JP6543048B2 - Non-emulsifiable pigment preparation containing erythema pigment and / or erythema yellow pigment - Google Patents

Description

  The present invention relates to non-emulsifiable pigment preparations containing erythema pigment and / or erythema yellow pigment.

  Ginseng pigment and ginseng yellow pigment are relatively stable heat-stable natural pigments, and they are very excellent in dyeability to proteins, so they can be processed fishery products, processed meat products, agricultural products, sweets and frozen desserts. Widely used in various applications including Currently, there are two main types of erythema pigment and erythema yellow pigment preparations in the market, which are liquid products and powder products, and they are appropriately used depending on the purpose and application.

  As a technique related to a red yeast pigment preparation, a method for producing a red yeast pigment preparation, which comprises dispersing a red yeast pigment, a hydrophobic protein and a polyphenol in an alcohol / water mixed solution and drying the obtained dispersion (see Patent Document 1) Powder product), preparation obtained by dissolving sage pigment in a solution containing 0.1% by weight or more of tryptophan, histidine, tyrosine or methionine (refer to Patent Document 2; liquid product), red yeast pigment extract, propylene glycol, BACKGROUND ART Oil-soluble dyes (see Patent Document 3) and the like that mix glycerin fatty acid esters and edible fats and oils are known.

JP, 2008-115233, A JP 2003-191 A Japanese Patent Application Laid-Open No. 60-75256

  Powdered products (powdered pigment preparations) have the advantage that the color tone change of the pigmented preparations during storage is small and they are suitable for long-term storage (for example, about 6 months to 12 months). However, on the other hand, it is lacking in convenience because powdering and lumping occur during coloring. For example, the problem is that it is difficult to uniformly color the target composition (the composition to be colored), or because it is necessary to make a primary dissolution in a solvent such as water when using a pigment preparation, the work efficiency is significantly reduced. It has a disadvantage such as causing it, and it is easy for the user to keep away from it. On the other hand, the liquid product (liquid dye preparation) is easily dispersed and dissolved in a to-be-colored composition, particularly an aqueous composition, so that the to-be-colored composition can be uniformly colored, and it has an advantage of high convenience. However, since the liquid component is likely to degrade the pigment component over time, the color tone change during storage of the preparation is large, and it is not suitable for long-term storage. Generally, the period in which the color tone change of the liquid product falls within an acceptable range is very short, at most about three months.

  The techniques disclosed in Patent Documents 1 and 2 are all techniques focusing on the point that the pigment after coloring the target composition is inferior in light resistance, and focused on the stability of the pigment preparation itself (suppression of color tone change) It's not a technology. Also, none of the techniques go beyond the range of properties possessed by the above-mentioned powder and liquid products. For example, the powder product disclosed in Patent Document 1 still causes powdering or lumping during coloring and lacks convenience. It is difficult to uniformly color the target composition, and is primarily dissolved in a solvent such as water during coloring. It has the disadvantage of being necessary. Similarly, the liquid product disclosed in Patent Document 2 also has a problem that the color tone change during storage of the preparation is large, and the period in which the color tone can be stably held is very short.

  The technology disclosed in Patent Document 3 can not be used for coloring aqueous compositions because it is a technology for oil solubilizing erythema pigment (technology related to emulsion pigment preparation). For example, even if the erythema pigment preparation is added to an aqueous solvent, the dye preparation does not become compatible with the aqueous solvent, so that the oil-solubilized pigment component and oil in the pigment preparation separate and sufficient coloring of the aqueous composition is In addition to being impossible, the commercial value of the composition to be colored is significantly reduced.

  In view of the above-mentioned prior art, it is an object of the present invention to provide a non-emulsification-type erythema pigment and / or erythema yellow pigment formulation which combines the convenience of liquid products and the storage stability of powder products.

As a result of intensive studies to solve the problems as described above, the present inventors selected glycerin and / or propylene glycol as a solvent for the non-emulsifiable pigment preparation, and used glycerin and / or propylene glycol and powdered red yeast pigment. The present invention provides a pigment preparation that can be stored for a long time comparable to powder products while having the advantage of being excellent in dispersibility and solubility in an aqueous solvent peculiar to liquid products by mixing and / or red yeast yellow pigment. I found out what I could do.
The present invention has been completed by further studies based on such findings.

The present invention relates to a non-emulsifying dye preparation having the following aspects;
Item 1. The powdery erythema pigment and / or the powdery erythema yellow pigment is
Characterized in that it is mixed with glycerin and / or propylene glycol,
Non-emulsifying dye formulation.
Item 2. The non-emulsifying dye preparation according to Item 1, wherein the water content of the dye preparation is 8% by mass or less.
Item 3. The non-emulsifiable pigment preparation according to Item 1 or 2, wherein the powdered erythema pigment and / or powdered erythema yellow powder is coated with a polysaccharide thickener.
Item 4. The non-emulsifiable pigment preparation according to item 3, wherein the polysaccharide thickener is one or more selected from the group consisting of gati gum, gum arabic, locust bean gum, pullulan, guar gum, xanthan gum, agar, soybean polysaccharide and gelatin. .
Item 5. The non-emulsifying pigment preparation according to any one of Items 1 to 4, which is a pigment preparation for coloring an aqueous composition.

