Carotene-containing composition and method for producing same

Abstract

The present invention relates to: a carotene-containing composition having an intermediate color between red and yellow; and a method for producing the carotene-containing composition. A carotene-containing composition according to the present invention has the following characteristic properties.　The median diameter (D50) of carotene particles is 0.15 μm to 0.55 μm inclusive; the proportion of carotene particles each having a particle diameter larger than 1.3 μm is 17% or less per 100% of the total volume of all carotene particles; and the color tone of an aqueous solution of the carotene-containing composition, which is adjusted so as to have a carotene concentration of 10 ppm, has a color hue angle θ of 50° to 65°, an a* value of 20 to 40, and a b* value of 40 to 52 in a L*a*b* color space system.

Description

Carotene-containing composition and method for producing same

[0001] The present invention relates to a carotene-containing composition having a specific color tone and a method for producing the same.

[0002] Carotene is a typical carotenoid that exhibits a red to yellow hue, and is divided into beta-carotene, which has a beta ring at both ends of the carotenoid skeleton, and alpha-carotene, which has a beta ring at one end. These are used as pigments due to their color, and because they are converted into vitamin A (retinol) in the animal body and function as vitamin A, they are also used for nutritional fortification as provitamin A.

[0003] Carotene pigments are classified by their origin (synthetic, plant-derived, or algae-derived). Synthetic carotene, known as beta-carotene, is designated as a designated food additive in Japan (INS160a(i) / E160a). In Japan, plant-derived carotenes such as carrot carotene and palm oil carotene, and algae-derived carotene such as Dunaliella carotene, are approved as food colorings (additives) for foods, beverages, and pharmaceuticals. Carrot carotene and palm oil carotene contain approximately 60-70% beta-carotene, and are mixtures containing carotenoids such as lutein, zeaxanthin, canthaxanthin, and beta-cryptoxanthin. Dunaliella carotene is 95% beta-carotene, with other carotenoids including alpha-carotene, lutein, and zeaxanthin.

[0004] Carotene is insoluble in water and only slightly soluble in fats and oils, and therefore is not suitable for uniformly or sufficiently coloring water-soluble substances (e.g., water-soluble foods and beverages).Furthermore, even when administered to the body as provitamin A, there is a problem in that the desired bioavailability is not obtained.

[0005] To overcome this problem of carotene's coloring (color-forming) properties on water-soluble substances or to improve its absorbability and bioavailability in the body, various methods have been proposed. These methods mainly involve reducing the crystal size of carotene or emulsifying fine particles of carotene in water.

[0006] For example, Patent Document 1 describes a method for reducing the crystal size of carotene by pulverizing carotene using a colloid mill to reduce the crystal size to a particle size of 2 to 10 μm.

[0007] Patent Document 2, for example, describes a method for emulsifying carotene fine particles by preparing a molecular dispersion of a carotenoid together with an edible oil in a water-miscible, volatile organic solvent, adding an aqueous solution of a protective colloid thereto to transfer the hydrophilic solvent component into the aqueous phase and forming a hydrophobic carotenoid phase as a nano-dispersed phase, heat-treating the resulting hydrogel at 40 to 90°C, and removing the solvent and water from the heat-treated hydrogel to obtain a water-dispersible dry powder. Patent Documents 3 and 4 also describe a method for preparing a carotenoid-containing dry powder by dissolving one or more carotenoids or oxidized carotenoids in a water-miscible organic solvent or a mixed solvent of water and a water-miscible organic solvent, or by dissolving the resulting solution in a water-immiscible organic solvent and then dispersing the resulting solution in an aqueous solution of a mixture of lactose and at least one soy protein, removing water and other solvents from the resulting dispersion, and then drying the resulting dispersion. Furthermore, Patent Document 5 describes a method for preparing a colored formulation of finely divided carotenoids, which comprises the steps of: (a) forming a suspension of carotenoids using a water-immiscible organic solvent, optionally containing an antioxidant and / or oil; (b) feeding the formed suspension to a heat exchanger and heating the suspension to 100-250°C; (c) rapidly cooling the prepared solution to 20-100°C; (d) removing the organic solvent; and (e) converting the obtained dispersion into a powder formulation. Patent Document 6 also describes a method for preparing a colored formulation of finely divided carotenoids, which comprises the steps of: (a) forming a suspension of carotenoids using a water-immiscible organic solvent, optionally containing an antioxidant and / or oil; (b) feeding the formed suspension to a heat exchanger and heating the suspension to 100-250°C; (c) rapidly cooling the prepared solution to 20-100°C; (d) removing the organic solvent; and (e) converting the obtained dispersion into a powder formulation. ４ A method for producing a carotenoid dispersion is described by dispersing a carotenoid in a hydrocarbon or mixture thereof in an aqueous phase, decompressing the mixture and separating the dispersion from the gaseous solvent.

[0008] The methods described in these patent documents all use organic solvents to dissolve carotenoids, and their removal is not only time-consuming and costly but also environmentally harmful. Furthermore, when solubilizing oils are used to dissolve carotenoids, the solubilizing oils are not easily removed during the production process and remain in the final product, so it is necessary to consider the impact on the properties of the final product and on health.

[0009] Meanwhile, Patent Document 7 describes a method for producing a powdered carotenoid composition that is easily dispersible in an aqueous medium without using an organic solvent and / or a solubilizing oil, and that has good stability and bioavailability in addition to high coloring power. Patent Document 7 describes the following steps as a method for preparing a solid carotenoid powder containing 10 to 25% by weight of carotenoid particles with an average size of 0.1 to 0.5 μm: a) melting an aqueous suspension containing 10 to 25% by weight of carotenoid crystals and 0.1 to 6% by weight of a surfactant by heating at a temperature sufficient to melt the carotenoid crystals, b) homogenizing the melted aqueous carotenoid suspension at a pressure in the range of 96.6 to 2759 bar (1400 to 40,000 psi) to obtain the carotenoid particles, and c) drying the homogenized and melted aqueous carotenoid suspension to obtain the solid carotenoid powder. However, this method requires a high temperature of 180 to 250°C to melt the carotenoid crystals (see paragraph

[0010] of Patent Document 7), which leads to problems such as excessive acceleration of thermal decomposition of carotene, resulting in a decrease in yield, and excessive progression of cis-isomerization, making it impossible to obtain carotene containing all-trans-β-carotene in the desired ratio.

[0010] International Publication WO91 / 06292 Pamphlet Japanese Patent Application Laid-Open No. 10-101954 Japanese Patent Application Laid-Open No. 2002-327133 Japanese Patent Application Laid-Open No. 2002-262824 Japanese Patent Application Laid-Open No. 2000-186224 Japanese Patent Application Laid-Open No. 2004-529206 Japanese Patent Application Laid-Open No. 10-046041 Japanese Patent No. 7358063 Japanese Patent No. 7128461 Japanese Patent No. 7080818

[0011] Shokuei Magazine, Vol.31, No.6, 527-531 (1990)

[0012] The first object of the present invention is to provide a carotene-containing composition having a specific color tone, and a method for producing the same. Specifically, the carotene-containing composition is prepared with water so that the carotene concentration of the composition is 10 ppm, and the color tone of the composition is adjusted to L. ＊ a ＊ b ＊ When evaluated in the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ The present invention aims to provide a carotene-containing composition having a value of 40 to 52, and a method for producing the same.

[0013] A second object of the present invention is to provide a carotene-containing composition having the above-mentioned specific color tone as well as emulsion stability (storage stability), turbidity, UHT sterilization resistance, acid resistance, salt resistance, and / or shaking resistance, and a method for producing the same.

[0014] Furthermore, a third object of the present invention is to provide a method (production method) for producing a carotene-containing composition having the above-mentioned properties by continuous and simple operations without using organic solvents and / or oils and fats.

[0015] The present inventors have conducted extensive research aimed at solving the first and third problems, and have discovered that it is possible to grow carotene crystals with a median diameter (D 50 The powder is then pulverized to a median diameter (D 50 The carotene-containing composition has spherical particles with a hue angle θ of 0.15 μm or more and 0.55 μm or less, and the carotene-containing composition has the desired color tone (hue angle θ, a ＊ value, and b ＊Furthermore, the carotene-containing composition has emulsion stability (storage stability), turbidity, UHT sterilization resistance, acid resistance, salt resistance, and / or shaking resistance. In particular, it was confirmed that a carotene-containing composition in which, in addition to the above-mentioned properties, the proportion of carotene particles having a particle size of more than 1.3 μm is 17% or less per 100% of the total volume of carotene particles, on a volume basis, has even better emulsion stability and / or turbidity, and it was confirmed that the carotene-containing composition of the present invention can solve the second problem.

[0016] The present invention has been completed as a result of further intensive research based on these various findings, and has the following embodiments. (I) Method for producing a carotene-containing composition (I-1) A method for producing a carotene-containing composition, comprising the following steps 1 to 3: Step 1: Carotene crystals are mixed in the presence of water and an emulsifier to obtain a carotene crystal having a median diameter (D 50 Step 2: subjecting the pulverized mixture prepared in Step 1 to a subcritical water treatment to prepare a subcritical water-treated product; and Step 3: cooling the subcritical water-treated product prepared in Step 2 to a cooling treatment to obtain a subcritical water-treated product. 50 a step of preparing a carotene-containing composition having spherical particles with a diameter of 0.15 μm or more and 0.55 μm or less; wherein the carotene-containing composition is prepared by dissolving an aqueous solution adjusted to a carotene concentration of 10 ppm in L ＊ a ＊ b ＊ When evaluated in the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ (I-2) The carotene-containing composition is characterized in that the lightness L of an aqueous solution adjusted to a carotene concentration of 10 ppm is 40 to 52. ＊(I-1) The method for producing a carotene-containing composition according to any one of (I-1) to (I-2), wherein the chroma C value of an aqueous solution of the carotene-containing composition adjusted to a carotene concentration of 10 ppm is 50 to 65, preferably 53 to 62, and more preferably 53 to 60. (I-4) The method for producing a carotene-containing composition according to any one of (I-1) to (I-3), wherein the emulsifier used in step 1 is at least one selected from the group consisting of low-molecular-weight gum ghatti, gum arabic, and modified starch. (I-5) The method for producing a carotene-containing composition according to any one of (I-1) to (I-4), wherein the subcritical water treatment step in step 2 is carried out in the presence of an emulsifier, and the emulsifier is at least gum ghatti. (I-6) The production method according to any one of (I-1) to (I-5), wherein the subcritical water treatment step of step 2 is a step of treating the pulverized mixture prepared in step 1 for 0.1 to 60 seconds at a temperature of 158 to 240°C and under a pressure equal to or greater than the saturated water vapor pressure. (I-7) The production method according to any one of (I-1) to (I-6), wherein both the pulverization step of step 1 and the subcritical water treatment step of step 2 are treatment steps carried out under conditions in which no organic solvents or oils or fats are present. (I-8) The production method according to any one of (I-1) to (I-7), wherein the carotene-containing composition prepared in step 3 contains 13-cis beta-carotene, 9-cis beta-carotene, and all-trans beta-carotene, and the proportion of all-trans beta-carotene relative to the total amount of these components (100% by mass) is 50% by mass or more. (I-9) The production method according to any one of (I-1) to (I-8), further comprising a step (step 4) of drying the carotene-containing composition prepared in step 3.

