 30 to 90 v / v%, preferably 40 to 80 v / v%.

The composition of the washing liquid is not particularly limited as long as it can wash the pigment of brown to brown which is not adsorbed on the anion exchange resin, and examples thereof include water.

In the anion exchange resin treatment, there are no particular limitations on the temperature condition, the passing speed of the solution containing the pigment from brown to brown, the passing speed of the washing liquid passing through as required, the passing speed of the washing liquid, It may be set in the same range as in the case of the adsorbent resin treatment.

The activated carbon treatment in the second method is a treatment for mixing or passing a solution containing a pigment of a brownish or brownish color against activated carbon, and a portion (non-adsorbed portion) through which the activated carbon is not adsorbed (I.e., a brown to brown pigment of the present invention) satisfying the characteristics of the present invention.

As the activated carbon used in the second method, those having an adsorption action similar to that of the adsorbent resin may be used. Also, there is no particular limitation on the temperature conditions and the like in the activated carbon treatment. For example, in the case of the adsorbent resin treatment It may be set in the same range.

In the second method, it is preferable to carry out any one treatment of adsorbent resin treatment, cation exchange resin treatment, anion exchange resin treatment, or activated carbon treatment on a solution containing a pigment from brown to brown, From the viewpoint of obtaining a pigment of a brown to brown type having a flame retardancy and / or a salt resistance, an adsorbent resin treatment is preferable, and an adsorbent resin treatment using a styrene resin is more preferable.

(The non-adsorbed portion by the adsorption resin treatment, the non-adsorbed portion by the cation exchange resin treatment, the adsorbed portion by the anion exchange resin treatment, or the activated carbon Adsorbed portion by treatment) may be used as a colorant for food and beverage as it is, and may be used as a colorant for a food or drink after being provided for treatment such as concentration and drying, if necessary.

The second method can be applied to the production of the brown to brown pigments of the present invention irrespective of the kind of the brown to brown pigments, and can be suitably used for the production of cacao pigments.

Dark brown  To Brown  Usage of pigment

The brown to brown pigments of the present invention are used as coloring agents for coloring food and drink. The brown to brown pigments of the present invention are not particularly limited to foods and beverages to be colored, and they can be used for foods and beverages of all pH and salt concentrations.

Conventional brown to brown pigments (in particular, cacao coloring matter) are disadvantageous in that they are unstable when added to foodstuffs of acidic foods and foods of high salt concentration, resulting in precipitation, spotting, coloring unevenness and the like. The brown to brown pigments have excellent acid resistance and / or salt resistance, and overcome the drawbacks of the conventional brown to brown pigments. Thus, even when added to an acidic food or a food having a high salt concentration, So that coloring is possible. In view of the effects of the present invention, as a suitable example of the foods and beverages to be added to the pigments of the brown to brown pigments of the present invention, acidic foods and foods with high salt concentration, Food and drink. The pH of the acidic food or drink to be added to the pigments of the brown to brown type of the present invention is specifically 2 to 6, preferably 2 to 5, and more preferably 2 to 4. The salt concentration of the high salt concentration food and beverage to be added to the pigments of the brown to brown type of the present invention is specifically 1 to 30% by weight, preferably 1 to 20% by weight, more preferably 5 to 20% by weight, 20% by weight. Here, the salt concentration of the salt-containing food or drink refers to the total concentration of the water-soluble inorganic salt (sodium chloride, potassium chloride, etc.) contained in the food or drink.

Specific examples of the acidic food or drink to be added to the pigments of the brown to brown type of the present invention include juice drinks, jellies, yogurt, pickles, carbonated drinks and the like. Specific examples of the foods and beverages of high salt concentration to be added to the pigments of the brown to brown type according to the present invention include safflower, sauces, soups, curries, pickles, and boiled foods. In addition, as the acidic foods and beverages of high salt concentration to be added to the pigments of the brown to brown type according to the present invention, there may be mentioned seasoning foods, pickles, sauces and the like.

When it is used as a coloring agent of the brown to brown pigments of the present invention, the amount added to the food and drink may be suitably set in accordance with the degree of coloring to be imparted to the food and drink.

The pigments of brown to brown type according to the present invention have excellent foamability and foam stability, and therefore can be used as foaming agents for foamable beverages or foam stabilizers. When the pigment of the present invention is used as a foaming agent or foam stabilizer, the beverage to be added is not particularly limited as long as it is required to have foamability and / or foam stability, For example, a foamable beverage may be mentioned. Specific examples of the foamable beverage include beverage, alcoholic beverage, alcoholic beverage such as sparkling wine, other bubbling brew, liqueur, and sparkling wine; Beer taste non-alcoholic beverage; Carbonated soft drinks such as cola and ginger ale; Sparkling orange juice drink, sparkling grape juice drink, foamable apple juice drink, and foamable lemon juice drink. When the pigment of the present invention is used as a foaming agent or a foam stabilizer, the pH of the foamable beverage to be added is not particularly limited, but from the viewpoint of imparting more excellent foamability and foam stability , The pH of the foamable beverage to be added is preferably 2 to 6, more preferably 3 to 5.

Particularly, the brown to brown dyes of the present invention can impart not only excellent foamability and foam stability but also a color tone ranging from brown to brown to the foamable beverage, so that the foamable beverage having a light brown to brown tone , It is particularly suitably used as a foamable coloring agent or a foam stabilizing coloring agent. Specific examples of the effervescent beverages exhibiting such a light brown to brownish hue include other effervescent brewers, malt and / or barley produced by using beer, sparkling wine, malt and / or barley as a part of raw materials as a part of raw materials Alcoholic beverage such as liqueur and sparkling red wine manufactured by using; Beer taste non-alcoholic beverage; Carbonated soft drinks such as cola and ginger ale; Fizzy orange juice drink, foamable juice drink of expandable grape juice, fizzy apple juice drink, and foamable juice drink such as fizzy lemon juice drink.

When the pigment of the present invention is used as a foaming agent or foaming stabilizer for foamable beverages, the amount added to the foamable beverage may be suitably set in accordance with the foaming power to be imparted to the foamable beverage, In an amount of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, more preferably 0.01 to 1% by weight in terms of a solution amount in which the color E is ^{10% (500 nm)} = 100.

Example

Hereinafter, the present invention will be described concretely with examples and the like, but the present invention is not limited to these examples.

Reference Test Example  1: Conventional cacao pigment Low pH condition  And High salt concentration  Evaluation of characteristics in conditions

1. Manufacture of cacao pigment

A cacao pigment was prepared by a conventional method. Specifically, a cacao pigment was produced by performing the following extraction step and purification step.

<Extraction Process>

100 g of cacao husk was added to 2000 ml of aqueous sodium hydroxide solution having pH of 12.52 and extraction treatment was carried out for 2 hours while stirring at 80 캜. After the extraction treatment, the solid content was removed, and an extract containing the cacao pigment was obtained.

<Purification step>

The extract obtained above was concentrated, acetone was added, the pH was adjusted to 3 in hydrochloric acid, and the mixture was allowed to stand at 5 占 폚 for 16 hours to precipitate impurities such as gum. Subsequently, the impurities were removed by filtration, the pH was adjusted to 10 with sodium hydroxide, and the mixture was allowed to stand at 5 占 폚 for 16 hours to precipitate a cacao dye component. The precipitated cacao dye was recovered and dissolved in water, followed by removal of acetone by concentration, followed by concentration, drying, and pulverization to give 10 g of cacao pigment powder.