The present invention also relates to a method of producing a non-emulsifying dye preparation having the following aspects;
Item 6. Powdery erythema pigment and / or powdery erythema yellow powder,
A method of producing a non-emulsifying dye preparation, comprising the step of mixing with glycerin and / or propylene glycol.
Item 7. A method for producing a non-emulsifying pigment preparation containing erythema pigment and / or erythema yellow pigment,
Coating a powdery red yeast pigment and / or a powdery red yeast yellow pigment using a polysaccharide thickener,
Mixing the coated powdered dye obtained in the above step with glycerin and / or propylene glycol,
A method of producing a non-emulsifying dye preparation, comprising:

  According to the present invention, it is possible to provide a non-emulsifiable pigment preparation containing erythema pigment and / or erythema yellow pigment and having the advantages of liquid and powder products. The pigment preparation of the present invention is excellent in dispersibility and solubility in an aqueous solvent as in the liquid product, and therefore, the composition to be colored, in particular, the aqueous composition can be easily colored. In addition, conventionally, the storage period in which the color tone change of the color preparation can be sufficiently suppressed has been limited to about 3 months at most in the liquid product, but the color change of the color preparation of the present invention is significantly suppressed during storage. As a powder product, long-term storage of 6 months or more is possible.

(I) Non-Emulsifying Pigment Formulation The non-emulsifying pigment formulation of the present invention contains erythema pigment and / or erythema yellow pigment.
The red yeast pigment targeted by the present invention is a naturally occurring red pigment based on ancaflavins and monskorbulins, which is obtained from a culture solution of the fungus Bacillus subtilis ( Monascus pilosus or Monascus purpureus ). The red yeast pigment can be obtained, for example, by extracting the cells of the fungus Bacillus subtilis with aqueous ethanol or aqueous propylene glycol. Red yeast yellow pigment is a natural yellow pigment based on xanthomonasins, which is obtained from a culture solution of the fungus Bacillus subtilis ( Monascus pilosus or Monascus purpureus ). The red yeast yellow pigment can be obtained, for example, by extracting the culture solution of Aspergillus niger and the culture solution of Aspergillus niger and drying it from ground and extracting with mild hydrochloric acid acidic ethanol and neutralizing it.

The non-emulsifying pigment preparation of the present invention uses glycerin and / or propylene glycol as a solvent.
Glycerin is a typical trihydric alcohol, also called glycerol. Glycerin is soluble in water and alcohol, and can be easily dispersed and dissolved in an aqueous solvent. In the present invention, commercially available glycerin can be used, and the purity of glycerin to be used is not limited, but the preferred purity is 95% or more.

  Propylene glycol is also referred to as 1,2-propanediol. Similar to glycerin, propylene glycol is soluble in water and alcohol, and can be easily dispersed and dissolved in an aqueous solvent. In the present invention, commercially available propylene glycol can be used, and the purity of propylene glycol is not limited, but the preferable purity is 98% or more. The propylene glycol used in the present invention preferably has a water content of 0.2% or less. When the water content exceeds 0.2%, the decomposition of erythema pigment and / or erythema yellow pigment may progress due to the water in the solvent, and the color tone change of the dye preparation may not be sufficiently suppressed.

  The above glycerin and propylene glycol are both suitable as a solvent for the non-emulsifiable pigment preparation targeted by the present invention, since both are easily dispersible in an aqueous solvent, but a particularly preferred solvent is glycerin. The content of glycerin and / or propylene glycol in the non-emulsifying dye preparation of the present invention is not particularly limited, but a preferable content is 20% by mass or more, more preferably 35% by mass or more, still more preferably 50% by mass or more, further more Preferably it is 70 mass% or more. Although the upper limit in particular is not restrict | limited, For example, 99 mass% is mentioned, and a preferable upper limit is 98 mass%.

The non-emulsifiable pigment preparation of the present invention is characterized in that the erythema pigment and / or erythema yellow powder is mixed with glycerin and / or propylene glycol in a powder state.
As the powdered erythema pigment and / or powdered erythema yellow powder, a pigment material of a powdery product in circulation may be used, or a powdered pigment material of a liquid product may be used. A well-known drying method can be used as powdering means. For example, spray drying, freeze drying, granulation and the like.
In the present invention, "powdery erythema pigment, powdered erythema yellow powder" means erythema pigment in a dry state and erythema yellow pigment, and the form is not particularly limited. For example, the pigment may be formed into granules.

  The pigment preparation of the present invention is a dispersion preparation in which powdered erythema pigment and / or powdered erythema yellow powder is mixed with glycerin and / or propylene glycol, and is a conventional oil-soluble preparation (emulsion formulation) Is different. In this regard, the dye preparation of the present invention is a non-emulsifying preparation. Therefore, the preferable fat and oil content in the non-emulsifying pigment preparation of the present invention is 1% by mass or less, more preferably 0.1% by mass or less, and further preferably containing no fat or oil.