[0017] (II) Carotene-containing composition (II-1) A carotene-containing composition containing spherical carotene particles, having the following characteristics: The median diameter (D ５０ ) is 0.15 μm or more and 0.55 μm or less, the proportion of carotene particles having a particle size of more than 1.3 μm is 17% or less per 100% of the total volume of carotene particles on a volume basis, and the color tone of an aqueous solution of the carotene-containing composition adjusted to a carotene concentration of 10 ppm is L ＊ a ＊ b＊ In the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ (II-2) A carotene-containing composition produced by any one of the production methods (I-1) to (I-9), wherein the carotene-containing composition is adjusted with water to a carotene concentration of 10 ppm, and the color tone of an aqueous solution of the carotene-containing composition is L ＊ a ＊ b ＊ When evaluated in the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ The carotene-containing composition is characterized in that the lightness L of an aqueous solution adjusted to a carotene concentration of 10 ppm is 40 to 52. (II-3) The carotene-containing composition is characterized in that the lightness L of an aqueous solution adjusted to a carotene concentration of 10 ppm is 40 to 52. ＊ The carotene-containing composition according to (II-1) or (II-2), having a chroma C value of 70 to 85, preferably 73 to 80, and more preferably 75 to 80. (II-4) The carotene-containing composition according to any one of (II-1) to (II-3), having a chroma C value of 50 to 65, preferably 53 to 62, and more preferably 53 to 60, of an aqueous solution adjusted to a carotene concentration of 10 ppm. (II-5) The carotene-containing composition according to any one of (II-1) to (II-4), containing 13-cis beta-carotene, 9-cis beta-carotene, and all-trans beta-carotene, wherein the proportion of all-trans beta-carotene relative to the total amount of these components (100% by mass) is 50% by mass or more. (II-6) The carotene-containing composition according to any one of (II-1) to (II-5), which is used as an additive for foods and beverages, cosmetics, pharmaceuticals, and / or quasi-drugs. (II-7) The carotene-containing composition according to (II-6), wherein the additive is a pigment preparation. (II-8) The carotene-containing composition according to any one of (II-1) to (II-7), wherein the additive is a solid formulation.

[0018] (III) Compositions colored with a carotene-containing composition (III-1) A colored composition comprising the carotene-containing composition according to any one of (II-1) to (II-8). (III-2) The colored composition according to (III-1), wherein the colored composition is a food or beverage, cosmetic, pharmaceutical, or quasi-drug. (III-3) The colored composition according to (III-1), wherein the colored composition is an aqueous food or beverage, cosmetic, pharmaceutical, or quasi-drug.

[0019] According to the present invention, it is possible to provide a carotene-containing composition having a specific color similar to that of CI FOOD YELLOW 3 (Sunset Yellow FCF, CAS RN: 2783-94-0) (Disodium 6-hydroxy-5-(4-sulfonatophenylazo)-2-naphthalene-sulfonate), and a method for producing the same. Specifically, the color of an aqueous solution of the carotene-containing composition, which is adjusted with water to a carotene concentration of 10 ppm, is measured using a method similar to that of the carotene-containing composition described above. ＊ a ＊ b ＊ When evaluated in the color space color system, the hue angle θ is 50° to 65°a ＊ Values ​​are 20 to 40, and b ＊ The present invention provides a carotene-containing composition having a value of 40 to 52, and a method for producing the same.

[0020] Furthermore, according to the present invention, it is possible to provide a carotene-containing composition that has the above-mentioned specific color tone and also has emulsion stability (storage stability), turbidity, UHT sterilization resistance, acid resistance, salt resistance, and / or shaking resistance, and a method for producing the same.

[0021] Furthermore, according to the production method of the present invention, the carotene-containing composition having the above-mentioned properties can be produced by a continuous and simple operation without using organic solvents and / or oils and fats.

[0022] 1 shows transmission electron microscope images confirming the shape of carotene in the ground mixture 2 (left image) before critical water treatment and the carotene-containing composition (Example 2) (right image) after the ground mixture 2 was subjected to critical water treatment.

[0023] (I) Carotene-containing composition and its manufacturing method The carotene-containing composition of the present invention (hereinafter also referred to as "the present carotene-containing composition") contains carotene and is a composition that can be added and blended during the production of foods and beverages, cosmetics, quasi-drugs, and / or pharmaceuticals. In other words, it is a composition that can be used as an additive during the production of foods and beverages, cosmetics, quasi-drugs, and / or pharmaceuticals. The composition is an edible composition at least when used as an additive for foods and beverages, or oral cosmetics, quasi-drugs, and / or pharmaceuticals.

[0024] Carotenes are known to include α-carotene, β-carotene, γ-carotene, and lycopene. The carotene targeted by the present invention is β-carotene. However, this does not limit the coexistence of α-carotene, γ-carotene, and / or lycopene with β-carotene in the carotene-containing composition, as long as the effects of the present invention are not impaired. However, even when these carotenes coexist, the proportion of β-carotene is 96% by mass or more when the total amount of α-carotene, β-carotene, γ-carotene, and lycopene is 100% by mass.

[0025] It is known that β-carotene exists in multiple cis-trans stereoisomers, including all-trans β-carotene, 9-cis β-carotene, 13-cis β-carotene, 15-cis β-carotene, 9,13-disis β-carotene, and 9,13'-disis β-carotene. The carotene-containing composition may contain at least all-trans β-carotene as β-carotene, provided that other stereoisomers are present. In this case, preferred examples of β-carotene other than all-trans β-carotene include 9-cis β-carotene and 13-cis β-carotene. When the total amount of all-trans β-carotene, 9-cis β-carotene, and 13-cis β-carotene is taken as 100% by mass, the proportion of all-trans β-carotene is 50% by mass or more and less than 100% by mass, preferably 75% by mass or more and less than 100% by mass.

[0026] When the carotene-containing composition is prepared using distilled water to give an aqueous solution with a carotene concentration of 10 ppm (0.001% by mass), the color of the aqueous solution (10 ppm) is L ＊ a ＊ b ＊ When evaluated in the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ The carotene is characterized by an intermediate color between red and yellow, specified by a color value of 40 to 52. Note that the term "aqueous solution" does not strictly mean that the carotene is completely dissolved in water. The term "aqueous solution" is used to encompass a liquid in which the carotene is dispersed in water.

[0027] In this specification, the expression "0 to △" (O and △ are arbitrary numbers, provided that △>O) means a range of "not less than 0 and not more than △."

[0028] Preferred hue angles θ, a ＊ value, and b ＊ The value ranges are as follows: Hue angle θ: preferably 50° to 62°, more preferably 52° to 62°, even more preferably 53° to 62°, and even more preferably 53° to 61°. ＊ Value: preferably 22 to 40, more preferably 22 to 36, even more preferably 23 to 35, even more preferably 24 to 35, even more preferably 25 to 35. ＊ Value: preferably 40 to 51, more preferably 41 to 51, even more preferably 42 to 50, even more preferably 42 to 49, and even more preferably 42 to 48. ＊ value, and b ＊ Any combination of values ​​can be selected.

[0029] Specifically, the hue angle θ, a ＊ value, and b ＊ The combination of values ​​includes all the combinations shown in Table 1.

[0030]

[0031] The combination includes a hue angle θ, a ＊ value, and b ＊This includes a mode in which all values ​​are combined in the same column, but it may also be a mode in which values ​​are combined in different columns.

[0032] For example, when the hue angle θ is in the range of one column, a ＊ The value is one column, and b ＊ The value is any combination selected from columns 2 to 6; ＊ The values ​​are in two columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are three columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are four columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 5 columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 6 columns, and b ＊ The values ​​can be any combination selected from columns 1-6.

[0033] When the hue angle θ is in the range of two columns, a ＊ The value is one column, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are in two columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are three columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are four columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 5 columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 6 columns, and b ＊ The values ​​can be any combination selected from columns 1-6.

[0034] When the hue angle θ is in the range of three columns, a ＊ The value is one column, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are in two columns, and b＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are three columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are four columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 5 columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 6 columns, and b ＊ The values ​​can be any combination selected from columns 1-6.

[0035] When the hue angle θ is in the range of four columns, a ＊ The value is one column, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are in two columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are three columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are four columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 5 columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 6 columns, and b ＊ The values ​​can be any combination selected from columns 1-6.

[0036] When the hue angle θ is in the range of 5 columns, a ＊ The value is one column, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are in two columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are three columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are four columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 5 columns, and b＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 6 columns, and b ＊ The values ​​can be any combination selected from columns 1-6.

[0037] When the hue angle θ is in the range of 6 columns, a ＊ The value is one column, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are in two columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are three columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are four columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 5 columns, and b ＊ The value is any combination selected from columns 1 to 6; ＊ The values ​​are 6 columns, and b ＊ The values ​​can be any combination selected from columns 1-6.

[0038] The carotene-containing composition is L ＊ a ＊ b ＊ In the color space color system, the color tone of the aqueous solution (10 ppm) is as described above, and the L ＊ The value is not particularly limited, but is preferably 70 to 85, more preferably 72 to 83, and even more preferably 74 to 81. The C value, which indicates saturation, is also not particularly limited, but is preferably 45 to 65, more preferably 46 to 63, more preferably 46 to 62, even more preferably 46 to 61, even more preferably 47 to 60, and even more preferably 50 to 60.

[0039] In the carotene-containing composition, the carotene described above has a median diameter (D 50 ) 0.15 to 0.55 μm spherical particles. Median diameter (D 50 ) is preferably 0.15 to 0.4 μm, more preferably 0.2 to 0.4 μm, and even more preferably 0.2 to 0.3 μm.

[0040] In the present invention, the median diameter (D 50 ) refers to the particle size at 50% of the cumulative value in the particle size distribution (volume basis) determined by the laser diffraction / scattering method. The particle size at 50% of the cumulative value is the particle size at which the number of particles reaches 50% of the total number of particles when the number of particles is counted from the smallest particle size. ５０ Also called "value."