2. Characterization of cacao pigment

Using the safflower liquid (pH 4.8, salt content 7% by weight) as a food having a low pH and a high salt concentration, coloring by the conventional cacao coloring obtained as described above was carried out. Specifically, the coloring seasoning solution was prepared by adding the cocoa pigment powder obtained above to the saucer solution having the composition shown in Table 1 so as to have 0.5% by weight in terms of color value E ^{10% (500 nm)} = 130.

Composition of sauce liquid Compounding ingredient content Soy sauce (Yamamori specialty product, product of Yamamori Co., Ltd.) 45 wt% Sugar 20 wt% Mirin 5 wt% water 30 wt% Sum 100 wt%

The obtained colored seasoning solution was subjected to centrifugation treatment at 1000 rpm for 30 minutes, and it was confirmed that an insoluble matter was generated (Fig. 1). Further, 40 g of the obtained coloring seasoning liquid was immersed in 40 g of pork for 1 hour at 25 DEG C and boiled at 74 DEG C for 1 hour to cook pork, and as a result, the pork was found to have spots and the coloring was uneven 2). Thus, from this test result, it was confirmed that conventional cacao coloring can not be homogeneous and good coloring for foods having low pH and high salt concentration.

Test Example  1: Production and performance evaluation of cacao dye of the present invention (1)

1. Manufacture of cacao pigment

215 g of cacao husk was added to 3000 ml of an aqueous solution of sodium hydroxide having a pH of 13.17 or 12.96 and air (oxygen content: about 20 v / v%) was added while stirring at 50 DEG C The treatment was carried out for 5 hours. After the extraction treatment, the solid content in the extract was removed to obtain an extract. Subsequently, the obtained extract was subjected to a purification step under the same conditions as in Reference Test Example 1 to obtain a cacao dye powder. The amount of cacao dye powder obtained was 8.1 g in Comparative Example 1, 9.0 g in Example 1, 7.9 g in Example 2, 9.0 g in Example 3, and 5.7 g in Example 4.

2. Characterization of cacao pigment

The obtained cacao pigments were evaluated for acid retention, maintenance of salt retention, stability under low pH condition and stability under high salt concentration, and coloring characteristics (1) by the following methods.

(Maintenance rate of acid use)

Under the temperature condition of 5 占 폚, each cacao pigment obtained above was added to 10 ml of purified water containing 1% by weight of citric acid so as to have a color value E of ^{10% (500 nm)} = 0.1 and sufficiently stirred. Subsequently, it was allowed to stand under a temperature condition of 5 캜 for 24 hours. Thereafter, the mixture was subjected to centrifugation at 3000 rpm for 30 minutes to sediment the insolubles. Further, the dissolved cacao dye was diluted with a citric acid buffer solution of pH 7, and the concentration of the cacao dye was measured by a spectrophotometer (product of U-3310 HITACH). The ratio of the dissolved cacao pigment to the total amount of the added cacao pigment was calculated as the maintenance ratio (%) by the acidification.

(Salt retention rate)

Under the temperature condition of 5 占 폚, 10 ml of the purified water containing 10% by weight of sodium chloride was added with each cacao colorant obtained so as to have a color value E of ^{10% (500 nm)} = 0.1 and sufficiently stirred. Subsequently, it was allowed to stand under a temperature condition of 5 캜 for 24 hours. Thereafter, the mixture was subjected to centrifugation at 3000 rpm for 30 minutes to sediment the insolubles. Further, the dissolved cacao dye was diluted with a citric acid buffer solution of pH 7, and the concentration of the cacao dye was measured by a spectrophotometer (product of U-3310 HITACH). The ratio of the dissolved cacao pigment to the total amount of added cacao pigment was calculated as a salt retention ratio (%).

(Stability at low pH and high salt concentration)

Each of the cacao dyes obtained above was adjusted to purified water so as to have a color value E of ^{10% (500 nm)} = 130 to obtain a cacao-colored small liquid. The coloring seasoning solution was prepared by adding 0.5% by weight of each cacao-colored microcapsules to the seasoning solution (pH 4.8, salt content 7% by weight) having the composition shown in Table 1 above and mixing them. The resulting colored seasoning solution was subjected to centrifugation treatment at 1000 rpm for 10 minutes to confirm the presence or absence of the formation of insolubles.

(Coloring characteristics (1))

40 g of each of the coloring seasonings obtained above was immersed in 40 g of pork at 25 DEG C for 1 hour and boiled at 74 DEG C for 1 hour to cook pork. The appearance of the pork after cooking was observed, and evaluation was made with respect to the coloring state (presence or absence of spots) of the pork.

The obtained results are shown in Table 2. As a result of observing the state after centrifugation at the time of measuring the acid retention, the salt retention, and the acid / salt retention, the state after centrifugation of the colored seasoning added with each cacao dye was observed, The results of observation of the appearance of the pork cooked with the colored seasoning added with the added seasoning are shown in Fig.

From these results, it became clear that when the cacao husk is subjected to the extraction treatment with an alkaline aqueous solution, the cacao dye having an acid dissolution retention ratio of 60% or more and a salt retention ratio of 90% or more can be obtained by passing air (gas containing oxygen). It was also confirmed that each of the obtained cacao dyes was able to obtain occurrence of precipitation, spotting, coloring unevenness and the like even under a condition of low pH or high salt concentration.

Extraction condition Abuse
Retention rate
(%) Do it
Retention rate
(%) In a colored seasoning solution
Of
Insoluble cargo
Whether or not On pork
Of
Presence of spots
pH Aeration rate (vvm) Comparative Example 1 13.17 0 29.1 86.3 has exist has exist Example 1 13.17 0.25 82.4 94.3 none none Example 2 13.17 0.50 80.1 94.9 none none Example 3 13.17 1.00 90.5 96.8 none none Example 4 12.96 1.00 86.9 94.9 none none

Test Example  2: The cacao pigment of the present invention In manufacturing  Examination of kinds of alkali in extraction process

1. Manufacture of cacao pigment

The alkali shown in Table 3 was added to purified water so as to have the pH shown in Table 3 to prepare an alkaline aqueous solution. 10 g of cacao husks was added to 140 ml of each of the obtained alkaline aqueous solutions and extraction treatment was carried out for 5 hours while air (oxygen content: about 20 v / v%) was passed through at a temperature of 50 캜 with stirring at a rate of 0.25 vvm or more. After the extraction treatment, the solid content was removed to obtain an extract. Subsequently, the resulting extract was subjected to a purification step under the same conditions as in Reference Test Example 1 to obtain a cacao dye.

2. Characterization of cacao pigment

With respect to each of the obtained cacao pigments, the acid-dissolution retention and the salt retention were evaluated in the same manner as in Test Example 1.

The obtained results are shown in Table 3. From this result, regardless of the kind of alkali when the cacao husk is subjected to the extraction treatment with the alkaline aqueous solution, the air (oxygen-containing gas) is passed through during the extraction treatment, It was confirmed that a cacao coloring matter of 90% or more was obtained.

Extraction condition Abuse
Retention rate (%) Do it
Retention rate (%) The alkali used in the extraction process pH Example 5 Potassium hydroxide 12.59 90.0 91.5 Example 6 Sodium phosphate 12.35 93.0 96.4 Example 7 Sodium carbonate 11.57 63.2 97.3 Example 8 Sodium carbonate 13.02 90.5 93.7

Test Example  3: The cacao pigment of the present invention In manufacturing  Examination of temperature condition during extraction process

1. Manufacture of cacao pigment

10 g of cacao husks was added to 140 ml of an aqueous solution of sodium hydroxide having a pH of 13.17 and air (oxygen content: about 20 v / v%) was added to the mixture while stirring at 50 캜 or 15 캜, The treatment was carried out for 5 hours. After the extraction treatment, the solid content in the extract was removed to obtain an extract containing the cacao dye. Subsequently, the obtained extract was purified under the same conditions as in Test Example 1 to obtain a cacao dye.