  A solvent other than glycerin and / or propylene glycol may be added to the non-emulsifying dye preparation of the present invention as long as the effects of the present invention are not impaired. For example, as solvents other than glycerin and / or propylene glycol, sugar solutions, glycerin fatty acid esters having an HLB of 6 or more, and the like can be mentioned.

The non-emulsifiable pigment preparation of the present invention exhibits extremely excellent color stability over a long period of time by maintaining the red yeast pigment and / or the red yeast yellow powder in a powder state. Therefore, in the present invention, the water content of the solvent used for the non-emulsifying dye preparation is preferably 5% by mass or less, more preferably 1% by mass or less.
Similarly, in consideration of the amount of water contained in the powdery red yeast pigment and / or powdery red yeast yellow pigment used as the raw material, the preferred water content in the non-emulsifying pigment preparation of the present invention is 8% by mass or less, more preferably Is 5% by mass or less, more preferably 2% by mass or less.
In addition, while conventional erythema pigment and / or erythema yellow liquid pigment preparations generally use water or ethanol as a solvent, the non-emulsifiable pigment preparations of the present invention have an ethanol content of 10% by mass or less. The content is preferably 5% by mass or less, more preferably 1% by mass or less.

  In the non-emulsifiable pigment preparation of the present invention, it is preferable that the powdered erythema pigment and / or the powdered erythema yellow powder be coated with a polysaccharide thickener. By coating powdery red yeast pigment and / or powdery red yeast yellow powder with a polysaccharide thickener, the stability of the powdery pigment present in the solvent is enhanced in combination with the above-mentioned solvent (glycerin and / or propylene glycol). It is possible to significantly improve and, as a result, to derive excellent storage stability of the non-emulsifying dye preparation.

  In the present invention, the term "coating" refers to a state in which a polysaccharide thickener is attached to part or all of the surface of powdery red yeast pigment and / or powdery red yeast yellow pigment. There are no particular limitations on the coating method, and various methods can be used. For example, a method of pulverizing (drying) a mixed solution containing erythema pigment and / or erythema yellow powder and a polysaccharide thickener, and preparing as a powdery erythema pigment and / or powdery erythema yellow powder On the other hand, the method etc. of spraying the solution containing polysaccharide thickener are mentioned. As the powdering (drying) means, various known drying methods can be used. For example, a spray drying method, a freeze drying method, a granulation method and the like can be mentioned. From the viewpoint of efficiently coating the powdery pigment, the solvent of the mixed solution containing the erythema pigment and / or the erythema yellow polysaccharide and the polysaccharide thickener, or the solution containing the polysaccharide thickener is water. Is desirable.

  The type of polysaccharide thickener used in the present invention is not particularly limited. For example, gati gum, gum arabic, locust bean gum, pullulan, guar gum, xanthan gum, agar, soybean polysaccharide, gelatin and the like can be mentioned. The polysaccharide thickener is expected to have an effect of coating powdery red yeast pigment and / or powdery red yeast yellow pigment and suppressing the dissolution of the powdery pigment in glycerin and / or propylene glycol as a solvent. Therefore, it is preferable to use a polysaccharide thickener which is poorly soluble or insoluble in glycerin and / or propylene glycol. In addition, since the non-emulsifying pigment preparation of the present invention is expected to be easily dissolved in an aqueous solvent, it is preferable to use a polysaccharide thickener that is soluble in an aqueous solvent. In view of this aspect, various polysaccharide thickeners can be selected besides the polysaccharide thickeners described above.

  Preferred polysaccharide thickeners used in the present invention are one or more selected from the group consisting of gati gum, gum arabic, locust bean gum, pullulan, guar gum and xanthan gum, more preferably gati gum and / or gum arabic.

Gati gum is a polysaccharide obtained from the sap (secretory fluid) of Gati ( Anogeissus latifolia Wallich ) and is a water-soluble polysaccharide which is usually dissolved in water to about 30% by mass under normal temperature to heating conditions. There are no particular limitations on the type of gati gum used in the present invention, and examples of commercially available gati gum products include "Gati Gum SD" from San-Ei Gen F.F.I.

  The gum arabic used in the present invention is a polysaccharide obtained from the sap of a legume Acacia plant. Although the molecular structure of gum arabic has not been clarified, it is known that galactose, arabinose, rhamnose and glucuronic acid are constituent sugars. The type of gum arabic used in the present invention is not particularly limited. For example, commercially available gum arabic products include "Gum Arabic" from San-Ei Gen F.F.I.

  The amount of polysaccharide thickener added is not particularly limited with respect to erythema pigment and / or erythema yellow pigment, but the preferable amount of polysaccharide thickener added is the solid content of erythema pigment and / or erythema yellow pigment (soluble The solid content is 0.001 to 100 parts by mass, preferably 0.01 to 10 parts by mass, and more preferably 0.02 to 5 parts by mass with respect to 1 part by mass of the solid content. In addition, as described later, an excipient may be used to adjust the color values of powdery erythema pigment and powdered erythema yellow pigment, but when an excipient is used, Alternatively, it is preferable to use the polysaccharide thickener added in the amount described above with respect to 1 part by mass of the solid content (total solid content) of erythema yellow powder and the excipient.