[0041] The spherical shape of the carotene particles contained in the carotene-containing composition can be confirmed by a microscope such as an optical microscope or a transmission electron microscope. In the present invention, "spherical" does not mean a strict shape such as a perfect sphere, but means a round shape like a ball. Irregular shapes whose shape cannot be specified are excluded.

[0042] The carotene-containing composition preferably contains a small proportion of coarse particles. Here, "coarse particles" refers to particles with a particle diameter of more than 1.3 μm. The particle diameter here is determined by a volumetric basis using a laser diffraction / scattering method.

[0043] The proportion of coarse particles contained in the present carotene-containing composition (by volume) is preferably 0 to 17% relative to 100% of the total volume of carotene particles. It is preferably 0 to 15%, and more preferably 0 to 10%. A low proportion of coarse particles of 17% or less reduces the risk of precipitation or ring formation, and emulsion stability can be maintained. Furthermore, a low proportion of coarse particles of 17% or less can impart a desired turbidity to the present carotene-containing composition. The turbidity of the present carotene-containing composition is related to color development and coloring effects. The present carotene-containing composition having a desired turbidity can enhance the coloring effect on target objects such as beverages.

[0044] (II) Method for Producing the Carotene-Containing Composition The carotene-containing composition described above can be produced by a method comprising the following steps: Step 1: Carotene crystals are grown in the presence of water and an emulsifier to a size smaller than the median diameter (D 50Step 1: wet-pulverizing the pulverized mixture prepared in Step 1 until the median diameter (D) is 0.55 μm or less to prepare a slurry-like pulverized mixture (pulverization step); Step 2: subcritical water-treating the pulverized mixture prepared in Step 1 to prepare a subcritical water-treated pulverized mixture (subcritical water treatment step); Step 3: cooling the subcritical water-treated pulverized mixture prepared in Step 2 to obtain a pulverized mixture having a median diameter (D 50 2.) A step of preparing a carotene-containing composition having spherical particles of 0.15 to 0.55 μm (cooling step). By the cooling step of step 3, a carotene-containing composition in which spherical particles of fat-soluble carotene are dispersed in water is prepared.

[0045] The carotene-containing composition prepared in step 3 can be further subjected to the following step 4, if necessary. A dried, solid carotene-containing composition can be prepared by step 4. Step 4: A step of preparing a solid carotene-containing composition by subjecting the carotene-containing composition prepared in step 3 to a drying treatment. Therefore, the present method for producing a carotene-containing composition is characterized by having steps 1 to 3 or steps 1 to 4.

[0046] Each of these steps will be explained below. (Step 1) Crushing Step In step 1, the raw material carotene crystals are crushed in the presence of water and an emulsifier to a size smaller than the median diameter (D 50 This process involves wet pulverizing the particles until the median diameter (D 50 A slurry composition can be prepared in which carotene crystals, which have been crushed to a particle size of 0.55 μm or less, are dispersed in an emulsifier and water.

[0047] The carotene crystals used as the raw material are solid carotenes, primarily composed of β-carotene. However, as described above, α-carotene, γ-carotene, and / or lycopene may be contained in addition to β-carotene, as long as the effects of the present invention are not impaired. The β-carotene is preferably all-trans-β-carotene, but may also contain other stereoisomers (9-cis-β-carotene, 13-cis-β-carotene, 15-cis-β-carotene, 9,13-disis-β-carotene, and 9,13'-disis-β-carotene, etc.). The β-carotene other than all-trans-β-carotene is preferably 9-cis-β-carotene and 13-cis-β-carotene. In this case, the proportion of all-trans-β-carotene can be 50% by mass or more, assuming that the total amount of all-trans-β-carotene, 9-cis-β-carotene, and 13-cis-β-carotene is 100% by mass. The content is preferably 75% by mass or more and less than 100% by mass, and more preferably 75% by mass or more and 99% by mass.

[0048] The raw material carotene crystals can be produced by known methods such as chemical synthesis, fermentation, and extraction from plants or algae. １４ , C １６ , C １９ Two molecules of aldehyde are bonded by Grignard reaction to form β-C ４０ This method produces β-carotene by converting it into a diol, dehydrating it, and then hydrogenating it to produce β-carotene. In Japan, β-carotene with a content of 96% or more produced by chemical synthesis is approved for use as a designated additive in pharmaceuticals, quasi-drugs, and food and beverages. The fermentation method produces β-carotene by co-fermenting two non-pathogenic and non-toxic fungi (Blakeslea trispora) in a specific ratio. β-carotene extracted from plants is also called extracted carotene, and examples include Dunaliella carotene prepared from the whole algae of Dunaliella, carrot carotene prepared from carrot roots, and palm oil carotene prepared from the fruit of the oil palm.

[0049] These carotene crystals are commercially available. Preferably, the β-carotene content is as high as 96% by mass or more, and carotene prepared by chemical synthesis or fermentation can be suitably used.

[0050] The emulsifier may be any edible emulsifier capable of improving the dispersibility of the pulverized material obtained by the pulverization process, and examples thereof include gum ghatti, low-molecular-weight gum ghatti, gum arabic (including modified gum arabic), and modified starch. These may be used alone or in any combination of two or more. Gum ghatti, low-molecular-weight gum ghatti, and gum arabic (including modified gum arabic) are preferred, and gum ghatti is more preferred. Gum ghatti is heat-resistant and therefore is not affected by decomposition or the like by the subcritical water treatment at high temperatures in Step 2 described below, and can continue to exert its effect as an emulsifier in Step 2.

[0051] Gum ghatti is a water-soluble polysaccharide prepared by drying and solidifying the sap secreted from cracks in the trunk of Anogeissus latifolia Wall. (Combretaceae). The water-soluble polysaccharide is composed of arabinose, galactose, mannose, xylose, and glucuronic acid, and contains approximately 3% by mass of protein, forming a polysaccharide-protein complex. For convenience, it is also called "native gum ghatti" to distinguish it from the low-molecular-weight gum ghatti described below. The weight-average molecular weight of this gum ghatti (native gum ghatti) is usually 0.6 x 10 ６ ~2 x 10 ６ , preferably 0.8×10 ６ ~2 x 10 ６ , more preferably 0.8×10 ６ ~1.2 × 10 ６ Such gum ghatti is commercially available, and examples of commercially available gum ghatti products include "Gutti Gum SD" manufactured by San-Ei Gen F.F.I. Co., Ltd.

[0052] Low-molecular-weight gum ghatti is gum ghatti obtained by subjecting the aforementioned gum ghatti to thermal decomposition, acid decomposition, and / or enzymatic decomposition, etc. The weight-average molecular weight of low-molecular-weight gum ghatti is not limited, but may be, for example, 0.020 × 10 ６ ~0.60 x 10 ６ Preferably, it can be less than 0.025×10 ６ ~0.50 x 10 ６ , more preferably 0.030 × 10 ６ ~0.40 x 10 ６ , more preferably 0.030 × 10 ６ ~0.35 x 10 ６ , and even more preferably 0.040 x 10 ６ ~0.35 x 10 ６ Low molecular weight gum ghatti can be prepared using the above-mentioned gum ghatti as a raw material, for example, according to the methods described in Japanese Patent No. 7358063 (Patent Document 8), Japanese Patent No. 7128461 (Patent Document 9), or Japanese Patent No. 7080818 (Patent Document 10), without being limited thereto.

[0053] The molecular weight and molecular weight distribution of gum ghatti and low molecular weight gum ghatti are measured by the following method. [Method for measuring molecular weight and molecular weight distribution] The molecular weight and molecular weight distribution are measured by GPC analysis under the following conditions: Detector: RI Mobile phase: 100 mM K2SO4 Flow rate: 1.0 ml / min Temperature: 40°C Column: TSKgel GMPWXL 30 cm (Guard PWXL) Injection: 100 μl Pullulan standard: Shodex STANDARD P-82.

[0054] Gum arabic is a polysaccharide obtained from the sap of Acacia plants (e.g., Acacia Senegal and Acacia Seyal), which are legumes. The molecular structure of gum arabic has not been fully elucidated, but it is known to contain galactose, arabinose, rhamnose, and glucuronic acid as its constituent sugars. Gum arabic is commercially available, and examples of such products include "Gum Arabic SD" manufactured by San-Ei Gen F.F.I. Co., Ltd.

[0055] The gum arabic may be modified gum arabic obtained by modifying the gum arabic. Modified gum arabic has a higher weight-average molecular weight and arabinogalactan protein content than regular gum arabic, and is therefore superior in emulsifying properties. The modified gum arabic has a weight-average molecular weight of 1.5 million or more, or an arabinogalactan protein content of 17% by weight or more. The weight-average molecular weight and arabinogalactan protein content of gum arabic can be determined by gel permeation chromatography (GPC-MALLS) using a multi-angle light scattering (MALLS) spectrophotometer and an RI (refractive index) detector connected online. Modified gum arabic is commercially available, and examples of such products include "SUPER GUM (trademark)" from San-Ei Gen F.F.I., Inc.

[0056] The modified starch that can be used is commercially available, for example, "Purity Gum BE" manufactured by Ingredion.

[0057] The pulverization treatment is carried out by pulverizing the raw material carotene crystals in the presence of the emulsifier and water using a known pulverization method, for example, a pulverization device such as a ball mill or a bead mill, to a median diameter (D 50 The temperature conditions during wet grinding may be any temperature at which the raw material carotene crystals can be ground in a solid state without melting, and are usually set and adjusted within the range of 0 to 80°C, preferably 5 to 60°C, and more preferably 15 to 40°C.

[0058] The median diameter of the crushed carotene crystals is not limited as long as it is 0.55 μm or less, but is preferably 0.15 to 0.5 μm, more preferably 0.2 to 0.4 μm, and even more preferably 0.2 to 0.3 μm.

[0059] The ratio of water to 1 part by mass of raw carotene crystals is not limited, but can typically be set in the range of 1 to 10,000 parts by mass. It is preferably 10 to 1,000 parts by mass, more preferably 15 to 1,000 parts by mass, and particularly preferably 15 to 500 parts by mass. If the water ratio is lower than the above-mentioned normal ratio, the viscosity of the ground mixture will increase significantly, which may significantly reduce handling in the grinding treatment, subcritical water treatment, and / or cooling treatment steps, and may cause problems such as scorching and pipe clogging during the subcritical water treatment. On the other hand, if the water ratio is higher than the above-mentioned normal ratio, the carotene concentration in the carotene-containing composition obtained by production will be too low, resulting in problems such as requiring a large amount to be used or requiring concentration upon use, which is undesirable.