2. Characterization of cacao pigment

With respect to each of the obtained cacao pigments, the acid-dissolution retention and the salt retention were evaluated in the same manner as in Test Example 1.

The obtained results are shown in Table 4. From these results, it was confirmed that the temperature at which the cacao husk was subjected to the extraction treatment with the aqueous alkaline solution had little effect on the acid retention retention and the salt retention retention of the finally obtained cacao pigment.

Temperature during extraction process Acid retention (%) Salt retention (%) Example 9 50 ℃ 85.0 93.9 Example 10 15 ℃ 86.4 93.8

Test Example  4: The cacao pigment of the present invention In manufacturing  Review of necessity of refining process

1. Manufacture of cacao pigment

10 g of cacao husks was added to 140 ml of an aqueous solution of sodium hydroxide having a pH of 13.17 and extraction treatment was carried out for 5 hours while passing air (oxygen content: about 20 v / v%) so that aeration rate was 0.25 vvm or more . After the extraction treatment, the solid content in the extract was removed, and an extract containing the cacao dye was obtained. Then, the obtained extract solution was concentrated to dryness and pulverized with induction to obtain a cacao dye powder.

2. Characterization of cacao pigment

With respect to each of the obtained cacao pigments, the acid-dissolution retention and the salt retention were evaluated in the same manner as in Test Example 1 above.

The obtained results are shown in Table 5. From these results, it was found that, even if the conventional purification process is not performed, the cacao husk is subjected to the extraction treatment using the alkaline aqueous solution and the oxygen supply treatment under the alkaline condition, It became clear that a pigment was obtained.

Acid retention (%) Salt retention (%) Example 11 82.8 91.2

Test Example  5: The cacao pigment of the present invention In manufacturing  Review of oxygen supply timing

1. Manufacture of cacao pigment

100 g of cacao husk was added to 2000 ml of aqueous sodium hydroxide solution having pH of 12.52 and extraction treatment was carried out for 2 hours while stirring at 80 캜. After the extraction treatment, the solid content was removed, and an extract containing the cacao pigment was obtained. After the obtained extract was concentrated, acetone was added and the pH was adjusted to 3 with hydrochloric acid. The mixture was allowed to stand at 5 占 폚 for 16 hours to precipitate impurities such as gum. Subsequently, the impurities were removed by filtration, the pH was adjusted to 10 with sodium hydroxide, and the solution was allowed to stand at 5 DEG C for 16 hours to precipitate a cacao dye component. The precipitated cacao dye was recovered and dissolved in water. Then, acetone was removed by concentration, and purified water was further added so that the color value was about 3% by weight in terms of E ^{( 10% ) (500 nm)} = 130 to obtain a purified cacao dye aqueous solution . Sodium hydroxide was added to the aqueous solution of the obtained purified cacao dye to adjust the pH to 12.56, and oxygen was supplied for 5 hours while passing air (oxygen content: about 20 v / v%) so as to have a flow rate of 0.5 vvm. After the oxygen supply treatment, the pH was adjusted to 7 with hydrochloric acid and the mixture was filtered. The filtrate was recovered and dried by spray drying to obtain 9 g of cacao dye powder.

2. Characterization of cacao pigment

Each of the obtained cacao dyes was evaluated in terms of acid dissolution retention, salting out retention, stability under low pH conditions and stability under high salt conditions, and coloring characteristics (1) in the same manner as in Test Example 1 above.

The obtained results are shown in Table 6. The results of observing the state after centrifugation of the colored seasoning added with the cacao dye and the appearance of the pork cooked with the colored seasoning added with the cacao dye are shown in Fig. This result shows that even when the cacao husk is subjected to the extraction treatment and the purification step using an alkaline aqueous solution and then subjected to the oxygen supply treatment under alkaline conditions, the cacao dye having an acid dissolution rate of 60% or more and a salt retention rate of 90% Can be obtained. It was also confirmed that the thus obtained cacao dye can inhibit the occurrence of precipitation, spots, coloring unevenness and the like even when used under conditions of low pH or high salt concentration.

Acid retention (%) Salt retention (%) Of the coloring seasoning solution
Presence or absence of insoluble cargo Presence or absence of pork Example 12 94.1 96.6 none none

Test Example  6: Production and performance evaluation of cacao pigment of the present invention (2)

1. Manufacture of cacao pigment

Extraction treatment of cacao pigment from cacao husks was carried out by the methods of extraction conditions 1 to 6 shown below to obtain an extract solution.

(Extraction condition 1)

100 g of cacao husk was added to 1400 ml of aqueous sodium hydroxide solution having pH of 12.12, and extraction treatment was carried out for 2 hours while stirring at 80 캜. On the other hand, during the extraction treatment, ventilation into the extraction solvent was not performed. After the extraction treatment, the solid content in the extract was removed, and an extract containing the cacao dye was obtained.

(Extraction condition 2)

Extraction treatment of cacao husk was carried out under the same conditions as in the above extraction condition 1, except that 4000 ml of an aqueous solution of sodium hydroxide having a pH of 12.73 was used as an extraction solvent. After the extraction treatment, the solid content in the extract was removed, and an extract containing the cacao dye was obtained.

(Extraction condition 3)

Extraction treatment of cacao husk was performed under the same conditions as in the above extraction condition 1, except that an aqueous sodium hydroxide solution having a pH of 12.73 was used as an extraction solvent. After the extraction treatment, the solid content in the extract was removed, and an extract containing the cacao dye was obtained.

(Extraction condition 4)

A commercially available cacao pigment (ChocoColor 610P: Glyco Nutrition Food Co., Ltd.) was used.

(Extraction condition 5)

Extraction treatment of cacao husks was carried out under the same condition as in the above extraction condition 3, except that cacao husks different from those used in extraction condition 3 were used. After the extraction treatment, the solid content in the extract was removed, and an extract containing the cacao dye was obtained.

(Extraction condition 6)

Extraction treatment of cacao husks was carried out under the same conditions as in the above extraction condition 3 except that cacao husks different from the cacao husks used in the extraction conditions 3 and 5 were used. After the extraction treatment, the solid content in the extract was removed, and an extract containing the cacao dye was obtained. The resulting extract was subjected to a purification step under the same conditions as in Reference Test Example 1 to obtain a cacao pigment. The amount of the obtained cacao colorant was 5.4 g in the extraction condition 1, 9.4 g in the extraction condition 2, 9.7 g in the extraction condition 3, 15.0 g in the extraction condition 5, and 11.8 g in the extraction condition 6.

Subsequently, each cacao pigment after purification was diluted with purified water so as to be 1% by weight in terms of color value E ^{10% (500 nm)} = 130 to prepare a cacao dye refined liquid. This cacao dye refined liquid was supplied to the adsorption resin treatment under the following conditions.

Adsorption resin A: Diaion HP20 (manufactured by Mitsubishi Chemical Corporation); Styrene resin, non-polar, pore radius 290 Å, specific surface area 590 m 2 / g

Amount of adsorbent resin A used: The column was packed so as to have a height of 24 cm on a column having an inner diameter of 2 cm.

Transmission condition: 60 ml of the cacao dye refining liquid was passed through under the condition that the space velocity (SV) was 0.3-0.6 / h. Thereafter, 80 ml of the washing liquid (ion-exchanged water) And 160 ml of a desalin solution (a 70% aqueous solution of ethanol (the pH adjusted to 3 with hydrochloric acid when it was difficult to desorb)) was passed at a space velocity (SV) of 0.8 to 1.2 / h.