Further, from the viewpoint of the coating method, it is desirable to adjust the type, addition amount, and the like of the polysaccharide thickener so that the viscosity of the solution containing polysaccharide polysaccharide is 7,000 mPa · s or less at the time of coating. . For example, if it is a method of pulverizing (drying) after preparing a mixed solution containing erythema pigment and / or erythema yellow polysaccharide and polysaccharide thickener, the viscosity of the mixed solution in the pulverizing step It is preferable that the kind and addition amount of polysaccharide thickener are adjusted so that it may become 7,000 mPa * s or less. Similarly, in the case of a method of spraying a solution containing a polysaccharide thickener with respect to powdery erythema pigment and / or powdery erythema yellow powder, a solution containing a polysaccharide thickener at the time of spraying is used. It is preferable that the viscosity be adjusted to 7,000 mPa · s or less.
In addition, the said viscosity is a value of the viscosity at the time of 12 rpm and 1 minute measured using a Brookfield viscometer on the temperature conditions at the time of a pulverization process and spraying. The lower limit value of the viscosity is not particularly limited, and can be, for example, 5 mPa · s.

  Further, in the present invention, in the case of using a polysaccharide thickener from the viewpoint of the dispersibility and solubility of the non-emulsifying pigment preparation in an aqueous solvent, the thickening polysaccharide content in the non-emulsifying pigment preparation is 45% by mass or less Is more preferably 20% by mass or less, still more preferably 10% by mass or less, and still more preferably 8% by mass or less. The lower limit of the polysaccharide thickener content in the non-emulsifiable pigment preparation is not particularly limited, but a preferable content is, for example, 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass. % Or more.

  Hereinafter, in the present specification, in the case of describing “powdery erythema pigment and / or powdery erythema yellow powder”, powdered erythema pigment and / or powdery erythema coated with polysaccharide thickener. Contains yellow pigment.

The color value of the powdery erythema pigment and / or the powdery erythema yellow pigment can be appropriately adjusted. The color value is not particularly limited, but is preferably 5 to 3000, more preferably 20 to 1000.
The color value can be adjusted using an excipient. For example, by increasing the addition amount of the excipient, it is possible to lower the color value of the obtained powdered erythema pigment and / or erythema yellow pigment. The type of excipient is not limited, and materials available for pigment preparations can be used. For example, dextrin, lactose, starch, processed starch, sucrose fatty acid ester and the like can be mentioned.
In addition, although an excipient can be used for the purpose of adjusting the color value, it does not significantly affect the stability of the non-emulsifying dye preparation.

  There are no particular restrictions on the mixing ratio of glycerin and / or propylene glycol and powdered erythema pigment and / or powdered erythema yellow pigment, and can be appropriately adjusted according to the color value of the final product, ie, the non-emulsifying pigment preparation. The preferred mixing ratio is 100 parts by mass or less of powdered erythema pigment and / or powdered erythema yellow powder, with respect to 100 parts by mass of glycerin and / or propylene glycol in the non-emulsifying pigment preparation, and more preferably 45 The content is at most parts by mass, more preferably at most 30 parts by mass, still more preferably at most 25 parts by mass. When the mixing ratio of powdery red yeast pigment and / or powdery red yeast yellow pigment to 100 parts by weight of glycerin and / or propylene glycol largely exceeds 100 parts by weight, the flowability of the non-emulsifiable pigment preparation is reduced, and the workability is improved. It may decrease.

The lower limit of the mixing ratio of the powdered erythema pigment and / or powdered erythema yellow powder to 100 parts by mass of glycerin and / or propylene glycol is not particularly limited. Is 0.1 parts by mass. The mixing ratio of the powdered erythema pigment and / or powdered erythema yellow powder to glycerin and / or propylene glycol can be appropriately adjusted based on the color value indicating the thickness of the pigment. For example, in the case of preparing a pigment preparation having the same color value, the higher the color value of powdery erythema pigment and / or erythema yellow powder used as the raw material, the smaller the content of the powdery pigment in the non-emulsifiable pigment preparation In order to save the amount, the mixing ratio of the powdered dye to glycerin and / or propylene glycol can be small. As an example, when mentioning the case of a non-emulsifiable pigment preparation using 1% by mass of a powdered pigment having a color number of 1,500, the color value of the obtained non-emulsifiable pigment preparation is the normal product currently marketed. Pigment and / or erythema preparation).
Further, among the pigment preparations distributed in the market, those having a color value of 1 or less are also present, so the addition amount of powdery erythema pigment and / or powdery erythema yellow pigment is appropriately selected according to the purpose. It can be adjusted.

  As described above, it is possible to design non-emulsifiable pigment preparations having various color values by appropriately adjusting the color values and addition amounts of powdery red yeast pigment and / or powdery red yeast yellow powder to be added. It becomes possible. The non-emulsifiable pigment preparation of the present invention may also contain a material used for a pigment preparation such as an antioxidant within the scope of not impairing the effects of the present invention.

  The thus obtained non-emulsifying dye preparation of the present invention can be easily dispersed and dissolved in an aqueous solvent because it uses glycerin and / or propylene glycol as a solvent. Therefore, the dosage form of the pigment preparation is not particularly limited, and various forms such as solid, paste and liquid can be taken. From the viewpoint of convenience, it is desirable that the pigment preparation has fluidity (for example, paste or liquid).