[0060] The ratio of emulsifier to 100 parts by mass of raw carotene crystals is not limited, but can typically be set in the range of 1 to 100,000 parts by mass. It is preferably 50 to 10,000 parts by mass, more preferably 50 to 5,000 parts by mass, and particularly preferably 50 to 3,000 parts by mass. If the emulsifier ratio is lower than the above-mentioned normal ratio, dispersion stability cannot be imparted to the pulverized carotene particles, and problems such as aggregation and precipitation may occur. On the other hand, if the emulsifier ratio is higher than the above-mentioned normal ratio, the viscosity of the pulverized mixture increases significantly, significantly reducing handling in the pulverization, subcritical water treatment, and / or cooling processes, and causing problems such as scorching and pipe clogging during the subcritical water treatment. The emulsifier is typically used in a state dissolved in water to the above-mentioned ratio.

[0061] The grinding process can also be carried out in the presence of a stabilizing component, such as an antioxidant or preservative, in addition to the water and emulsifier, as long as the effects of the present invention are not impaired. Examples of components with antioxidant activity include antioxidants that can be incorporated into foods and beverages, such as vitamin E (tocopherol, tocotrienol), butylated hydroxytoluene, butylated hydroxyanisole, vitamin C and its derivatives (ascorbic acid, ascorbate, ascorbyl palmitate), BHT, BHA, enzyme-modified isoquercitrin, bayberry extract, and sunflower seed extract. Examples of components with preservative activity include preservatives that can be incorporated into foods and beverages, such as propylene glycol, glycerin, ethanol, benzoic acid, benzoates, parahydroxybenzoic acid esters, sorbic acid, and sorbates.

[0062] Furthermore, the pH of the composition to be subjected to the grinding treatment is not limited, but is in the range of pH 2 to 6, and preferably pH 3 to 5. In order to adjust the pH of the composition during grinding to fall within this range, the raw material carotene crystals can be blended with, in addition to water and an emulsifier, an edible organic acid such as citric acid, malic acid, tartaric acid, acetic acid, lactic acid, phosphoric acid, ascorbic acid, or phytic acid.

[0063] After the pulverization treatment, the prepared pulverized mixture in a slurry state can be subjected to a homogenization treatment (homogenization treatment) as needed. By performing the homogenization treatment, the carotene crystal powder that has aggregated in the pulverized mixture can be uniformly dispersed. The homogenization treatment can be carried out by a method known per se, for example, using a high-pressure homogenizer.

[0064] (Step 2) Subcritical Water Treatment Step Step 2 is a step (subcritical water treatment step) in which the slurry-like ground mixture containing the carotene crystals (ground product) prepared in Step 1, water, and an emulsifier is subjected to subcritical water treatment to prepare a subcritical water-treated product.

[0065] During the subcritical water treatment, a new emulsifier may be added to the pulverized mixture obtained in step 1. Since emulsifiers other than gum ghatti have low heat resistance, it is preferable to add gum ghatti newly during the subcritical water treatment, particularly when an emulsifier other than gum ghatti is used in step 1. Even when gum ghatti is used in step 1, gum ghatti may be added in step 2 as needed. In this case, the amount of gum ghatti added can be appropriately selected from the range of 0.1 to 5,000 parts by mass per 100 parts by mass of carotene in the pulverized mixture. Furthermore, the concentration in 100% by mass of the pulverized mixture can be selected from the range of 0.1 to 50% by mass.

[0066] In the present invention, the subcritical water treatment is a treatment in which the slurry-like pulverized mixture prepared in step 1 is heated under conditions of a high temperature of 100°C or higher but lower than the critical temperature of water, and a high pressure of equal to or higher than the saturated water vapor pressure.

[0067] When the pressure of water is raised to 22.1 MPa and the temperature to 374.2°C, it reaches a state that is neither liquid nor gas. This point is called the critical point of water, and the pressure is called the critical pressure and the temperature is called the critical temperature. Hot water that is at a high temperature above 100°C but below the critical temperature and above the saturated water vapor pressure is called subcritical water, and this state is called the subcritical water state.

[0068] In the present invention, the subcritical water treatment can be carried out by placing the slurry-like pulverized mixture to be treated in a heat-resistant and pressure-resistant container made of metal, ceramics, etc., sealing the container, and heating and pressurizing the pulverized mixture so that the water in the pulverized mixture becomes subcritical. Although not limited thereto, the subcritical water treatment can be carried out using various commercially available heat sterilization devices.

[0069] The temperature used in subcritical water treatment is set so that carotene crystals melt and the median diameter (D 50 ) The temperature can be set in the range of 158 to 240°C, preferably 160 to 240°C, because spherical particles of 0.15 to 0.55 μm can be efficiently obtained. The temperature is more preferably in the range of 160 to 220°C, even more preferably in the range of 160 to 200°C, and particularly preferably in the range of 160 to 180°C.

[0070] The pressure used in the subcritical water treatment is not particularly limited, as long as it is equal to or greater than the saturated vapor pressure at each temperature employed in the subcritical water treatment. For example, the pressure can be set within the range of 0.1 MPa to 30 MPa. The range is preferably 0.2 MPa to 20 MPa, more preferably 0.3 MPa to 15 MPa, particularly preferably 0.5 MPa to 10 MPa, and even more preferably 1.0 MPa to 5.0 MPa. If the pressure in the subcritical water treatment is significantly lower than 0.1 MPa, the water tends to boil and not be heated sufficiently, which is undesirable. Furthermore, if the pressure in the subcritical water treatment is increased to a level significantly higher than 30 MPa, the equipment used must have a high level of pressure resistance, which is undesirable as it incurs excessive costs.

[0071] Although the subcritical water treatment time varies depending on the amount of the ground mixture to be treated, the temperature, and the pressure conditions, it is usually preferably carried out for 0.1 to 60 seconds (the holding time after the temperature and pressure of the subcritical water treatment are reached). The time is preferably 0.1 to 40 seconds, and more preferably 1 to 40 seconds. If the treatment time is shorter than 0.1 second, a sufficient color change will not occur, while if the treatment time is too long, exceeding 60 seconds, carotene and gum ghatti may be decomposed.

[0072] From the above, suitable conditions for the subcritical water treatment of the pulverized mixture can be exemplified as a temperature of 158 to 180°C, a pressure of 0.1 to 5.0 MPa (however, not less than the saturated vapor pressure at the temperature where the subcritical water treatment is performed), and a treatment time of 0.1 to 60 seconds.

[0073] By such subcritical water treatment, a subcritical water treatment product can be obtained in a state where fine emulsified particles of dissolved carotene are dispersed in water (carotene-water dispersion). This state includes an emulsion state.

[0074] (Step 3) Cooling Step In step 3, the subcritical water treated product prepared in step 2 is cooled to reduce the median diameter (D 50 ) is a step for preparing a carotene-containing composition having spherical particles of 0.15 to 0.55 μm.

[0075] The cooling treatment can be carried out by cooling the high-temperature subcritical water treated product prepared in step 2 to a temperature of 100°C or less. The preferred temperature condition is 5 to 60°C, more preferably room temperature (25°C ± 5°C). Thus, the median diameter (D 50 A carotene-containing composition can be obtained in a state where carotene fine particles having a particle size of 0.15 to 0.55 μm are stably dispersed in water (carotene-water dispersion). This state includes an emulsion state.

[0076] The median diameter (D 50 ) is 0.15 to 0.55 μm as described above. Although there is no particular limitation within this range, it is preferably 0.15 to 0.4 μm, more preferably 0.2 to 0.3 μm. Here, the median diameter (D 50 The definition, measurement method, and method for confirming that the particles are spherical are as described above.

[0077] The cooling treatment can be carried out using, but is not limited to, a double-pipe heat exchanger, a multi-pipe heat exchanger, a plate-type heat exchanger, a coil-type heat exchanger, or the like.

[0078] The carotene-containing composition thus prepared can be used as it is in the form of a carotene-water dispersion or emulsion, but may also be prepared as a semi-solid or solid preparation by concentrating or drying, if necessary.

[0079] (Step 4) Drying Step Step 4 is a step of preparing a solid carotene-containing composition by subjecting the carotene-containing composition prepared in Step 3 to a drying treatment. The drying treatment can be carried out by a method known per se, such as forced air drying, spray drying, freeze drying, vacuum drying, or fluidized bed drying, as long as it does not impair the effects of the present invention.

[0080] In the drying process, in order to increase the stability of carotene against oxidative degradation, antioxidants such as vitamin E (tocopherol, tocotrienol), butylated hydroxytoluene, butylated hydroxyanisole, vitamin C and its derivatives (ascorbic acid, ascorbate, ascorbyl palmitate), BHT, BHA, or enzyme-treated isoquercitrin, bayberry extract, sunflower seed extract, etc., and stabilizers such as cyclodextrin may be added and blended in addition to the carotene-containing composition.

[0081] The carotene-containing composition in a solid form thus prepared can be further prepared into a desired dosage form (e.g., powder, granules, tablets, etc.), preferably, but not limited to, a formulation in a powder form (powder formulation).

[0082] The carotene-containing composition can be produced by a series of steps, namely, steps 1 to 3 or steps 1 to 4. These steps are preferably treatment steps that do not use organic solvents or fats or oils.

[0083] Organic solvents include water-miscible and water-immiscible organic solvents. Water-miscible solvents are water-miscible, heat-stable, volatile solvents containing only carbon, hydrogen, and oxygen, such as alcohols, ethers, esters, ketones, and acetals. More specifically, they are at least 10% water-miscible, have a boiling point below 200°C, and / or have fewer than 10 carbon atoms, including methanol, ethanol, n-propanol, isopropanol, 1,2-butanediol 1-methyl ether, 1,2-propanediol, 1-n-propyl ether, tetrahydrofuran, and acetone.

[0084] Water-immiscible organic solvents are organic solvents that have a solubility in water of less than 10% at atmospheric pressure, and include, for example, halogenated aliphatic hydrocarbons (e.g., methylene chloride, chloroform, and carbon tetrachloride), carboxylic acid esters (e.g., dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl formate, methyl acetate, ethyl acetate, and isopropyl acetate), and ethers (e.g., methyl tert-butyl ether).

[0085] Fats and oils include solid fats (e.g., meat fat and lard) and oils that are liquid at room temperature (e.g., vegetable oils such as sesame oil, corn oil, cottonseed oil, soybean oil, and peanut oil), as well as esters of medium-chain vegetable fatty acids.

[0086] The carotene-containing composition thus prepared has the composition and properties described in (I).