The recovered portion (non-adsorbed portion) during the passage of the extract and the washing liquid was concentrated and dried, followed by pulverization by pulverization to obtain a cacao dye (Examples 13 to 18). Also, the recovered portions (adsorbed portions) during the passage of the desorption liquid were subjected to drying treatment in the same manner to obtain cacao pigments (Comparative Examples 2, 4, 6, 8, 10 and 12). Furthermore, the extract solution was also obtained for the cacao pigments (Comparative Examples 3, 5, 7, 9, 11 and 13) which were dried by the same method without providing the adsorbent resin treatment.

2. Characterization of cacao pigment

Each of the obtained cacao dyes was evaluated in terms of acid dissolution retention, salting out retention, stability under low pH conditions and stability under high salt conditions, and coloring characteristics (1) in the same manner as in Test Example 1 above. Further, for each of the obtained cacao pigments, the acid / salt retention and the coloring characteristics (2) were evaluated by the following methods.

(Acid / salt retention rate)

The cocoa pigment obtained above was added to 10 ml of purified water containing 1% by weight of citric acid and 10% by weight of sodium chloride under a temperature condition of 25 占 폚 to give a color value E of ^{10% (500 nm)} = 0.1 and sufficiently stirred. Subsequently, it was allowed to stand under a temperature condition of 5 캜 for 24 hours. Thereafter, the mixture was subjected to centrifugation at 3000 rpm for 30 minutes to sediment the insolubles. Further, the dissolved cacao dye was diluted with a citric acid buffer solution of pH 7, and the concentration of the cacao dye was measured by a spectrophotometer (product of U-3310 HITACH). The ratio of the dissolved cacao pigment to the total amount of added cacao pigment was calculated as acid / salt retention ratio (%).

(Coloring property 2)

One boiled egg was immersed in the colored seasoning solution (coloring seasoning solution to which the cocoa pigment of Example 13 was added) prepared at the time of evaluation of the coloring characteristics (1) at 25 캜 for 2 hours to prepare egg planting. Then, the egg stew was taken out and immersed in 50 g of ion exchange water at 25 ° C for 24 hours. Before and after the immersion of the ion exchange water, the coloring state of the egg planting was observed.

For comparison, preparations of egg planting and immersion of ion-exchanged water were carried out under the same conditions as above using commercially available caramel colorants (caramel colorants 1 and 2) instead of the cacao colorant of Example 13, The coloring state of the stewed egg was observed. On the other hand, the addition amount of the caramel coloring to the coloring seasoning solution was adjusted to such an amount that the same color value as that of the cacao pigment was obtained.

The obtained results are shown in Table 7. Fig. 5 shows the result of observing the state after centrifugation at the time of measuring the acid-dissolution retention and the salt retention. 6 shows the result of observing the state after centrifugation in measuring the acid / salt solution retention ratio. Fig. 7 shows the result of observing the state after centrifugation of the colored seasoning added with each cacao dye. The appearance of the pork cooked with the colored seasoning added with the cocoa pigment of Example 13 and Comparative Examples 2 to 3 was observed, and the results are shown in Fig. Fig. 9 shows the results of observing the state before and after the immersion of the ion-exchanged water in the preparation of the egg prepared using the colored seasoning added with the cocoa pigment of Example 11 or a commercial caramel coloring agent.

As apparent from these results, in the cacao dye (Examples 13 to 18) recovered from the portion that was not adsorbed on the adsorbent resin, (1) the acid retention ratio of 60% or more, and (2) And a salt retention rate of 80% or more. In addition, in the cacao dye of Examples 17 and 18, the acid / salt solution retention ratio was 20% or more (on the other hand, the acid / salt solution retention ratio was not measured for the cacao dye of Examples 13 to 16). In addition, in the cacao colorants of Examples 13 to 18, insoluble matter was suppressed in the colored seasoning with acidity and high salt concentration, and the dissolved state of the cacao pigment was stably maintained. Moreover, when the pork was cooked using the colored seasoning solution to which the cocoa pigment of Examples 13 to 18 was added, it was possible to uniformly color the pork without generating spots.

On the other hand, in the case of the cacao dye (Comparative Examples 1, 3, 5, 7 and 9) recovered from the portion not adsorbed by the adsorption resin, the acid dissolution retention was less than 15%. In the colored seasoning solution containing the cacao dye, The generation of cargo was recognized, and the cacao pigment could not be maintained in a dissolved state. Further, when the pork was cooked using the colored seasoning solution to which the cocoa pigment (Comparative Examples 2, 4, 6, 8, 10 and 12) had been added, the pork was spotted and the coloring became uneven. Furthermore, even in the cacao pigments (Comparative Examples 3, 5, 7, 9, 11 and 13) obtained from the extract obtained by extracting cacao husks with an aqueous solution of sodium hydroxide, the acid retention ratio was low and the coloring seasoning liquid containing the cacao pigment The production of insoluble cargo was recognized. Moreover, when the pork was cooked using the coloring seasoning liquid to which the cacao pigment was added, the pork was spotted.

In addition, when the prepared seasoning liquid containing the cocoa pigment of Example 13 was used to prepare an egg planted preparation, dark coloration as in smoked was recognized, and even when dipped in ion-exchanged water, there was no discoloration and a dark coloring state was maintained I could. On the other hand, in the preparation of an egg prepared using a coloring seasoning solution to which a caramel coloring matter was added, no sufficient deep coloration was observed, and furthermore, when immersed in ion-exchanged water,

From the above results, it can be seen that (1) the acid dissolution rate is 60% or more, (2) the acid dissolution rate is 40% or more and the salt dissolution rate is 80% or more, and / or (3) It has become clear that the use of a coloring matter suppresses the occurrence of precipitation, spots, staining and the like even under a low pH condition or a high salt concentration condition, thereby enabling uniform coloring.

Manufacturing conditions Abuse
Retention rate
(%) Do it
Retention rate
(%) mountain/
Do it
Retention rate
(%) Presence or absence of insoluble content in colored seasoning solution In pork
Presence of spots Extraction condition Collection part ^{# 1} by adsorption resin treatment Example 13
Extraction condition 1
The non-adsorbed portion (42.0%) 61.1 72.4 - none none Comparative Example 2 Adsorption part (31.8%) 9.3 46.9 - has exist has exist Comparative Example 3 No adsorption resin treatment 17.9 93.0 - has exist has exist Example 14
Extraction condition 2
Unsorbed portion (39.7%) 62.8 94.1 - none none Comparative Example 4 Adsorption part (55.3%) 13.9 62.9 - has exist has exist Comparative Example 5 No adsorption resin treatment 24.5 88.8 - has exist has exist Example 15
Extraction condition 3
The non-adsorbed portion (44.4%) 82.4 87.5 - none none Comparative Example 6 Adsorption part (36.7%) 3.6 65.0 - has exist has exist Comparative Example 7 No adsorption resin treatment 26.2 71.7 - has exist has exist Example 16
Extraction Condition 4
The non-adsorbed portion (34.7%) 83.8 83.7 - none none Comparative Example 8 Adsorption part (50.4%) 12.2 81.3 - has exist has exist Comparative Example 9 No adsorption resin treatment 6.2 73.5 - has exist has exist Example 17
Extraction Condition 5
The non-adsorbed portion (44.0%) 81.6 92.2 34.2 none none Comparative Example 10 Adsorption part (40.8%) 2.8 93.0 1.8 has exist has exist Comparative Example 11 No adsorption resin treatment 20.4 92.1 15.0 has exist has exist Example 18
Extraction condition 6
The non-adsorbed portion (46.6%) 83.9 92.4 40.1 none none Comparative Example 12 Adsorption part (38.4%) 4.3 91.7 2.7 has exist has exist Comparative Example 13 No adsorption resin treatment 21.1 93.2 15.2 has exist has exist

The percentage (%) described in the parentheses in the column of the recovery part by the # 1 adsorbent resin treatment represents the recovery rate of the cacao pigment in each part when the amount of the cacao color before the resin treatment is taken as 100%.