  The color value of the non-emulsifiable pigment preparation (erythema pigment preparation, erythema yellow pigment preparation) of the present invention is not particularly limited, but a preferable color value is 5 to 1000, more preferably 10 to 500, still more preferably 20 to 20. It is 200.

  The non-emulsifiable pigment preparation of the present invention is characterized in that the color tone change of the preparation is significantly suppressed during long-term storage. The presence or absence of color tone change, the degree of measurement of “color value” using a spectral irradiator (JASCO V-560), and “L, a, b values”, hue (Hue) and saturation (Chroma) It can be evaluated by measuring the color tone.

The color value can be expressed as a numerical value (E ^10% _{1 cm 2} ) obtained by measuring the absorbance at the maximum absorption wavelength in the visible portion of the solution containing the non-emulsifying dye preparation and converting it to the absorbance of the 10 w / v% solution. In the present invention, the color value of the non-emulsifiable pigment preparation can be measured and calculated according to the method described in “Eighth Edition of Food Additive Standard”.

  Since the maximum absorption wavelength is derived from the red yeast pigment and / or the erythema yellow material used, the maximum absorption wavelength of the non-emulsifiable pigment preparation immediately after preparation is measured, and the absorbance at the maximum absorption wavelength is calculated. As a standard, the maximum absorption wavelength of erythema pigment is 480 to 520 nm (50 v / v% ethanol), and the maximum absorption wavelength of erythema yellow pigment is 458 to 468 nm (50 v / v% ethanol).

The control of actual absorbance measurement is a test solution adjusted so that the absorbance falls within the range of 0.3 to 0.7. In the present invention, the test solution is prepared as follows. Accurately measure the amount of sample, put in a measuring flask and dissolve (or dilute) by adding about 10 ml of 50 v / v% ethanol aqueous solution, and add 50 v / v% ethanol aqueous solution to make exactly 100 ml, if necessary Centrifuge or filter to give a sample solution. This sample solution is used as a test solution for measuring absorbance (dilution factor = 1). However, if the absorbance of the sample solution does not fall within the range of 0.3 to 0.7, a solution diluted with a 50 v / v% aqueous ethanol solution is used as a test solution.
The dilution ratio at this time is (sample solution (ml) + 50 v / v% aqueous ethanol solution (ml)) / sample solution (ml).
Specifically, the absorbance is measured by a spectrophotometer (V-560 (Nippon Bunko Co., Ltd.) or an equivalent thereof) with an optical path length of 10 mm.

The color value at the maximum absorption wavelength is calculated according to the following.
Color value = ((10 x A x F) / amount of sample collected (g))
[A is the absorbance of the test solution at the maximum absorption wavelength. F is a dilution factor adjusted so that the measured absorbance falls within the range of 0.3 to 0.7. ]

  For example, in the present invention, a test solution is prepared by diluting a non-emulsifying dye preparation with a 50 v / v% ethanol aqueous solution so that the absorbance at the maximum absorption wavelength falls within the range of 0.3 to 0.7. The color value of the non-emulsifying dye preparation can be calculated by measuring the absorbance of the solution. When the color value of the non-emulsifiable dye preparation immediately after preparation and the color value of the non-emulsifiable dye preparation at the time of storage are respectively calculated, the less the change in the numerical value (color value) of the two, the more the fading of the dye is suppressed It can be evaluated that it is a pigment preparation having high storage stability.

From the viewpoint of the stability of the pigment preparation, the non-emulsifiable pigment preparation of the present invention is a preparation having a color value retention of 95% or more after 5 months under refrigeration (5 ± 3 ° C.) after preparation. preferable. More preferably, it is desirable that the color value retention rate after 6 months, and further, the dye retention rate after 12 months is 95% or more.
(Color value retention rate) = (Color value at passage (storage) / Color value immediately after preparation) × 100 (%)

  The color tone can be confirmed by obtaining “L, a, b values”, hue (Hue) and saturation (Chroma). Specifically, the dye preparation is dissolved in ion-exchanged water, filled in a 1 cm cell, and HunterLab color system (Lab system) with a spectrophotometer (V-560 (JASCO Corporation) or equivalent). The tristimulus values of are determined, and the hue (Hue) and saturation (Chroma) are measured with the reflected light. The measurement of color tone can be carried out by adding a non-emulsifying dye preparation to ion exchange water so that the absorbance at the maximum absorption wavelength falls within the range of 0.3 to 0.8.

  The Hunter Lab color system (Lab system) is a color system that forms a color solid composed of orthogonal coordinates consisting of a and b axes indicating chromaticity and an L axis perpendicular to this, and a is positive. An increase on the side means reddish, an increase on the negative side increases greenish, an increase on b positive means yellowish, and an increase on negative side means bluish. The L value corresponds to the lightness, white when L = 100, black when L = 0, and the tone tends to be brighter as the L value is larger.