[0087] Specifically, the carotene-containing composition contains 0.01 to 10% by mass of β-carotene, which contains at least 13-cis β-carotene, 9-cis β-carotene, and all-trans β-carotene, and is characterized in that the proportion of all-trans β-carotene relative to the total amount (100% by mass) of these components is 50% by mass or more, preferably 75% by mass or more but less than 100% by mass, and more preferably 75% by mass or more but less than 99% by mass.

[0088] Furthermore, when the carotene-containing composition is dissolved (including dispersed) in water (distilled water) so that the carotene concentration becomes 10 ppm, the color is L ＊ a ＊ b ＊ In the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ The color is characterized by a red to yellow (neutral color) having a value of 40 to 52. ＊ and a chroma C value of 45 to 65, particularly 50 to 65.

[0089] Furthermore, as shown in the experimental examples described later, the carotene-containing composition is characterized by excellent emulsion stability, turbidity, acid resistance, salt resistance, shaking resistance, UHT sterilization resistance, and / or light resistance. Here, the methods for evaluating emulsion stability, turbidity, acid resistance, salt resistance, shaking resistance, UHT sterilization resistance, and / or light resistance, and their definitions, are explained in the experimental examples described later, and the descriptions therein can be used as a reference.

[0090] The carotene-containing composition can be used as an ingredient in foods and beverages, cosmetics, pharmaceuticals, or quasi-drugs. As described above, the carotene-containing composition has a neutral color between red and yellow and is excellent in emulsion stability, turbidity, acid resistance, salt resistance, shaking resistance, UHT sterilization resistance, and / or light resistance, and therefore can be suitably used as a colorant preparation (colorant, pigment) for foods and beverages, cosmetics, pharmaceuticals, or quasi-drugs.

[0091] When used as a colorant (coloring agent, pigment), the carotene concentration of the carotene-containing composition can be adjusted appropriately depending on the intended use of coloring so that the carotene concentration is in the range of 1 to 100 ppm. The carotene concentration of the carotene-containing composition is preferably 1 to 30 ppm, more preferably 5 to 20 ppm.

[0092] In addition to the carotene and emulsifier or antioxidant described above, the carotene-containing composition may also contain excipients, disintegrants, binders, surfactants, wetting agents, lubricants, pH adjusters, preservatives, or fragrances, etc., to the extent that the effects of the present invention are not impaired.

[0093] (II) Compositions Colored with the Carotene-Containing Composition The carotene-containing composition has excellent acid resistance even under acidic conditions of pH 4.5 or less, and can therefore be suitably used to color various compositions without being limited by the pH of the composition to be colored. In particular, the carotene-containing composition can be suitably used to color compositions with a pH of 2 to 4, particularly compositions with a pH of 2 to 3.5.

[0094] The composition to be colored (colored composition) is not particularly limited. Examples include foods and beverages, cosmetics, quasi-drugs, and pharmaceuticals. Acidic foods and beverages with a pH of 4.5 or less and edible compositions used in the production of such foods and beverages are preferred.

[0095] Foods and beverages that can be colored with the present carotene-containing composition are not particularly limited, and examples thereof include beverages (including soft drinks, carbonated drinks, lactic acid drinks, and dairy drinks), frozen desserts, desserts (e.g., jelly, bavarois, yogurt, etc.), sugar confectioneries (e.g., candy, gummies, etc.), chewing gum, jam, soup, pickles, and seasonings (e.g., dressings, sauces, etc.). Particularly preferred foods and beverages are beverages, desserts, and sugar confectioneries. Because beverages, desserts, sugar confectioneries, and other foods and beverages often have a pH of around 3, it has been difficult to stably color them using conventional carotene pigments. Furthermore, beverages, desserts, and sugar confectioneries often have high transparency, and the formation of aggregates is likely to directly lead to a decrease in commercial value. In contrast, the present carotene-containing composition, particularly the present carotene-containing composition prepared using an emulsifier other than modified starch, significantly suppresses carotene aggregation or precipitation and adhesion to plastic containers such as PET, even in foods and beverages with a pH of 3.5 or less, and allows the target foods and beverages to be stably colored to the desired color tone.

[0096] The food and drink to be colored by the present carotene-containing composition preferably includes acidic drinks (for example, carbonated drinks, non-carbonated drinks, and alcoholic drinks).

[0097] The amount of the carotene-containing composition added to the composition to be colored (composition to be colored) can be adjusted appropriately depending on the type and purpose of the composition. For example, it is desirable to add the carotene-containing composition so that the carotene content in the composition to be colored is 0.01 to 0.2% by mass.

[0098] The coloring method of the present invention can be carried out by adding the present carotene-containing composition to a composition to be colored and mixing them. Because the present carotene-containing composition has the desired turbidity, acid resistance, salt resistance, and UHT sterilization resistance, the timing of addition of the colorant preparation or the manufacturing method is not limited, and the composition can be colored by a method similar to or different from conventional carotene pigments.

[0099] As described above, in this specification, the terms "comprise" and "contain" encompass the meanings of "consist of" and "consist essentially of."

[0100] The present invention will be described below using experimental examples to aid in understanding the configuration and effects of the present invention. However, the present invention is not limited by these experimental examples. Unless otherwise specified, the following experiments were carried out at room temperature (25±5°C) and atmospheric pressure. Unless otherwise specified, "%" and "parts" in the following descriptions mean "% by mass" and "parts by mass," respectively.

[0101] The materials used in the following experimental examples are as follows. Raw carotene (carotene crystals): San-Ei Gen F.F.I. Beta-carotene content: 97% by mass. Contains 13-cis beta-carotene, 9-cis beta-carotene, and all-trans-beta-carotene, with the proportion of all-trans-beta-carotene relative to the total amount (100% by mass) of these. Gum ghatti: Gum ghatti SD (manufactured by San-Ei Gen F.F.I.), weight-average molecular weight: 800,000. Low-molecular-weight gum ghatti: Prepared according to the manufacturing method described in Example 13 of Japanese Patent No. 7358063. Weight-average molecular weight: 150,000. Gum arabic: SUPER GUM (trademark) (manufactured by San-Ei Gen F.F.I.) Modified starch: Purity Gum BE (manufactured by Ingredion)

[0102] The measurement and testing methods used in the following experimental examples are as follows: (1) Particle size distribution and median diameter (D 50 Measurement of the median diameter (D) of carotene crystals in the milled mixture 50 : μm), and the median diameter of carotene particles in the carotene-containing composition (D 50 The refractive index (refractive index: 1.81, measurement range: 0.021 to 2000 μm, particle size distribution: volume basis) was measured using a laser diffraction particle size distribution analyzer Microtrac MT-3000II (Microtrac Bell).

[0103] (2) Method for calculating the proportion of coarse particles (particles with a particle diameter exceeding 1.3 μm) The proportion (%) of coarse particles in a carotene-containing composition was measured using a laser diffraction particle size distribution analyzer, Microtrac MT-3000II (manufactured by Microtrac Bell) (refractive index: 1.81, measurement range: 0.021 to 2000 μm, particle size distribution: volume basis), and calculated from the obtained particle size distribution data. Specifically, in the cumulative volume distribution of the measured particle size distribution data, the volume percentage of the range with a particle diameter exceeding 1.3 μm was confirmed, and the proportion of that volume to the total was calculated as the proportion (%) of coarse particles.

[0104] (3) Color Tone Evaluation Test of Carotene-Containing Composition The carotene-containing composition to be tested was uniformly diluted (dissolved and dispersed) with distilled water so that the carotene concentration was 10 ppm, and the L ＊ a ＊ b ＊ The values ​​were measured, and the hue angle θ and saturation C value were calculated under the following conditions: Colorimetry: Reflection measurement (L*a*b*) Hue angle θ (+,+): tan-1 (b / a) Saturation C: √(a2 + b2).

[0105] (4) Measurement of Carotene Content A predetermined amount of the carotene-containing composition to be tested (sample weight) was weighed out and diluted with water to a predetermined dilution ratio, and then acetone was added to dissolve the carotene. This was then subjected to a spectrophotometer (JASCO Corporation, Spectrophotometer V-660) to measure the absorbance at the maximum absorption wavelength (455 nm). The carotene content (%) was calculated from the obtained absorbance using the following formula: [Formula] Carotene content (%) = [Absorbance × Dilution ratio] / [2450 × sample weight (g)]

[0106] (5) Component Analysis (Quantitative Analysis of Three Types of β-Carotene) The carotene-containing composition to be tested (test carotene-containing composition) was diluted with tetrahydrofuran, and then n-hexane was added to dissolve the carotene. This was subjected to high-performance liquid chromatography (HPLC) analysis under the following conditions. 13-cis β-carotene, 9-cis β-carotene, and all-trans β-carotene were identified based on the description in Non-Patent Document 1 ( Journal of Food and Hygiene, Vol. 31, No. 6, pp. 527-531 (1990)). The peak positions and peak areas were compared to quantify the content of each component in the test carotene-containing composition.

[0107] (HPLC measurement conditions) HPLC apparatus: JASCO LC-2000 Plus Stationary phase: L-Colomn ODS (4.6 x 250 mm, 5 µm) Mobile phase: methanol: acetonitrile: n-hexane: diethyl ether = 15:70:10:5 (volume ratio) Flow rate: 1 mL / min Column temperature: 40°C Detector: UV detector (detection wavelength: 455 nm).

[0108] (6) Acid Resistance Evaluation Test A test carotene-containing composition (test carotene-containing composition) was adjusted with ion-exchanged water to a final carotene concentration of 10 ppm, and citric acid (anhydrous) was added to the composition to a final concentration of 2% by mass to prepare a test solution for evaluating acid resistance at pH 2. This was heated at 95°C for 5 minutes, and the appearance of the test solution was visually observed to evaluate changes before and after heating. As a control, a test solution (final carotene concentration: 10 ppm) (blank) prepared in the same manner using ion-exchanged water except that citric acid (anhydrous) was not added was also heated under the same conditions, and changes before and after heating were evaluated.

[0109] (7) Salt Tolerance Evaluation Test A test carotene-containing composition to be tested (test carotene-containing composition) was adjusted with ion-exchanged water to a final carotene concentration of 10 ppm, and salt was added to the composition to a final concentration of 10% by mass to prepare a test solution for evaluating salt tolerance. This was heated at 95°C for 5 minutes, and the appearance of the test solution was visually observed to evaluate any changes before and after heating. As a control, a test solution (final carotene concentration: 10 ppm) (blank) prepared in the same manner but without the addition of salt was also heated under the same conditions, and the changes before and after heating were evaluated.