Test Example  7: The cacao pigment of the present invention In manufacturing Adsorption resin treatment  And ion exchange resin treatment

1. Manufacture of cacao pigment

Extraction treatment of cacao husk was carried out under the same conditions as the extraction condition 3 or 5 in Test Example 6. [ After the extraction treatment, the solid content in the extract was removed, and an extract containing the cacao dye was obtained. Thereafter, the extract was purified under the same conditions as in Test Example 6 to obtain a cacao dye refined liquid. Subsequently, each resin of the obtained cacao dye refined liquid was passed through under the same conditions as in Test Example 6, except that the following adsorbent resins B, C and cation exchange resins A were used in place of the adsorbent resin A:

Adsorbent resin B: Amberlite XAD1180N (manufactured by Rohm and Haas); Styrene type resin, pore radius of 250 Å, specific surface area of 620 m 2 / g

Adsorption resin C: Amberlite HXAD7HP (manufactured by Rohm and Haas); Acrylic resin, pore radius 50 Å, specific surface area 500 m 2 / g

Cation exchange resin A: Amberlite 200CT (from Rohm and Haas); Functional group -SO ₃ M, pore radius 50 Å

The recovered portion (non-adsorbed portion) during the passage of the extract and the washing liquid was concentrated to dryness and pulverized by pulverization to obtain a cacao dye (Examples 17 to 20). Also, the recovered portion (adsorbed portion) during the passage of the desorption liquid was subjected to drying treatment in the same manner to obtain cacao pigments (Comparative Examples 14, 16 and 18). Further, the extract solution was also passed through cyanine dyes (Comparative Examples 15, 17, 19 and 20) which had been dried by the same method without passing through the resin.

2. Characterization of cacao pigment

With respect to each of the obtained cacao dyes, the stability and the coloring characteristics (1) of the acid dissolution retention, the salt retention, the acid / salt retention, the stability under the low pH condition and the high salt condition, Respectively.

The obtained results are shown in Table 8. Fig. 10 shows the results of observing the state after centrifugation in measuring the acid-solution retention, the salt retention, and the acid / salt retention. Fig. 11 shows the result of observing the state of the colored seasoning added with each cacao dye after centrifugation.

From these results, it was confirmed that the cacao dye recovered from the adsorbed portion of the adsorbent resin had (1) an acid dissolution retention rate of 60% or more, (2) the acid-dissolution retention ratio of 40% or more and the salt retention ratio of 80% or more, and / or (3) the acid / salt retention ratio of 20% or more. It was also confirmed that the cacao pigment recovered from the portion adsorbed on the cation exchange resin could satisfy the above characteristics even when the extract liquid subjected to the extraction treatment with the alkaline aqueous solution was provided in the cation exchange resin treatment. (2) the acid-dissolution retention ratio is 40% or more and the salt retention ratio is 80% or more; and / or (3) the acid / salt retention ratio is It was confirmed that the occurrence of precipitation, spotting, coloring unevenness, and the like can be suppressed even when the cacao colorant having 20% or more is used under a low pH condition or a high salt concentration condition, and the food can be uniformly colored.

Manufacturing conditions Acid dissolution rate
(%) Do it
Retention rate
(%) mountain/
Do it
Retention rate
(%) Presence or absence of insoluble content in colored seasoning solution Pork
Presence or absence of spots in Extraction condition Type of resin used In adsorbent resin treatment
Recall part ^{# 1 by} Example 19 extraction
Condition
3 absorption
Resin B The non-adsorbed portion (42.8%) 82.4 89.9 - none none Comparative Example 14 Adsorption section (26.7%) 3.6 66.0 - has exist has exist Comparative Example 15 No adsorption resin treatment 26.2 71.7 - has exist has exist Example 20 extraction
Condition
5 absorption
Resin B The non-adsorbed portion (50.9%) 71.7 92.2 35.9 none none Comparative Example 16 Adsorption portion (31.2%) 4.3 88.6 15.0 has exist has exist Comparative Example 17 No adsorption resin treatment 20.4 92.1 2.6 has exist has exist Example 21 extraction
Condition
3 absorption
Resin C The non-adsorbed portion (39.5%) 46.7 89.7 - none none Comparative Example 18 Adsorption section (35.1%) 7.2 83.0 - has exist has exist Comparative Example 19 No adsorption resin treatment 26.2 71.7 - has exist has exist Example 22 extraction
Condition
3 Cation
exchange
Resin A The non-adsorbed portion (32.8%) 72.2 99.4 - none none Comparative Example 20 No adsorption resin treatment 26.2 71.7 - has exist has exist

The percentage (%) described in the parentheses in the column of the recovery part by the # 1 adsorbent resin treatment represents the recovery rate of the cacao pigment in each part when the amount of the cacao color before the resin treatment is taken as 100%.

Test Example  8: Dark brown  To Brown  Preparation and performance evaluation of pigments

One. Dark brown  To Brown  Manufacture of pigments

(Cacao coloring)

100 g of cacao husks was added to 2000 ml of aqueous sodium hydroxide solution having a pH of 12.30, and extraction treatment was carried out for 2 hours while stirring at 80 캜. After the extraction treatment, the solid content was removed, and an extract containing the cacao pigment was obtained. After the obtained extract was concentrated, acetone was added to adjust the pH to 3 with hydrochloric acid, and the mixture was allowed to stand at 5 占 폚 for 16 hours to precipitate impurities such as gum. Subsequently, the impurities were removed by filtration, the pH was adjusted to 10 with sodium hydroxide, and the mixture was allowed to stand at 5 占 폚 for 16 hours to precipitate a cacao dye component. The precipitated cacao dye was recovered and dissolved in water. Then, acetone was removed by concentration, and purified water was further added to give a color value E of ^{10% (500 nm)} = 1.6 to obtain a purified cacao dye aqueous solution. To the 200 ml of the obtained purified cacao dye aqueous solution was added 30% by weight aqueous sodium hydroxide solution to adjust the pH to 13. The air (oxygen content: about 20 v / v%) was added so as to have a flow rate of 0.5 vvm with stirring while being kept at 50 캜 And the oxygen supply treatment was performed for 24 hours by ventilation. Hydrochloric acid was added to the aqueous solution of purified cacao dye before the oxygen supply treatment and after 24 hours of the oxygen supply treatment to adjust the pH to 7, and then the solution was filtered to recover the filtrate and dried by spray drying to obtain a cacao pigment powder.

(Tamarind coloring matter)

^{(500 nm)} = 1.6 with respect to the tamarind coloring matter of the commercially available product (the one in the standard described in "Fourth edition original additive volatile standard" (issued by Japan Food Additives Association on Oct. 13, 2008) To obtain a purified tamarind pigment aqueous solution. The obtained purified tamarind dye aqueous solution was subjected to oxygen supply treatment under the same conditions as the aqueous solution of the purified cacao dye to obtain a tamarind pigment powder.