The hue (Hue) is obtained by converting the angle of a and b into a Munsell color standard, and indicates that the yellowishness is as the value is larger and the reddish as it is smaller at 0 to 90 degrees. At 270 to 360 degrees, the larger the value, the reddish, and the smaller the value, the more purple.
The chroma (Chroma) is the length from the origin in the Hunter Lab color system, and indicates that the larger the value, the brighter. Specifically, the chroma (Chroma) can be measured according to the following (Equation 1).

Formula 1

In the present invention, ΔE (color difference) is used to evaluate color tone change. ΔE is determined according to the following (Equation 2), and the value of ΔE increases as the difference between the two color tones to be compared increases, indicating that the color tone is different. In general, it is recognized that when ΔE (color difference) is 3.0 or less, it is not a difference that causes a problem in practical use with the naked eye.
In the present invention, it is preferable that ΔE (color difference) measured according to the following (formula 2) is 5 or less for a non-emulsifiable pigment preparation after 12 months under refrigeration (5 ± 3 ° C.). More preferably it is 3 or less, still more preferably less than 2.

Formula 2

  In the formula, L1, a1 and b1 show L, a, b values after storage in a refrigerator (5 ± 3 ° C.) after preparation of the non-emulsifying dye preparation, and L2, a2 and b2 are non-emulsified immediately after preparation The L, a, b values of the pigment preparation are shown.

  In the past, the change in color tone of a liquid product of erythema pigment or erythema yellow pigment was very short, at most about three months, at most within the allowable range, but according to the present invention, six months As described above, it is possible to provide a non-emulsifying pigment preparation in which color tone change is significantly suppressed over a long period of time, such as 12 months to 24 months.

  The non-emulsifying dye preparation of the present invention is preferably stored by storage under refrigeration or freezing. Although frozen storage has the advantage that it is easier to control color change compared to cold storage, it costs more to install and manage the freezer, it is difficult to thaw only the amount used, and color change is caused by repeated thawing It has problems such as being promoted. On the other hand, refrigeration storage is highly convenient because the amount used can be taken out each time and the thawing process is unnecessary, but when conventional products (pigment preparations of liquid products) are stored under refrigeration, color tone changes can not be suppressed and long-term storage In the case of heat shock due to the opening and closing of the refrigerator, the storage period was further shortened. In this respect, the non-emulsifying pigment preparation of the present invention is very useful because it is a pigment preparation in which color tone change is significantly suppressed over a long period of time even under refrigeration storage.

  The non-emulsifiable pigment preparation of the present invention is suitable for coloring an aqueous composition because it is excellent in dispersibility and solubility in an aqueous solvent. For example, it can be usefully used as a colorant for aqueous compositions such as food and drink, cosmetics, medicines, quasi-drugs and feeds prepared using water as one of the raw materials. In this respect, the non-emulsifying dye preparation of the present invention is also an invention relating to an aqueous dye preparation. In particular, beverages (for example, milk, drink yogurt, etc.), confectionery (for example, baked confectionery, fried confectionery, etc.), fishery products (eg, paste products, fish meat pickles, etc.), processed meat products (eg, grilled pork, terrine, etc.) And agricultural products (for example, pickles, jams, etc.), frozen desserts, baked foods, etc.

(II) Method for Producing Non-Emulsifiable Dye Formulation The present invention also relates to a method for producing a non-emulsifying pigment formulation containing a red yeast pigment and / or a red yeast pigment that combines the advantages of liquid and powder products.
The method for producing the non-emulsifying dye preparation of the present invention comprises the following steps:
Powdery erythema pigment and / or powdery erythema yellow powder,
Mixing with glycerin and / or propylene glycol.
The details of the powdery erythema pigment, erythema yellow pigment, glycerin, propylene glycol and the like used in the present invention can be referred to the above-mentioned "(I) non-emulsifiable pigment preparation".

The method for producing the non-emulsifying dye preparation of the present invention preferably comprises the following production steps;
(Step 1)
Coating a powdery red yeast pigment and / or a powdery red yeast yellow pigment with a polysaccharide thickener to produce a coating dye powder;
(Step 2) A step of mixing the coating dye powder obtained by the above step with glycerin and / or propylene glycol.

(Step 1) is a step of coating powdery erythema pigment or powdered erythema yellow powder using polysaccharide thickener to produce a coating dye powder. A conventionally known coating method can be used in this step. For example, the following methods (Step 1-1) and (Step 1-2) can be mentioned. From the viewpoint of simplification of the production process, the preferred coating method is (step 1-1).

(Step 1-1)
A step of mixing a red moth pigment and / or erythema yellow powder with a polysaccharide thickener in a solution (preferably in an aqueous solution) to prepare a dye mixture solution, and a step of pulverizing the dye mixture solution.
(Step 1-2)
A step of spraying a solution containing a polysaccharide thickener on powdered erythema pigment and / or powdered erythema yellow powder;

  The solution containing the pigment mixture solution obtained in (Step 1-1) and the solution containing a polysaccharide thickener used in (Step 1-2) preferably has a viscosity of 7,000 mPa · s or less, 5, The viscosity is more preferably 000 mPa · s or less, still more preferably 3,000 mPa · s or less. The lower limit of the viscosity of the solution is not particularly limited, and may be, for example, 5 mPa · s.