[0110] (8) Simulated Seasoning Liquid Test A simulated seasoning liquid (test liquid) (pH 2.5) was prepared containing 0.1% by mass of citric acid (anhydrous), 10% by mass of salt, 5% by mass of ethanol, a carotene-containing composition (adjusted to a final concentration of 10 ppm), and the remainder being ion-exchanged water. After heating this at 95°C for 5 minutes, the appearance of the test liquid was visually observed and the changes before and after heating were evaluated. As a control, a test liquid (blank) consisting of a carotene-containing composition (adjusted to a final concentration of 10 ppm) and the remainder being ion-exchanged water was prepared and heated under the same conditions, and the changes before and after heating were evaluated.

[0111] (9) Turbidity Evaluation Test The turbidity was evaluated by measuring the absorbance of the test sample at 720 nm using the following device and cell: Device: Spectrophotometer V-660 (manufactured by JASCO Corporation) Cell: Quartz cell 10 mm x 10 mm

[0112] (10) Turbidity Evaluation Test of Carotene-Containing Compositions The turbidity of the carotene-containing composition (test sample) was measured by diluting the test sample with ion-exchanged water to a final carotene concentration of 10 ppm, and measuring the absorbance at 720 nm (720 nm Abs) of the diluted test sample using the above-described device and cell. Absorbance (720 nm Abs) of 0.15 or less was evaluated as "insufficient turbidity" (rating ×), while absorbance (720 nm Abs) greater than 0.15 was evaluated as "sufficient turbidity" (rating ◯). Carotene-containing compositions with an absorbance (720 nm Abs) greater than 0.15 have carotene particles uniformly dispersed in water, which indicates good emulsion stability and stable color tone. Furthermore, as mentioned above, turbidity enhances color development and coloring effects, improving the visual appeal of the final product. Therefore, carotene-containing compositions with an absorbance (720 nm Abs) greater than 0.15 have a high coloring effect and are useful as pigment preparations.

[0113] Experimental Example 1 Preparation of the Carotene-Containing Composition and Color Evaluation (Part 1) (1) Production of the Carotene-Containing Composition (a) Preparation of a Crushed Mixture of Carotene Crystals (Step 1) A mixture (pH 3.5) prepared by mixing the raw materials listed in Table 2 was finely crushed in a wet crusher (a completely sealed horizontal bead mill: DYNO-MILL KDL (manufactured by WAB)), and then homogenized (500 kg / cm) using a homogenizer (15MR-8TA, manton-gaulin). 2 × 5 times) to prepare slurry-like crushed mixtures (Crushed Mixtures 1 and 2). The median diameter (D 50 ) was about 0.2 to 0.3 μm.

[0114]

[0115] (b) Subcritical Water Treatment (Step 2) and Cooling Treatment (Step 3) The slurry-like ground mixtures (ground mixtures 1 and 2) (pH 3.5) prepared above were subjected to a nanoemulsion production apparatus (SFW-E40S (AKICO)), where the ground mixtures were exposed for a predetermined time under temperature and pressure conditions set to produce a subcritical water state (see Table 3 for each condition) (Step 2: Subcritical Water Treatment). The subcritical water-treated product thus obtained was cooled to room temperature in a cooling device connected to the apparatus (Step 3), and various carotene-containing compositions in an emulsion state (Example 1, Comparative Example 1, Example 2) were recovered.

[0116] (c) Drying Treatment (Step 4) Of the prepared carotene-containing compositions, the carotene-containing composition of Example 2 was dried by spray drying (inlet 165°C, outlet 95°C) using a spray dryer L-8i model (manufactured by Okawara Kakoki Co., Ltd.) to prepare a carotene-containing composition in a dry powder state (Example 2D). For comparison, the pulverized mixture 2 before the critical water treatment of Example 2 was also dried under the same spray drying conditions as above to prepare a dried product of pulverized mixture 2 (pulverized mixture 2D) (see Table 4).

[0117] (2) Evaluation of the Carotene-Containing Composition The particle size (median diameter (D 50 The following measurements were taken: turbidity, color tone, and carotene content. The results are shown in Tables 3 and 4. In the tables, "coarse particles" refers to carotene particles with a particle diameter of more than 1.3 μm (volume basis). The same applies to the following tables.

[0118]

[0119]

[0120] Furthermore, the pulverized mixture 2 before the critical water treatment (i.e., the pulverized mixture 2 itself) and the carotene-containing composition after the critical water treatment (Example 2) were each subjected to a transmission electron microscope (JEM-3100FEF, manufactured by JEOL Ltd.) to confirm the shape of the carotene contained in each composition. The results are shown in Figure 1. The image on the left is of the pulverized mixture 2 before the critical water treatment, and the image on the right is of the carotene-containing composition after the critical water treatment (Example 2). As shown in Figure 1, it was confirmed that the carotene in the pulverized mixture 2 had an irregular shape, whereas the carotene in the carotene-containing composition after the critical water treatment (Example 2) was present in the form of spherical particles.

[0121] As shown in Table 3, raw carotene is wet-ground in the presence of an emulsifier (gum ghatti), and then subjected to subcritical water treatment in the presence of the emulsifier (gum ghatti) at a high temperature of 160°C or higher under pressure for a short period of time (within 60 seconds), followed by cooling. This results in a carotene-containing composition with spherical carotene particles having a median diameter of 0.15 to 0.55 μm and a coarse particle ratio of 17% or less; no significant decrease in the carotene content is observed during the manufacturing process; and a water-diluted solution of the carotene-containing composition (carotene concentration 10 ppm) has a L ＊ a ＊ In the b* color space color system, the hue angle θ is 50° to 65°, ＊ Values ​​are 20 to 40, and b ＊ It was confirmed that the value was in the range of 40 to 52, and the desired color (a color intermediate between red and yellow) was obtained.

[0122] Although the carotene content differed by about two times between Example 1 and Example 2, no significant difference in color tone was observed between the two. This confirms that the production method of the present invention makes it possible to control color tone independently of the ratio of raw carotene blended in the ground carotene mixture, and to prepare a carotene-containing composition having a desired color tone.

[0123] Furthermore, the results in Table 4 confirm that the carotene-containing composition (emulsion state) prepared by the above method can be powdered by spray drying without significantly affecting the particle size, color, and carotene content of the carotene.

[0124] (3) Evaluation of the carotene-containing composition after long-term storage The carotene-containing composition of Example 1 (emulsion state) and the dried carotene-containing composition of Example 2 (Example 2D) prepared above were placed in light-shielded sealed containers and stored under various conditions (14 days at 60°C, 6 months at 25°C, and 6 months at 5°C). After storage, particle size evaluation (median diameter, proportion of coarse particles), color evaluation, and carotene content were measured. The results are shown in Table 5.

[0125]

[0126] As shown in Table 5, the carotene-containing composition, whether undried or dried, retained the particle size (D 50 ), the proportion of coarse particles, color tone, and carotene content were maintained, confirming stability.

[0127] (4) Evaluation of Acid Resistance, Salt Resistance, and Stability in Simulated Seasoning Liquid of the Carotene-Containing Composition The dried product of Example 2 (Example 2D) of the carotene-containing composition prepared above was used to carry out the acid resistance evaluation test, salt tolerance evaluation test, and simulated seasoning liquid test described above. The results are shown in Table 6. As can be seen from these results, the carotene-containing composition exhibited good stability under acidic conditions, in the presence of salt, and in simulated seasoning liquid.

[0128]

[0129] Experimental Example 2 Preparation of the Carotene-Containing Composition and Color Tone Evaluation (Part 2) (1) Production of the Carotene-Containing Composition (a) Preparation of a Crushed Mixture of Carotene Crystals (Step 1) A mixture (pH 4.5) prepared by mixing the raw materials listed in Table 7 was subjected to a fine crushing treatment in the same manner as in Experimental Example 1 (1) (a), and then to a homogenization treatment (500 kg / cm 2 × 5 times), a slurry-like ground mixture (ground mixture 3) was prepared.

[0130]

[0131] (b) Subcritical Water Treatment (Step 2) and Cooling Treatment (Step 3) The slurry-like pulverized mixture (pulverized mixture 3) prepared above was subjected to subcritical water treatment in a nanoemulsion production apparatus in which the temperature and pressure conditions were set to produce a subcritical water state (see Table 8). The subcritical water-treated product was then cooled to room temperature in a cooling device attached to the apparatus (Step 3), and various carotene-containing compositions in an emulsion state (Examples 3-1 and 3-2) were recovered.

[0132] (2) Evaluation of the Carotene-Containing Composition The pulverized mixture 3 and each of the carotene-containing compositions prepared by the above method (Example 3-1, Example 3-2) were measured for particle size (median diameter (D 50 The following items were measured: particle size, percentage of coarse particles, turbidity, color, and carotene content. Component analysis was also performed (quantitation of three types of β-carotene [13-cis β-carotene, 9-cis β-carotene, and all-trans β-carotene]). The results are also shown in Table 8.

[0133]

[0134] As shown in Table 8, raw carotene is wet-ground in the presence of an emulsifier (gum ghatti), and then subjected to subcritical water treatment in the presence of the emulsifier (gum ghatti) under pressure at a high temperature of 160°C or higher for a short period of time (within 60 seconds), followed by cooling. This results in a carotene-containing composition having spherical carotene particles with a median diameter of 0.15 to 0.55 μm and a coarse particle ratio of 17% or less; no significant decrease in the carotene content is observed during the manufacturing process; and a water-diluted solution of the carotene-containing composition (carotene concentration 10 ppm) has a L ＊ a ＊ b ＊ In the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ It was confirmed that the value was in the range of 40 to 52, and the desired color (a color intermediate between red and yellow) was obtained.

[0135] It was also confirmed that the carotene-containing compositions of Examples 3-1 and 3-2 contained all-trans-β-carotene, 9-cis-β-carotene, and 13-cis-β-carotene as β-carotene; the proportion of all-trans-β-carotene in these three components was in the range of 75 to 97% by mass.

[0136] (3) Evaluation of the Carotene-Containing Composition After Long-Term Storage The carotene-containing compositions prepared above (Examples 3-1 and 3-2) were placed in light-shielded sealed containers and stored under various conditions (14 days at 60°C, 6 months at 25°C, and 6 months at 5°C). After storage, particle size evaluation (median diameter), proportion of coarse particles, color evaluation, and carotene content were measured. The results are shown in Table 9.

[0137]

[0138] As shown in Table 9, the carotene-containing compositions (Examples 3-1 and 3-2) retained the particle size (D 50 ), the proportion of coarse particles, color tone, and carotene content were largely maintained, confirming stability.

[0139] (4) Evaluation of Acid Resistance, Salt Tolerance, and Stability in Simulated Seasoning Liquid of the Carotene-Containing Composition The carotene-containing compositions prepared above (Examples 3-1 and 3-2) were used to carry out the acid resistance evaluation test, salt tolerance evaluation test, and simulated seasoning liquid test described above. The results are shown in Table 10. As can be seen from these results, the carotene-containing composition exhibited good stability under acidic conditions, in the presence of salt, and in simulated seasoning liquid.