(Onion coloring)

Purified water is added so that the color value E is ^{10% (500 nm)} = 1.6 with respect to the commercially available onion coloring matter (the one in the standard described in "Fourth edition original additive volatile standard" (issued by Japan Food Additives Association on Oct. 13, 2008) To obtain a purified aqueous solution of onion dye. The resulting purified onion dye aqueous solution was subjected to an oxygen supply treatment under the same conditions as the aqueous solution of the purified cacao dye to obtain an onion dye powder.

(High pigment)

^{(500 nm)} = 1.6 with respect to the high-color pigment of the commercial product (the one in the standard described in "Fourth edition edition of the additive self-standard" (issued by Japan Food Additives Association on Oct. 13, 2008 ⁾ To obtain an aqueous solution of a purified high-pigment dye. Oxygen supply processing was performed on the resulting purified high-chroma dye aqueous solution under the same conditions as the aqueous solution of the purified cacao dye to obtain a high-color pigment powder.

2. Dark brown system Brown  Characterization of pigment

Each of the resulting brown to brown dyes was evaluated in terms of acid dissolution retention and salt dissolution retention by the same method as in Test Example 1 above.

The results obtained are shown in Table 9. Fig. 12 shows the result of observing the state after centrifugation at the time of measurement of the acid-dissolution retention and the saline solution retention. As a result, not only the cocoa pigment but also the brown to brown pigments such as tamarind pigments, onion pigments and high color pigments can be subjected to the oxygen supply treatment under the alkaline condition, so that the acid retention ratio is 40% It is clear that a brown to brown pigment having a retention rate of 80% or more can be obtained.

Acid retention (%) Salt retention (%) Cacao pigment
Example 23 (after 24 hours of oxygen supply treatment) 59.6 95.1 Comparative Example 21 (before oxygen supply treatment) 3.7 79.8 Tamarind pigment
Example 24 (after 24 hours of oxygen supply treatment) 96.5 95.5 Comparative Example 22 (before oxygen supply treatment) 33.1 98.6 Onion color
Example 25 (after 24 hours of oxygen supply treatment) 80.2 96.8 Comparative Example 23 (before oxygen supply treatment) 77.9 46.9 High pigment
Example 26 (after 24 hours of oxygen supply treatment) 63.4 93.8 Comparative Example 24 (before oxygen supply treatment) 1.8 1.1

Test Example  9: Cacao coloring Acidic beverage  Evaluation of stability in

A commercially available carbonated beverage ("Mitsuya Cider", product of Asahi Beverage Co., Ltd., containing fructose glucose liquid sugar, sugar, flavor, acidulant) was adjusted to pH 2.5 with citric acid to obtain an acidic drink. Subsequently, the cacao colorant, commercial cacao colorant (ChocoColor 610P, manufactured by Glyco Nutrition Food Co., Ltd.) or commercially available caramel colorants (caramel colorants 1 and 2) obtained in Example 3 was adjusted to have a color value E ^{10% (500 nm)} = 270 The pigment solution dissolved in purified water was added to the acidic beverage so as to have a concentration of 0.05% by weight. The acidic beverage to which each pigment was added was allowed to stand at 5 占 폚 for 72 hours under a wide range of 24000 lux, and color fading was visually confirmed. Further, the acidic beverages before and after the wide range were measured for absorbance at 500 nm, and the residual percentage (%) of the coloring matter was calculated according to the following formula.

[Equation 1]

(%) = (Absorbance after wide width / absorbance before wide width) 占 100

Table 10 shows the results of the residual coloring ratios. Fig. 13 shows the results of observing the appearance of the acidic beverage before and after wide-angle heating. As a result, in the caramel coloring matter of the current product, precipitation was observed in the acidic beverage, and in the caramel coloring matter, sedimentation was not recognized, but remarkable discoloration of the coloring matter was recognized by the wide range. On the other hand, in the case of the cacao dye obtained in Example 3, precipitation did not occur, and fading due to the wide width was further suppressed.

Colorant remaining ratio (%) The cocoa pigment obtained in Example 3 - Commercial cacao pigment 91.0 Caramel coloring 1 23.0 Caramel coloring 2 43.3

Test Example  10: Evaluation of foamability and foam stability of cacao pigment

The temperature at the extraction treatment was changed to 50 DEG C, the oxygen supply processing time was changed to 26 hours, and sodium hydroxide was added to the purified cacao dye aqueous solution to adjust the pH to 12.63 , A cacao dye powder (Example 27) was prepared under the same conditions as in Example 12. [

Separately, 21 g of citric acid was weighed and dissolved by adding water, and the total amount was adjusted to 1000 ml to obtain a first solution. Further, 71.6 g of disodium phosphate was weighed and dissolved by adding water, and the total amount was adjusted to 1000 ml to obtain a second solution. A proper amount of the first solution and the second solution was mixed to prepare a buffer solution of pH 3, pH 4, and pH 5. Subsequently, the cacao pigment powder obtained above was dissolved in a buffer solution having a color value E of ^{10% (500 nm)} = 70 in terms of a solution of 70, and 10 ml of the cacao pigment powder was placed in a 15 ml capacity tube. . The bubbles immediately afterwards were confirmed.

The obtained results are shown in Fig. As is clear from Fig. 14, bubbles were observed in any of the buffers at pH 3, pH 4, and pH 5. Particularly, it was confirmed that bubbles were remarkably produced in the range of pH 3 to 4, which is a general pH in an alcoholic beverage having no beer flavor, and it was confirmed to be useful as a foaming agent in beer flavored nonalcoholic beverages.

Test Example  11: Evaluation of foamability and foam stability of cacao pigment

1. Manufacture of cacao pigment

The cacao pigment powder obtained in Examples 2, 12 and 27 and the safflower in the specification of caramel I described in the &quot; eighth edition of the Food Additives Processing Division, Ministry of Health, Labor & Welfare Reprinted Edition &quot; (Japan Food Additives Association, issued on Aug. 31, 2007) Caramel color. Separately, cacao dye powder (Examples 28 to 30) was prepared in the following manner.

(Examples 28 to 30)

100 g of cacao husk was added to 2000 ml of an aqueous sodium hydroxide solution having a pH of 12.52 and extraction treatment was carried out for 2 hours while stirring at 80 캜. After the extraction treatment, the solid content was removed, and an extract containing the cacao pigment was obtained. After the obtained extract was concentrated, acetone was added, the pH was adjusted to 3 with hydrochloric acid, and the mixture was allowed to stand at 5 占 폚 for 16 hours to precipitate impurities such as gum. Subsequently, the impurities were removed by filtration, the pH was adjusted to 10 with sodium hydroxide, and the mixture was allowed to stand at 5 占 폚 for 16 hours to precipitate a cacao dye component. The precipitated cacao dye was recovered and dissolved in water. Then, acetone was removed by concentration, and purified water was further added thereto so as to have a color value of about 1% by weight in terms of E ^{10% (500 nm)} = 130 to obtain a purified cacao dye aqueous solution .

This cacao dye refined liquid was provided for the adsorption resin treatment under the following conditions.

Adsorption resin A: Diaion HP20 (manufactured by Mitsubishi Chemical Corporation); Styrene resin, non-polar, pore radius 290 Å, specific surface area 590 m 2 / g

Cation exchange resin A: Urbanite 200CT (from Rohm and Haas); Functional group -SO ₃ M, pore radius 50 Å

Adsorbent resin B: Amberlite XAD1180N (manufactured by Rohm and Haas); Styrene type resin, pore radius of 250 Å, specific surface area of 620 m 2 / g

Amount of resin used: A column having an inner diameter of 2 cm was filled with a height of 24 cm.