(Step 2) can be achieved by mixing the coating dye powder obtained in step 1 with glycerin and / or propylene glycol. The mixing method is not particularly limited, and conventionally known mixing means can be used.

  Hereinafter, the contents of the present invention will be specifically described using the following examples and comparative examples, but the present invention is not limited to these.

EXPERIMENTAL EXAMPLE 1 Ginseng Pigment Preparations and Ginseng Yellow Pigment Preparations According to the formulations shown in Tables 1 and 2, non-emulsifiable pigment preparations containing Ginseng pigment or Ginseng yellow pigment were produced. The numerical values in Table 1 indicate% by mass.
(Powdered erythema pigment, powdered erythema yellow pigment)
Dissolve the pigment (monascus pigment, persimmon yellow pigment), excipient (dextrin), and, if necessary, polysaccharide thickener (Gattigum, gum arabic, locust bean gum, pullulan, guar gum, xanthan gum) in water The dye mixture solution was prepared. Next, the prepared dye mixture solution was dried using a spray drier to obtain 30 g each of powdery red yeast pigment and powdery red yeast yellow pigment (Example 1-1 to Example 1-11). The color value of the dye powder after spray drying was 720 for the powdered erythema pigment and 310 for the powdered erythema yellow powder.

Note 1) The viscosity of the dye mixture solution at the time of spray drying was 7,000 mPa · s or less in all cases.

(Non-emulsifying dye preparation)
According to Table 2, mixing the powdered dye (Example 1-1 to Example 1-11) obtained in the step 1 with glycerin or propylene glycol so that the color value of the final dye preparation is 60. Then, a non-emulsifiable pigment preparation containing erythema pigment or erythema yellow pigment was prepared.
Specifically, a erythema pigment preparation is prepared by mixing 8.4% by mass of powdered erythema pigment and 91.6% by mass of glycerin or propylene glycol, and the erythema yellow pigment preparation is prepared as a powdered erythema powder. It was prepared by mixing 19.4% by mass of yellow element and 80.6% by mass of glycerin or propylene glycol.
The water content of each of the obtained non-emulsifying dye preparations was 1% or less.

Note 5) Use glycerin with a purity of 95% or more.
Note 6) Use propylene glycol with a purity of 98% or more and a water content of 0.2% or less.

(Evaluation of color value and color tone change 1)
About Example 1-1-A and Example 1-3-A, the obtained non-emulsifiable pigment preparation (monascus pigment preparation) was stored under refrigeration at 8 ° C. for 18 months in a refrigerator and evaluated for color value and color tone change .
On the other hand, for comparison and control, the red yeast pigment preparation currently available on the market (conventional product 1) was similarly stored under refrigeration at 8 ° C. for 5 months in a refrigerator, and color value and color tone change were measured. As the conventional product 1, "San red (registered trademark) MR" manufactured by San-Ei Gen F.F.I. Inc. was used. "Sun Red MR" is an aqueous solution formulation (liquid formulation) of scarlet pigment containing 50 v / v% of alcohol. Note that “Sun Red MR” has a large change in color tone after 5 months, so it is stored data for up to 5 months.
(Color value)
Each pigment preparation was diluted 1000 times with 50 v / v% ethanol aqueous solution, filled in a 1 cm cell, and the absorbance at the maximum absorption wavelength was measured with a spectrophotometer (V-560 (JASCO Corp.)) Near, crimson yellow pigment: around 460 nm).
(Color tone)
0.53 g of each pigment preparation was added to 100 mL of ion exchange water and filled in a 1 cm cell. The tristimulus values of the HunterLab color system (Lab system) were determined with a spectrophotometer (V-560 (Nippon Bunko Co., Ltd.)), and the hue (Hue) and saturation (Chroma) were measured with reflected light. Further, ΔE (color difference) was calculated according to (Expression 3). The results are shown in Table 3.

Note 7) Lab values of the dye preparation after storage were calculated according to the following formula 3 using L1, a1 and b1 and Lab values of the dye preparation immediately after preparation as L2, a2 and b2.

Formula 3

(result)
The standard (guarantee standard) of the range in which the color tone change is permitted is 95% or more of the color value residual ratio and 5 or less in ΔE (color difference).
The conventional product 1 currently distributed in the market had its color value reduced to 90% after 5 months, and the color tone was separated up to ΔE 7.5. Furthermore, the difference in hue changed significantly with 0.8. In general, it is said that the difference in hue (hue) of 0.5 or less does not cause any practical problem with the naked eye. Accordingly, it can be seen that the conventional product 1 has already undergone a large color tone change after 5 months.
On the other hand, the non-emulsifiable pigment preparation (erythema pigment preparation) of Example 1-1-A has a color value retention of 99% after 8 months, a ΔE of 4.0, and a difference in hue (hue) of 0. A clear improvement was seen as compared to .6 and the conventional product 1. Furthermore, the non-emulsifiable pigment preparation of Example 1-3-A in which powdery erythema pigment is coated with Gati gum, the color value retention rate 99%, ΔE is 1.3, and the storage stability is maintained after 18 months. It was an extremely excellent pigment preparation.