[0140]

[0141] Experimental Example 3 Preparation of the Carotene-Containing Composition and Evaluation of Color Tone (Part 3) (1) Production of the Carotene-Containing Composition (a) Preparation of a Crushed Mixture of Carotene Crystals (Step 1) A mixture (pH 3.5) prepared by mixing the raw materials listed in Table 11 was subjected to a fine crushing treatment in the same manner as in Experimental Example 1 (1) (a), and then to a homogenization treatment (500 kg / cm 2 × 5 times), slurry-like crushed mixtures (Crushed Mixtures 4 to 6) were prepared.

[0142]

[0143] (b) Subcritical Water Treatment (Step 2) and Cooling Treatment (Step 3) The slurry-like pulverized mixtures prepared above (Pulverized Mixtures 4 to 6) were subjected to subcritical treatment in a nanoemulsion production apparatus in which the temperature and pressure conditions were set to produce a subcritical water state (see Tables 12 and 13). The subcritical water-treated products were then cooled to room temperature in a cooling device continuously attached to the apparatus (Step 3), and various carotene-containing compositions in an emulsion state (Examples 4-1 to 4-3, Examples 5-1 to 5-4, and Examples 6-1 to 6-2) were recovered.

[0144] (2) Evaluation of the Carotene-Containing Compositions The pulverized mixtures 4 and 5 and the carotene-containing compositions prepared by the above method (Examples 4-1 to 4-3, Examples 5-1 to 5-4, Examples 6-1 and 6-2) were analyzed for particle size (median diameter (D 50 The results are shown in Tables 12 to 15.

[0145]

[0146] As shown in Table 12, raw carotene is wet-ground in the presence of an emulsifier (gum ghatti), and then subjected to subcritical water treatment in the presence of the emulsifier (gum ghatti) under pressure at a high temperature of 200°C or higher for a short period of time (within 10 seconds), followed by cooling. This results in a carotene-containing composition having spherical carotene particles with a median diameter of 0.15 to 0.55 μm and a coarse particle ratio of 17% or less; no significant decrease in the carotene content is observed during the manufacturing process; and a water-diluted solution of the carotene-containing composition (carotene concentration 10 ppm) has a L ＊ a ＊ b ＊ In the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ It was confirmed that the value was in the range of 40 to 52, and the desired color (a color intermediate between red and yellow) was obtained.

[0147]

[0148]

[0149] As shown in Tables 13 and 14, raw carotene is crushed in the presence of an emulsifier (gum ghatti), and then subjected to subcritical water treatment in the presence of the emulsifier (gum ghatti) under pressure at a high temperature of 160°C or higher for a short period of time (within 60 seconds), followed by cooling. This results in a carotene-containing composition containing spherical carotene particles with a median diameter of 0.15 to 0.55 μm and a ratio of coarse particles of 17% or less; no significant decrease in the carotene content is observed during the manufacturing process; and a water-diluted solution of the carotene-containing composition (carotene concentration 10 ppm) has a L ＊ a ＊ b ＊ In the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ It was confirmed that the value was in the range of 40 to 52, and the desired color (a color intermediate between red and yellow) was obtained.

[0150] (3) Evaluation of the carotene-containing composition after long-term storage The carotene-containing compositions prepared above (Examples 5-1 to 5-4, Examples 6-1 and 6-2) were each placed in a light-shielded sealed container and stored at 25°C for one month. After storage, particle size evaluation (median diameter, proportion of coarse particles), color evaluation, and carotene content were measured. The results are shown in Table 15.

[0151]

[0152] As shown in Table 15, the carotene-containing compositions (Examples 5-1 to 5-4, Examples 6-1 and 6-2) retained the particle size (D 50 ), the proportion of coarse particles, color tone, and carotene content were largely maintained, confirming stability.

[0153] Experimental Example 4 Preparation of beverages and evaluation of beverages A model beverage (pH 3) was prepared using the dried product of Example 2 (Example 2D), and a storage stability evaluation test, a UHT sterilization resistance test, a shaking resistance test, and a light resistance test were carried out.

[0154] (1) Preparation of Model Beverage A beverage (pH 3) consisting of 13.3% by mass of high fructose glucose syrup, 0.3% by mass of citric acid (anhydrous), 0.05% by mass of trisodium citrate, 0.04% by mass of L-ascorbic acid, a carotene-containing composition (Example 2D) (adjusted to a final concentration of 10 ppm), and the remainder being ion-exchanged water was hot-packed into a 500 mL PET bottle at 93°C, and the resulting beverage was used as a model beverage to carry out the following tests.

[0155] (2) Storage Stability Evaluation Test The model beverages filled in PET bottles were stored in a cool, dark place at the temperatures and for the periods shown in Table 16. The turbidity and color of the beverages were then measured. The results are also shown in Table 16. As can be seen from the results, the beverage (pH 3) prepared using the present carotene-containing composition maintained the same turbidity and color as immediately after preparation even after long-term storage, confirming its good stability.

[0156]

[0157] (3) UHT Sterilization Resistance Test Model beverages filled in PET bottles were placed in the following device and subjected to UHT sterilization under the following conditions: Sterilization conditions: 115°C, 30 seconds Device: UHT / HTST Lab-25 HVHW (Micro Thermics)

[0158] The turbidity, color tone, and appearance (visual inspection) of the beverage were evaluated before UHT sterilization, after UHT sterilization, and after storage in a dark place after UHT sterilization. The results are also shown in Table 17. As can be seen, no change in color tone or turbidity was observed before or after UHT sterilization. Furthermore, even after long-term storage after UHT sterilization, the turbidity and color tone before and immediately after sterilization were almost maintained, confirming good stability. From this, it was confirmed that the beverage (pH 3) prepared using this carotene-containing composition has good resistance to UHT sterilization.

[0159]

[0160] (4) Shaking Resistance and Resistance to Adhesion to Containers A model beverage filled in a PET bottle was subjected to a shaking test under the following conditions using the following equipment: Shaker NR-150 (manufactured by Taitec Corporation). Shaking test: Amplitude 2 cm, 140 strokes / min, 18 hours. After the shaking test, the beverage was removed from the PET bottle (container), and the interior of the container was rinsed with 20 mL of water and then dried at 60°C. 30 mL of hexane was added to the container to dissolve the carotene adhering to the container's inner wall. Sodium sulfate was added to the hexane solution, which was then dehydrated, filtered through a cotton plug, and concentrated in an evaporator. The concentrate was diluted to 10 mL with hexane. The absorbance at the maximum absorption wavelength near 470 nm was measured, using hexane as a control (blank). The amount of carotene adhering to the container's inner wall was calculated using the following formula: Carotene absorption coefficient (1%, 1cm) = 2500 Carotene adhesion amount (μg / piece) = absorbance x 1000 x 10 / 2500

[0161] The results are shown in Table 18. This amount of adhesion corresponds to 0.002% by mass of the total amount of carotene added to the beverage (100% by mass). As can be seen from this, even when shock due to vibration was applied, there was almost no disruption of emulsification of carotene particles and consequent adhesion to the container. This confirmed that the beverage (pH 3) prepared using this carotene-containing composition has good resistance to shaking and adhesion to the container.

[0162]

[0163] (5) Lightfastness A model beverage (pH 3) filled in a PET bottle was subjected to a lightfastness test using the following device under the following conditions: Device: Xenon Long Light Fade Meter XML-75R (manufactured by Suga Test Instruments) Test conditions: 600 W / m 2 (300-700 nm), 20°C, (500 Langrey, 1000 Langrey). The turbidity and color tone of the beverage were evaluated before and after the light fastness test. The results are also shown in Table 19. As can be seen, no significant changes in color tone or turbidity were observed before and after the light fastness test. This confirmed that the beverage (pH 3) prepared using the present carotene-containing composition has good light fastness.

[0164]

[0165] Experimental Example 5 Preparation of the Carotene-Containing Composition and Color Tone Evaluation (Part 4) (1) Production of the Carotene-Containing Composition (a) Preparation of a Crushed Mixture of Carotene Crystals (Step 1) A mixture prepared by mixing the raw materials listed in Table 20 was subjected to a fine crushing treatment in the same manner as in Experimental Example 1 (1) (a), followed by a homogenization treatment (500 kg / cm 2 × 5 times) to prepare slurry-like crushed mixtures (Crushed Mixtures 7 and 8). The median diameter (D 50 The proportions of large particles (particles exceeding 1.3 μm) and coarse particles (particles exceeding 1.3 μm) were adjusted to be in the range of 0.15 to 55 μm and 17% or less, respectively, by changing the grinding time.

[0166]

[0167] (b) Subcritical Water Treatment (Step 2) and Cooling Treatment (Step 3) The slurry-like ground mixtures 7 and 8 prepared above were mixed with the components listed in Table 21 to prepare compositions, which were then fed to a nanoemulsion production apparatus in which the temperature and pressure conditions were set to produce a subcritical water state (see Table 22), and subcritical treatment was carried out (Step 2). The prepared subcritical water-treated product was then cooled to room temperature in a cooling device continuously attached to the apparatus (Step 3), and various carotene-containing compositions in an emulsion state (Example 7-1, Examples 8-1 to 8-2) were recovered.

[0168]

[0169] (2) Evaluation of the Carotene-Containing Composition The pulverized mixtures 7 and 8 and each of the carotene-containing compositions prepared by the above method (Example 7-1, Examples 8-1 to 8-2, Comparative Example 8) were analyzed for particle size (median diameter (D 50 The results are shown in Table 22.

[0170]

[0171] As shown in Table 22, raw carotene is crushed in the presence of an emulsifier (gum ghatti), and then subjected to subcritical water treatment in the presence of the emulsifier (gum ghatti) under pressure at a high temperature of 160°C or higher for a short period of time (within 60 seconds), followed by cooling. This results in a carotene-containing composition having spherical carotene particles with a median diameter of 0.15 to 0.55 μm, with the proportion of coarse particles with a particle diameter of more than 1.3 μm being 17% or less; and a water-diluted solution of the carotene-containing composition (carotene concentration 10 ppm) has a L ＊ a ＊ b ＊ In the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ It was confirmed that the values ​​were in the range of 40 to 52, and that the desired color (an intermediate color between red and yellow) was exhibited. It was also confirmed that the carotene-containing compositions having a proportion of coarse particles of 17% or less (Examples 8-1, 8-2, and 7-1) had superior turbidity compared to the carotene-containing composition having a proportion of coarse particles greater than 17% (Comparative Example 8).

[0172] Experimental Example 6 Preparation of the Carotene-Containing Composition and Evaluation of Color Tone (Part 5) (1) Production of the Carotene-Containing Composition (a) Preparation of a Crushed Mixture of Carotene Crystals (Step 1) A mixture prepared by mixing the raw materials listed in Table 23 was subjected to a fine crushing treatment in the same manner as in Experimental Example 1 (1) (a), followed by a homogenization treatment (500 kg / cm 2 × 5 times), slurry-like crushed mixtures (Crushed Mixtures 9 and 10) were prepared. The median diameter (D 50 The proportions of large particles (particles exceeding 1.3 μm) and coarse particles (particles exceeding 1.3 μm) were adjusted to be in the range of 0.15 to 0.55 μm and 17% or less, respectively, by changing the grinding time (see Table 24).

[0173]

[0174] (b) Subcritical Water Treatment (Step 2) and Cooling Treatment (Step 3) The slurry-like ground mixtures prepared above (ground mixtures 9 and 10) were subjected to subcritical treatment in a nanoemulsion production apparatus in which the temperature and pressure conditions were set to produce a subcritical water state (see Table 24) (Step 2). The subcritical water-treated product was then cooled to room temperature in a cooling device continuously attached to the apparatus (Step 3), and various carotene-containing compositions in an emulsion state (Examples 9-1 to 9-2, Examples 10-1 to 10-2) were recovered.

[0175] (2) Evaluation of the Carotene-Containing Composition The pulverized mixtures 9 and 10 and the carotene-containing compositions prepared by the above method (Examples 9-1 to 9-2, Examples 10-1 to 10-2) were analyzed for particle size (median diameter (D 50 The results are shown in Table 23.

[0176]

[0177] As shown in Table 24, raw carotene is ground in the presence of an emulsifier (gum ghatti), and then subjected to subcritical water treatment in the presence of the emulsifier (gum ghatti) under pressure at a high temperature of 158°C or higher for a short period of time (within 60 seconds). This treatment is followed by cooling. This results in a carotene-containing composition having spherical carotene particles with a median diameter of 0.15 to 0.55 μm, with the proportion of coarse particles with a particle diameter of more than 1.3 μm being 17% or less; the composition has excellent turbidity; and a water-diluted solution of the carotene-containing composition (carotene concentration 10 ppm) has a L ＊ a ＊ b ＊ In the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ It was confirmed that the value was in the range of 40 to 52, and the desired color (a color intermediate between red and yellow) was obtained.

[0178] (3) Evaluation of the carotene-containing composition after long-term storage The carotene-containing compositions prepared above (Examples 9-1 to 9-2, Examples 10-1 to 10-2) were placed in light-shielded sealed containers and stored at 60°C for 14 days and at 25°C for 1 month. After storage, the particle size evaluation (median diameter), the proportion of coarse particles, color evaluation, and carotene content were measured. The results are shown in Table 25.

[0179]

[0180] As shown in Table 25, the carotene-containing compositions (Examples 9-1 to 9-2, Examples 10-1 to 10-2) retained the particle size (D 50 ), the proportion of coarse particles, color tone, and carotene content were largely maintained, confirming stability.

[0181] Experimental Example 7 Preparation of the Carotene-Containing Composition and Evaluation of Color Tone (Part 6) (1) Production of the Carotene-Containing Composition (a) Preparation of a Crushed Mixture of Carotene Crystals (Step 1) A mixture prepared by mixing the raw materials listed in Table 26 was subjected to a fine crushing treatment in the same manner as in Experimental Example 1 (1) (a), followed by a homogenization treatment (500 kg / cm 2 × 5 times) to prepare slurry-like crushed mixtures (crushed mixtures 11 to 15). The median diameter (D50 The proportions of large particles (particles exceeding 1.3 μm) and coarse particles (particles exceeding 1.3 μm) were adjusted to be in the range of 0.15 to 55 μm and 17% or less, respectively, by changing the grinding time.

[0182]

[0183] (b) Subcritical Water Treatment (Step 2) and Cooling Treatment (Step 3) The slurry-like ground mixtures 11 to 13 prepared above were blended with the components listed in Table 27 to prepare compositions, which were then fed to a nanoemulsion production apparatus in which the temperature and pressure conditions were set to produce a subcritical water state (see Table 28), and subjected to subcritical treatment (Step 2). The subcritical water-treated product was then cooled to room temperature in a cooling device continuously attached to the apparatus (Step 3), and various carotene-containing compositions in an emulsion state (Examples 11-1 to 11-2, Examples 12-1 to 12-2, and Examples 13-1 to 13-2) were recovered.

[0184]

[0185]

[0186] (3) Evaluation of the carotene-containing composition after long-term storage The carotene-containing compositions prepared above were placed in light-shielded sealed containers and stored at 60°C for 14 days, at 25°C for 1 month, and at 5°C for 1 month. After storage, particle size evaluation (median diameter, proportion of coarse particles), turbidity, color evaluation, and carotene content were measured. The results are shown in Table 29.

[0187]

[0188] As shown in Table 29, the carotene-containing composition retained the particle size (D 50 ), the proportion of coarse particles, color tone, and carotene content were largely maintained, confirming stability.

[0189] Experimental Example 8 Preparation of Beverages and Evaluation Thereof (1) Drying Treatment of the Carotene-Containing Compositions A mixture of 43% by mass of the carotene-containing compositions prepared in the above Experimental Examples (Examples 9-2, 10-2, 11-1, 11-2, 14-1, 14-2, and 15-1), 38% by mass of maltodextrin, and 19% by mass of water was dried by spray drying (inlet 165°C, outlet 95°C) using a spray dryer L-8i (manufactured by Okawara Kakoki Co., Ltd.) to prepare carotene-containing compositions in a dry powder state (Examples 9-2D, 10-2D, 11-1D, 11-2D, 14-1D, 14-2D, and 15-1D).

[0190] (2) Preparation of Beverages Model beverages (pH 3) were prepared using the carotene-containing compositions in a dry powder state (Examples 9-2D, 10-2D, 11-1D, 11-2D, 14-1D, 14-2D, and 15-1D) in the same manner as in Experimental Example 4. The carotene concentration in the beverage was adjusted to 10 ppm.

[0191] (3) Storage Stability Test As in Experimental Example 4, the model beverages filled in PET bottles were stored in a cool, dark place at the temperatures and for the periods shown in Table 30. The turbidity and color of the beverages were then measured, and visual evaluations (such as container adhesion) were also performed. The results are also shown in Table 30. As can be seen from the results, the beverage (pH 3) prepared using the present carotene-containing composition maintained the same turbidity and color as immediately after preparation even after long-term storage, confirming its good stability. However, when the present carotene-containing composition was prepared using modified starch as an emulsifier in the grinding process, adhesion to the container was confirmed after long-term storage. For this reason, it was determined that gum ghatti, low-molecular-weight gum ghatti, and gum arabic are preferred as emulsifiers to be used in the manufacturing process, with gum ghatti being particularly preferred.

[0192]

Claims

1. A carotene-containing composition containing spherical carotene particles, characterized in that: the median diameter (D ５０ ) is 0.15 μm or more and 0.55 μm or less, the proportion of carotene particles having a particle size of more than 1.3 μm is 17% or less per 100% of the total volume of carotene particles on a volume basis, and the color tone of an aqueous solution of the carotene-containing composition adjusted to a carotene concentration of 10 ppm is L ＊ a ＊ b ＊ In the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ The value is 40 to 52.

2. The color tone of the aqueous solution is less than the brightness L ＊ The carotene-containing composition according to claim 1, having a color saturation value of 70 to 85 and / or a chroma C value of 45 to 65.

3. The carotene-containing composition according to claim 1, which contains 13-cis beta-carotene, 9-cis beta-carotene, and all-trans-beta-carotene, and the proportion of all-trans-beta-carotene relative to the total amount (100% by mass) of these components is 50% by mass or more.

4. A method for producing a carotene-containing composition, comprising the following steps 1 to 3: Step 1: Carotene crystals are sized to have a median diameter (D ５０ Step 2: subjecting the pulverized mixture prepared in Step 1 to a subcritical water treatment to prepare a subcritical water-treated product; and Step 3: cooling the subcritical water-treated product prepared in Step 2 to a median diameter (D ５０ a step of preparing a carotene-containing composition having spherical carotene particles with a diameter of 0.15 μm or more and 0.55 μm or less; wherein the carotene-containing composition is an aqueous solution adjusted to have a carotene concentration of 10 ppm, ＊ a ＊ b ＊ In the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ It is characterized by having a color tone with a value of 40 to 52.

5. The carotene-containing composition is prepared by adjusting the brightness L of an aqueous solution so that the carotene concentration is 10 ppm. ＊ 5. The method according to claim 4, wherein the chroma value is 70 to 85, and / or the chroma C value is 45 to 65.

6. The method according to claim 4, wherein the emulsifier used in step 1 is at least one selected from the group consisting of gum ghatti, low molecular weight gum ghatti, gum arabic, and modified starch.

7. The method according to claim 4, wherein the subcritical water treatment step of step 2 is carried out in the presence of an emulsifier, and the emulsifier is at least gum ghatti.

8. The manufacturing method according to claim 4, wherein the subcritical water treatment step of step 2 is a step of treating the ground mixture prepared in step 1 at a temperature of 158 to 240°C and a pressure equal to or higher than the saturated water vapor pressure for 0.1 to 60 seconds.

9. The method according to claim 4, wherein both the grinding step (step 1) and the subcritical water treatment step (step 2) are carried out under conditions that do not contain organic solvents or fats or oils.

10. The method according to claim 4, further comprising a step (step 4) of drying the carotene-containing composition prepared in step 3.

11. A carotene-containing composition produced by the method of claim 4, wherein the carotene-containing composition contains spherical carotene particles, and the median diameter (D ５０ ) is 0.15 μm or more and 0.55 μm or less, and the color tone of an aqueous solution of the carotene-containing composition adjusted to have a carotene concentration of 10 ppm is L ＊ a ＊ b ＊ In the color space color system, the hue angle θ is 50° to 65°, a ＊ Values ​​are 20 to 40, and b ＊ The carotene-containing composition, wherein the value is 40 to 52.

12. The carotene-containing composition according to claim 1 or 11, which is used as an additive for foods, beverages, cosmetics, pharmaceuticals and / or quasi-drugs.

13. The carotene-containing composition according to claim 12, wherein the additive is a pigment preparation.

14. A coloring composition comprising the carotene-containing composition according to claim 1 or 11.

15. The coloring composition according to claim 14, which is a food or drink, cosmetic, pharmaceutical, or quasi-drug.

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