Transmissive condition: 50 ml of the cacao dye refining liquid was passed through under the condition that the space velocity (SV) was 0.3-0.6 / h, and then 80 ml of the washing liquid (ion-exchanged water) was added under the condition that the space velocity (SV) And 160 ml of a desalin solution (a 70% by volume aqueous ethanol solution (in the case of difficulty in desorption, the pH adjusted to 3 with hydrochloric acid)) was passed through under conditions such that the space velocity (SV) was 0.8 to 1.2 / h.

The recovered portion (non-adsorbed portion) during the passing of the extract and the washing liquid was recovered to obtain a cacao dye solution. A cacao dye (7.4 g, E ^{10% (500 nm)} = 2.59) obtained by treating the cacao dye (16.3 g, E ^{10% (500 nm)} = 0.99) obtained by treating with the adsorption resin A with the cation exchange resin A of Example 28, (18.1 g, E ^{10% (500 nm)} = 0.85) obtained in Example 29 and the adsorbent resin B was used as Example 30.

2. Characteristic evaluation of each pigment (1)

With respect to each of the cacao pigments, the acid-dissolution retention and the salt retention were evaluated in the same manner as in Test Example 1 above.

The foams and foam stability were evaluated for each pigment by the following methods. First, 21 g of citric acid was weighed and dissolved by adding water, and the total amount was adjusted to 1000 ml to obtain a first solution. Further, 71.6 g of disodium phosphate was weighed and dissolved by adding water, and the total amount was adjusted to 1000 ml to obtain a second solution. An appropriate amount of the first solution and the second solution was mixed to prepare a buffer solution of pH 3.5. Then, the cacao dye solution obtained above was dissolved in the obtained buffer solution so as to have a color value E of ^{10% (500 nm)} = 100 in terms of a solution of 100, and a 100 ml volume graduated cylinder (product of Cherry Co., inner diameter: 2.9 cm, height : 25 cm), and the hands were vibrated up and down 20 times at the same time. The volume of the foam immediately after and 5 minutes after the vibration was read from the scale of the measuring cylinder and measured. For each dye, this experiment was performed three times.

The obtained results are shown in Table 11 and Fig. From these results, it was confirmed that the cocoa pigments of Examples 2, 12, and 27 to 30 all had excellent foamability and foam stability.

Abuse
Retention rate (%) Do it
Retention rate (%) First (foam volume) Second (foam volume) 3rd (foam volume) vibration
Immediately after (mL) 5 minutes later
(mL) vibration
Immediately after (mL) 5 minutes later
(mL) vibration
Immediately after (mL) 5 minutes later
(mL) Caramel color - - 8 5 8 5 8 4.5 Example 2 80.1 94.9 7 6 7 6 7 6 Example 12 94.1 96.6 15 10 15 10 13 8 Example 27 91.2 94.7 15 12 15 12 13 11 Example 28 46.1 85.1 10 5 10 5 9 4.5 Example 29 85.3 86.1 8 5 8 5 8 5 Example 30 50.7 87.6 12 7 11 7 10 6

3. Characteristic evaluation of each pigment (2)

For each pigment, foaming and foam stability were evaluated in the following manner. First, 21 g of citric acid was weighed and dissolved by adding water, and the total amount was adjusted to 1000 ml to obtain a first solution. Further, 71.6 g of disodium phosphate was weighed and dissolved by adding water, and the total amount was adjusted to 1000 ml to obtain a second solution. A proper amount of the first solution and the second solution was mixed to prepare a buffer solution of pH 3.5. Then, the cacao dye powder obtained above was dissolved in the obtained buffer solution so as to have a color value E of ^{10% (500 nm)} = 100 in terms of a solution, and a test tube with a cap of 15 ml capacity (manufactured by Nichiden Rikashishi Co., Inner diameter: 1.2 cm, height: 15 cm), and the hands were simultaneously vibrated up and down 100 times in total. The state of the foam was confirmed immediately after the vibration, 5 minutes, 10 minutes, 20 minutes, 30 minutes, and 60 minutes, and the height of the foam was measured. The height of the foam was measured by using a reference scale (10 mm) of a color correction color Casmatch (manufactured by Bear Medical Co., Ltd.). Further, the height of the foam immediately after the vibration was taken as 100%, and the ratio of the height of the foam after the vibration was calculated as the foam retention (%).

The obtained results are shown in Table 12 and Fig. From these results, it was also confirmed that the cacao pigments of Examples 2, 12, and 27 to 30 had foamability and foam stability obtained. In particular, the cocoa dyes of Examples 2, 12, and 27 to 30 were able to maintain bubbles even after 20 minutes of vibration, and had excellent foam stability as compared with caramel dyes known to have foam stability.

vibration
Immediately After vibration 5 minutes later After 10 minutes After 20 minutes 30 minutes later After 60 minutes Caramel color 0.18 0.14 (77.8) 0.13 (72.2) 0 (0.0) 0 (0.0) 0 (0.0) Example 2 0.76 0.68 (89.5) 0.60 (78.9) 0.58 (76.3) 0.57 (75.0) 0.50 (65.8) Example 12 1.43 0.91 (63.6) 0.74 (51.7) 0.56 (39.2) 0.40 (28.0) 0.21 (14.7) Example 27 1.50 1.50 (100.0) 1.45 (96.7) 1.39 (92.7) 1.33 (88.7) 1.26 (84.0) Example 28 0.62 0.62 (100.0) 0.63 (101.6) 0.63 (101.6) 0.60 (96.8) 0.56 (90.3) Example 29 0.48 0.46 (95.8) 0.46 (95.8) 0.46 (95.8) 0.42 (87.5) 0.39 (81.3) Example 30 0.68 0.70 (102.9) 0.67 (98.5) 0.56 (82.4) 0.53 (77.9) 0.49 (72.1)

The values outside the parentheses in the table are the height of the foam (unit: cm), and the value in parentheses is the bubble retention rate (unit:%).

Test Example  12: Dark brown  To Brown  Evaluation of foamability and foam stability of pigment

1. Dark brown system Brown  Manufacture of pigments

(Cacao coloring)

100 g of cacao husks was added to 2000 ml of aqueous sodium hydroxide solution of pH 12.30 and extraction treatment was carried out for 2 hours with stirring at 80 캜. After the extraction treatment, the solid content was removed, and an extract containing the cacao pigment was obtained. After the obtained extract was concentrated, acetone was added to adjust the pH to 3 with hydrochloric acid, and the mixture was allowed to stand at 5 占 폚 for 16 hours to precipitate impurities such as gum. Subsequently, the impurities were removed by filtration, the pH was adjusted to 10 with sodium hydroxide, and the mixture was allowed to stand at 5 占 폚 for 16 hours to precipitate a cacao dye component. The precipitated cacao dye was recovered and dissolved in water. Then, acetone was removed by concentration, and purified water was further added to obtain a color value E of ^{10% (500 nm)} = 7.5 to obtain a purified cacao dye aqueous solution.

The obtained purified cacao dye aqueous solution was adjusted to pH 13 by adding a 30 wt% sodium hydroxide solution to 200 ml, and air (oxygen content: about 20 v / v%) was added thereto while stirring at a temperature of 50 캜, The oxygen supply process was performed for 6 hours. After 6 hours, the pH was adjusted to 7 with 30% by weight hydrochloric acid aqueous solution, and the filtrate was recovered by filtration to obtain a cacao liquid. The color value E ^{10% (500 nm)} at this time was 2.88.

(Onion coloring)

Added to purified water so that the onion color of the commercial product (in the standard described in "Fourth edition original additive volatile standard" (issued by Japan Food Additives Association on Oct. 13, 2008) was ^{10% (500 nm)} To obtain a purified onion dye aqueous solution. The resulting purified onion dye aqueous solution was subjected to an oxygen supply treatment under the same conditions as the aqueous solution of the purified cacao dye to obtain an onion coloring matter test solution (color value E ^{10% (500 nm)} = 2.76).

(High pigment)

Added to purified water in such a manner that the colorant E ^{10% (500 nm)} = 7.5, a high-color pigment of a commercially available product (the one in the standard described in "Fourth edition edition of the additive volatile standard" issued by Japan Food Additives Association on Oct. 13, 2008) To obtain a purified high-purity dye aqueous solution. Oxygen supply treatment was performed on the resulting purified high-chroma dye aqueous solution under the same conditions as the aqueous solution of the purified cacao dye to obtain a high color dye solution (color value E ^{10% (500 nm)} = 2.36).

2. Characterization of each pigment

Each coloring matter test liquid was dried to obtain a coloring matter powder. With respect to this coloring matter powder, the acid-dissolution retention and the saline solution retention were evaluated in the same manner as in Test Example 1 above.

In addition, foamability and foam stability were evaluated by the following method using each coloring matter test liquid. First, 21 g of citric acid was weighed and dissolved by adding water, and the total amount was adjusted to 1000 ml to obtain a first solution. Further, 71.6 g of disodium phosphate was weighed and dissolved by adding water, and the total amount was adjusted to 1000 ml to obtain a second solution. A proper amount of the first solution and the second solution was mixed to prepare a buffer solution of pH 3.5. Then, each coloring matter test liquid was added to the obtained buffer solution so that the color value became ^{10% (500 nm)} = 100 in terms of a solution of color value E of ^10% , and a test tube having a cap capacity of 15 ml (manufactured by Nichiden Rika Shoshiki Co., : 1.2 cm, height: 15 cm), and the hands were simultaneously vibrated up and down 100 times in total. The state of the bubbles was confirmed immediately after the vibration, after 5 minutes, 30 minutes, and 60 minutes. For comparison, the commercial caramel color within the specification of caramel I described in the &quot; Reprinted version of the eighth edition of the Food Additive Processing Regulations of the Ministry of Health, Labor & Welfare &quot; (Japan Food Additives Association, issued on August 31, 2007) .

The obtained results are shown in Table 13 and Fig. From this result, it has become clear that not only cacao coloring but also onion coloring and high coloring coloring can be provided to the oxygen supplying treatment under alkaline conditions, thereby providing excellent foamability and foam stability.

Acid retention (%) Salt retention (%) Example 31 (cocoa pigment) 72.4 91.3 Example 32 (onion pigment) 81.2 92.4 Example 33 (high coloring matter) 65.6 92.5

Test Example  13: Evaluation of the relationship between concentration of cacao pigment and foamability

Using the cacao pigment powder obtained in Example 27, the relationship between the concentration of the cacao pigment and the foaming property was evaluated by the following method.

Separately, 21 g of citric acid was weighed and dissolved by adding water, and the total amount was adjusted to 1000 ml to obtain a first solution. Further, 71.6 g of disodium phosphate was weighed and dissolved by adding water, and the total amount was adjusted to 1000 ml to obtain a second solution. A proper amount of the first solution and the second solution was mixed to prepare a buffer solution of pH 3.5. Then, the cocoa colorant powder obtained in Example 27 was dissolved in the obtained buffer solution so as to be 0.001% by weight, 0.01% by weight, 0.1% by weight and 1% by weight in terms of solution of color value E ^{10% (500 nm)} . Subsequently, 5 ml of each dye solution was added to a test tube (manufactured by Nichiden Rikashishi Co., Ltd., inner diameter: 1.2 cm, height: 15 cm) having a cap of 15 ml capacity, and simultaneously vibration was made by hand up and down 100 times in total. And the state of bubble generation immediately after the vibration was confirmed. The same test was carried out using a buffer solution of pH 3.5 without a cacao dye powder as a control.

The obtained results are shown in Fig. From these results, it was found that when the cacao colorant powder obtained in Example 27 had a concentration of 0.001% by weight or more, the foamability was recognized, and when the concentration was 0.01% by weight or more, particularly 0.1% by weight or more, remarkably excellent foamability was recognized.

Claims (18)

A brownish or brownish coloring matter having at least one of the following characteristics (i) to (iii):
(i) citric acid is added to the dye solution obtained by dissolving a pigment of a brown to brown color system in water such that the color value E is ^{10% (500 nm)} = 0.1, so that 60% Or more.
(ii) citric acid is added to the dye solution obtained by dissolving the pigment of the brown to brown type in water such that the color value E is ^{10% (500 nm)} = 0.1, so that 40% Of sodium chloride is added so as to be 10% by weight to the coloring matter solution in which the pigment is dissolved in water so as to maintain the state in which the pigment is dissolved in water to obtain a color value E of ^{10% (500 nm)} = 0.1. More than 80% of the brown pigment remains dissolved.
(iii) When 1 wt% of citric acid and 10 wt% of sodium chloride are added to a coloring solution obtained by dissolving a coloring agent of a brown to brown color system in water such that the color value E is ^{10% (500 nm)} = 0.1, 20% or more of the dye in the system remains dissolved. The method according to claim 1,
A brownish or brownish coloring matter having at least two of the above characteristics (i) to (iii). 3. The method according to claim 1 or 2,
Wherein the coloring agent is at least one colorant selected from the group consisting of cocoa pigment, high color pigment, onion colorant and tamarind colorant. 4. The method according to any one of claims 1 to 3,
A brown to brown coloring matter which is used for coloring a food or drink having a pH of 2 to 6 and / or a salt concentration of 1 to 30% by weight. A coloring agent for seasoning ornamental plants containing the pigment of the brown to brown type according to any one of claims 1 to 4. A seasoning paste containing the pigment of brown to brown type according to any one of claims 1 to 4. A foaming agent or foam stabilizer for a foamable beverage containing a pigment of a brownish to brownish color according to any one of claims 1 to 4. The effervescent drink containing the pigment of the brown to brown type according to any one of claims 1 to 4. Use of the brown to brown pigment according to any one of claims 1 to 4 for the coloring of seasonings. Use of the brownish or brownish coloring matter according to any one of claims 1 to 4 as foaming agent or foam stabilizer in a foamable beverage. Use for coloring an effervescent beverage of a brown to brown color pigment according to any one of claims 1 to 4. A method for producing a pigment from brown to brown based on which a dye solution of a brown to brown color system is obtained by supplying an oxygen gas under a alkaline condition to a pigment of a brown to brown color system. 13. The method of claim 12,
Wherein the oxygen source gas is supplied under alkaline conditions to a plant raw material containing a pigment of a brown to brown type. The method according to claim 12 or 13,
And supplying air as the oxygen gas. 15. The method according to any one of claims 12 to 14,
Wherein the supply rate of the oxygen gas is 0.01 vvm or more. 16. The method according to any one of claims 12 to 15,
Wherein the pH at the time of supplying the oxygen gas is 8 or more. 17. The method according to any one of claims 12 to 16,
A cacao coloring matter, a high coloring matter pigment, an onion coloring matter, and a tamarind coloring matter. A solution containing a pigment of a brown to brown color system is subjected to an adsorption resin treatment, a cation exchange resin treatment, an anion exchange resin treatment, or an activated carbon treatment, and a solution containing a non-adsorbed portion by adsorption resin treatment, a cation exchange resin treatment And recovering a non-adsorbed portion by anion exchange resin treatment, or a non-adsorbed portion by an activated carbon treatment.

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