  In addition, when the non-emulsifiable pigment preparations of Examples 1-1-A and 1-3-A are each dissolved in an aqueous solvent (water), they are easily dispersed and dissolved without formation of lumps, and an aqueous solvent (water ) Could be colored clear red.

(Evaluation of color value and color tone change 2)
Similarly, with regard to the non-emulsifiable pigment preparations containing erythema yellow, Example 1-2-A, Example 1-4-A, and the currently available red erythema preparations currently marketed (conventional products 2. "San-Euro (registered trademark) NO. 1244") was stored in a refrigerator at 8 ° C for 18 months, and evaluated for color value and color tone change. The results are shown in Table 4.
"San-Euro (registered trademark) NO. 1244" is a red yeast pigment preparation manufactured by San-Ei Gen F.F.I. Inc., and is an aqueous solution preparation containing 20 v / v% of alcohol. The data shown in Table 4 is stored data for up to 5 months, since the change in color tone after 5 months is large for "San-Euro NO. 1244".

(result)
The conventional product 2 (red berry yellow pigment preparation, liquid product) currently distributed in the market shows good storage stability up to 3 months, but the color tone changes significantly after 4 months, After 5 months, ΔE (color difference) was 10 or more.

On the other hand, the non-emulsifiable pigment preparation of Example 1-2-A (monascus yellow pigment preparation) shows good values for the pigment residual rate and ΔE after 6 months and 12 months, respectively. A significant improvement was seen in comparison. However, after 18 months, ΔE increased to 10, and the color tone became pale yellow.
The non-emulsifiable pigment preparation of Example 1-4-A, in which powdery erythema yellow powder is coated with gati gum, the storage stability is further improved in comparison with Example 1-2-A, and 18 months have passed. Even after that, the color tone change was suppressed significantly

  In addition, when the non-emulsifiable pigment preparations of Examples 1-2-A and 1-4-A are respectively dissolved in an aqueous solvent (water), they are easily dispersed and dissolved without formation of lumps, and an aqueous solvent (water ) Could be colored clear yellow.

(Evaluation of color value and color tone change 3)
Similarly to the evaluation 2 of color value and color tone change, the non-emulsifiable pigment preparation obtained in Example 1-3-A to Example 1-11-B is stored in a refrigerator at 8 ° C. for 18 months, and the color value and color tone Evaluated for change. The results are shown in Table 5. In Table 5, the upper stage shows the dye residual rate (%), and the lower stage shows ΔE (color difference).

(result)
The standard (guarantee standard) of the range in which the color tone change is permitted is 95% or more of the color value residual ratio and 5 or less in ΔE (color difference).
As is clear from Table 5, each of the non-emulsifiable pigment preparations coated with the polysaccharide thickener (Examples 1-3-A to 1-1-1 B) satisfies the above conditions until 15 months. The pigment preparation was extremely excellent in storage stability. Conventionally, the storage period in which the color tone change is allowed is as short as about 3 months, and it can be seen that the storage period is extended by a factor of 5 or more compared to the conventional product, and the storage stability is significantly improved.
In particular, non-emulsifiable pigment preparations using glycerol as a solvent (Examples 1-3-A to 1-11-A) have ΔE (color difference) of 3.0 or less after 18 months. The A value of Δ 3.0 or less is a value that is generally recognized as not a difference (color tone change) that causes a practical problem with the naked eye, and it can be seen that the pigment preparation is extremely excellent in storage stability.

Furthermore, all non-emulsifiable pigment preparations of Examples 1-3-A to 1 1-1 B were added to the aqueous solvent (water), and the dispersibility and solubility were confirmed. Any non-emulsifiable dye preparation is easily dispersed and dissolved in an aqueous solvent (water) without any damage, and the non-emulsifiable dye preparation of the present invention is a preparation having both the convenience of liquid product and the storage stability of powder product. Met.

Claims (6)

The powdery erythema pigment and / or the powdery erythema yellow pigment is
Characterized in that it is mixed with glycerin and / or propylene glycol,
A non-emulsifying dye preparation ,
The pigment | dye formulation whose water content of the said pigment | dye formulation is 8 mass% or less . The non-emulsifiable pigment preparation according to claim 1, wherein the powdered erythema pigment and / or powdered erythema yellow powder is coated with a polysaccharide thickener or gelatin . The non-emulsifiable pigment preparation according to claim 2, wherein the polysaccharide thickener is one or more selected from the group consisting of gati gum, gum arabic, locust bean gum, pullulan, guar gum, xanthan gum, agar, and soybean polysaccharides. . The non-emulsifiable pigment preparation according to any one of claims 1 to 3 , which is a pigment preparation for coloring an aqueous composition. Powdery erythema pigment and / or powdery erythema yellow powder,
Characterized in that it comprises the steps of mixing with glycerin and propylene glycol,
The manufacturing method of the non-emulsifying pigment formulation whose water content is 8 mass% or less . A method for producing a non-emulsifying pigment preparation containing erythema pigment and / or erythema yellow pigment,
Coating powdery red yeast pigment and / or powdery red yeast yellow pigment with polysaccharide thickener or gelatin ;
Mixing the coated powdered dye obtained in the above step with glycerin and / or propylene glycol,
A method of producing a non-emulsifying dye preparation, comprising: