JP5317794B2 - Benikouji pigment preparation and method for producing the same - Google Patents

Benikouji pigment preparation and method for producing the same Download PDF

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JP5317794B2
JP5317794B2 JP2009081064A JP2009081064A JP5317794B2 JP 5317794 B2 JP5317794 B2 JP 5317794B2 JP 2009081064 A JP2009081064 A JP 2009081064A JP 2009081064 A JP2009081064 A JP 2009081064A JP 5317794 B2 JP5317794 B2 JP 5317794B2
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JP2009263650A (en
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聖子 川田
浩一 原田
英知 菊池
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Riken Vitamin Co Ltd
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Description

本発明は、光に対する安定性が改善されたベニコウジ色素製剤およびその製造方法に関する。   The present invention relates to a beige mushroom pigment preparation with improved light stability and a method for producing the same.

ベニコウジ色素は食品や化粧品等の天然着色料として従来から広く使用されている。しかしながら、ベニコウジ色素は光に対する安定性が悪いので、ベニコウジ色素を使用して着色した食品等が蛍光灯や太陽光などの光に曝されると、ごく短時間の間に退色が起こり、商品性を損なうという欠点があった。   Benikouji pigment has been widely used as a natural colorant for foods and cosmetics. However, because Benikouji dyes are not stable to light, foods that are colored using Benikouji dyes are exposed to light such as fluorescent light or sunlight, and fading occurs in a very short time. There was a disadvantage of damaging.

この光照射によるベニコウジ色素の安定性を改善するために、紅麹色素にセサモリン誘導体を添加する方法(特許文献1)、ベニコウジ色素を脱酸素剤と共に密封保存する方法(特許文献2)、ベニコウジ色素にトリプトファン等を添加する方法(特許文献3)、抽出トコフェロールおよびフェルラ酸を含有する色素の退色防止剤(特許文献4)などが検討されているが、未だ十分に満足しうる方法は見出されていない。   In order to improve the stability of the beech mushroom dye by this light irradiation, a method of adding a sesamorin derivative to the red yeast rice dye (Patent Document 1), a method of sealing and storing the bemoji dye together with an oxygen scavenger (Patent Document 2), A method of adding tryptophan or the like to a pigment (Patent Document 3), an anti-fading agent for a pigment containing extracted tocopherol and ferulic acid (Patent Document 4) has been studied, but a method that is still satisfactory can be found. Not.

特開平10−110109号公報JP-A-10-110109 特開2002−253168号公報JP 2002-253168 A 特開2003−191号公報Japanese Patent Laid-Open No. 2003-191 特開2004−222649号公報JP 2004-222649 A

本発明は、加工食品等の着色に用いられる、光に対する安定性が改善されたベニコウジ色素製剤を提供することを目的とする。   An object of the present invention is to provide a beige mushroom pigment preparation with improved light stability, which is used for coloring processed foods and the like.

本発明者は、上記課題を解決するため鋭意検討した結果、ベニコウジ色素を含有する水相と、特定の物性を有するポリグリセリン縮合リシノール酸エステルおよび食用油脂を含有する油相とを乳化して得られる油中水型乳化組成物を減圧乾燥して得られるベニコウジ色素製剤を添加して着色した食品は、光に対する安定性が改善されたものであることを見出し、この知見に基づいて本発明をなすに至った。   As a result of intensive studies to solve the above-mentioned problems, the present inventor obtained by emulsifying an aqueous phase containing Benikouji pigment and an oil phase containing polyglycerin condensed ricinoleic acid ester and edible fats and oils having specific physical properties. It was found that foods colored by adding a beige mushroom pigment preparation obtained by drying a water-in-oil emulsion composition obtained under reduced pressure have improved stability to light. It came to an eggplant.

すなわち、本発明は、次の(1)〜(3)からなっている。
(1)(a)ベニコウジ色素、(b)下記乳化力試験における乳化相の割合が81〜89%であるポリグリセリン縮合リシノール酸エステルおよび(c)食用油脂を含有するベニコウジ色素製剤。
<乳化力試験>
1)500ml容ビーカーに菜種白絞油(ボーソー油脂社製)200gおよびポリグリセリン縮合リシノール酸エステル0.80gを入れて混合し、60℃に加温して油相とする。
2)1)の油相をミキサー部と邪魔板との間隙を2.5cmに固定した乳化機(型式:T.K.ホモミクサーMARKII 2.5型;プライミクス社製)を用いて3000rpmで撹拌しながら、該油相に60℃に加温した精製水200gを90秒間かけて加える。
3)さらに、60℃に調温しながら10000rpmで3分間撹拌して油中水型乳化物を得る。
4)3)で得た油中水型乳化物を100ml容有栓メスシリンダーに100ml入れ37℃の恒温器で120時間保存する。保存後、油相、乳化相および水相に分離したメスシリンダーの内容物について乳化相の体積(ml)を測定し、次式に基づいて乳化相の割合(%)を計算する。
That is, this invention consists of following (1)-(3).
(1) (a) Benikouji pigment, (b) Benikouji pigment preparation containing polyglycerin-condensed ricinoleic acid ester having an emulsified phase ratio of 81 to 89% in the following emulsification test and (c) edible oil and fat.
<Emulsifying power test>
1) In a 500 ml beaker, 200 g of rapeseed white squeezed oil (manufactured by Borso Oil & Fats Co., Ltd.) and 0.80 g of polyglycerin condensed ricinoleate are mixed and heated to 60 ° C. to obtain an oil phase.
2) The oil phase of 1) was stirred at 3000 rpm using an emulsifier (model: TK homomixer MARK II 2.5 type; manufactured by Primix Co., Ltd.) in which the gap between the mixer part and the baffle plate was fixed at 2.5 cm. Then, 200 g of purified water heated to 60 ° C. was added to the oil phase over 90 seconds.
3) Furthermore, stirring at 10000 rpm for 3 minutes while adjusting the temperature to 60 ° C., a water-in-oil emulsion is obtained.
4) Add 100 ml of the water-in-oil emulsion obtained in 3) to a 100 ml stoppered graduated cylinder and store it in a thermostat at 37 ° C. for 120 hours. After storage, the volume (ml) of the emulsified phase is measured for the contents of the graduated cylinder separated into an oil phase, an emulsified phase and an aqueous phase, and the proportion (%) of the emulsified phase is calculated based on the following formula.

Figure 0005317794
Figure 0005317794

(2)ベニコウジ色素がベニコウジ色素粉末であり、該ベニコウジ色素粉末について下記親水性判別試験を実施した場合の分配係数が−1.2〜−0.1である、(1)のベニコウジ色素製剤。
<親水性判別試験>
1)ベニコウジ色素粉末(色価1000換算)0.002gを50ml容共栓付比色管に入れ、イオン交換水15mlを加え、よく混合して溶解液を得る。
2)1)の溶解液に1−オクタノール(試薬特級;和光純薬工業社製)15mlを加え、前記比色管を上下に180度づつ回転させながら5分間振とうする(回転数20回/分)。
3)振とう後、前記比色管の内容物を50ml容遠心ボトルに入れ、遠心分離機を使用して遠心加速度12000×gで15分間遠心分離を行う。
4)遠心分離後、前記遠心ボトル内の1−オクタノール相および水相を採取し、これらの相の各々について、分光光度計を使用して可視極大吸収波長における吸光度および660nmにおける吸光度を測定する。
5)1−オクタノール相の可視極大吸収波長における吸光度をO1、1−オクタノール相の660nmにおける吸光度をO2、水相の可視極大吸収波長における吸光度をW1、水相の660nmにおける吸光度をW2とし、次式に基づいて分配係数を計算する。
(2) The beech mushroom pigment preparation according to (1), wherein the beco mushroom pigment is a bem moji pigment powder, and the partition coefficient is -1.2 to -0.1 when the following hydrophilicity discrimination test is performed on the bem moji pigment powder.
<Hydrophilicity discrimination test>
1) Put 0.002 g of Benikouji pigment powder (converted to a color value of 1000) into a 50 ml capacitative colorimetric tube, add 15 ml of ion exchange water, and mix well to obtain a solution.
2) Add 15 ml of 1-octanol (special grade reagent; manufactured by Wako Pure Chemical Industries, Ltd.) to the solution of 1) and shake for 5 minutes while rotating the colorimetric tube 180 degrees up and down (rotation number 20 times / Min).
3) After shaking, the contents of the colorimetric tube are placed in a 50 ml centrifuge bottle and centrifuged for 15 minutes at a centrifugal acceleration of 12000 × g using a centrifuge.
4) After centrifugation, the 1-octanol phase and the aqueous phase in the centrifuge bottle are collected, and the absorbance at the visible maximum absorption wavelength and the absorbance at 660 nm are measured for each of these phases using a spectrophotometer.
5) The absorbance at the visible maximum absorption wavelength of the 1-octanol phase is O1, the absorbance at 660 nm of the 1-octanol phase is O2, the absorbance at 660 nm of the aqueous phase is W1, and the absorbance at 660 nm of the aqueous phase is W2. Calculate the distribution coefficient based on the formula.

Figure 0005317794
Figure 0005317794

(3)(a)ベニコウジ色素を含有する水相と、(b)上記乳化力試験における乳化相の割合が81〜89%であるポリグリセリン縮合リシノール酸エステルおよび(c)食用油脂を含有する油相とを乳化して油中水型乳化組成物を得る工程と、該油中水型乳化組成物を減圧乾燥する工程とを含むことを特徴とするベニコウジ色素製剤の製造方法。 (3) an oil containing (a) an aqueous phase containing a beech powder, (b) a polyglycerin condensed ricinoleic acid ester in which the proportion of the emulsified phase in the emulsifying ability test is 81 to 89%, and (c) an edible oil / fat A method for producing a beige mushroom pigment preparation, comprising: a step of emulsifying a phase to obtain a water-in-oil emulsion composition; and a step of drying the water-in-oil emulsion composition under reduced pressure.

本発明のベニコウジ色素製剤を用いて着色したカマボコなどの食品の光に対する安定性は実用上十分に満足できるものである。   The stability to light of foods such as sea urchins colored with the beech powder dye preparation of the present invention is sufficiently satisfactory in practice.

ベニコウジ色素製剤
本発明のベニコウジ色素製剤は、(a)ベニコウジ色素、(b)上記乳化力試験における乳化相の割合が81〜89%であるポリグリセリン縮合リシノール酸エステルおよび(c)食用油脂を含有するものである。
Benikouji pigment preparation The Bencouge pigment formulation of the present invention comprises (a) Bencouge pigment, (b) polyglycerin condensed ricinoleic acid ester in which the proportion of the emulsified phase in the emulsifying ability test is 81 to 89%, and (c) edible oil and fat. To do.

ベニコウジ色素
本発明において用いられるベニコウジ色素は、ベニコウジ菌(即ち、Monascus属の糸状菌)の培養生成物から抽出して得られる水溶性の赤色色素であり、その主成分はモナスコルブリン類、アンカフラビン類などである。
Benikouji pigment The Benikouji pigment used in the present invention is a water-soluble red pigment obtained by extraction from a culture product of Beniculomycetes (i.e., filamentous fungi of the genus Monascus), and the main components thereof are monascorbrins and anchors. Such as flavins.

本発明のベニコウジ色素製剤の製造に用いられるベニコウジ色素の形態に特に制限はなく、ベニコウジ色素水/アルコール溶液やベニコウジ色素粉末などが挙げられるが、好ましくはベニコウジ色素粉末であり、その製造方法の概略は以下の通りである。   There are no particular restrictions on the form of the beech powder used for the production of the bemoji dye preparation of the present invention, and examples include water solution / alcohol solution of bemoji dye and powder of bemoji dye, preferably bemoji dye powder, and an outline of the production method thereof Is as follows.

水/アルコール混合液を抽出溶媒としてベニコウジ菌の培養生成物からベニコウジ色素を抽出し、ベニコウジ色素水/アルコール溶液を調製する。次いで、該ベニコウジ色素水/アルコール溶液を賦形剤(例えば、デキストリンなど)と共に混合液とし、該混合液を常法により噴霧乾燥してベニコウジ色素粉末を得る方法、或いは該ベニコウジ色素水/アルコール溶液を濃縮し、真空凍結乾燥する方法などによりベニコウジ色素粉末を得る。   Using a water / alcohol mixed solution as an extraction solvent, Benikouji pigment is extracted from the culture product of B. niger, and a water solution of alcohol with a beetle pigment / alcohol solution is prepared. Next, a method of obtaining the powdered beech powder by spraying the mixed solution with the excipient (for example, dextrin) and the mixture and spray-drying the mixed solution by a conventional method, or the solution of the colored water / alcohol solution Concentrate and obtain a beige powder pigment by a method such as vacuum lyophilization.

本発明に用いられるベニコウジ色素は、下記親水性判別試験を行った場合の分配係数が−2.0〜1.5であるベニコウジ色素粉末が好ましく、該分配係数が−1.5〜0.7のベニコウジ色素粉末がさらに好ましく、該分配係数が−1.2〜−0.1のベニコウジ色素粉末が特に好ましい。該分配係数が−1.2〜−0.1の範囲であると、本発明のベニコウジ色素製剤を用いて着色した食品の光に対する安定性がさらに向上する。
<親水性判別試験>
1)ベニコウジ色素粉末(色価1000換算)0.002gを50ml容共栓付比色管に入れ、イオン交換水15mlを加え、よく混合して溶解液を得る。
2)1)の溶解液に1−オクタノール(試薬特級;和光純薬工業社製)15mlを加え、前記比色管を上下に180度づつ回転させながら5分間振とうする(回転数20回/分)。
3)振とう後、前記比色管の内容物を50ml容遠心ボトルに入れ、遠心分離機を使用して遠心加速度12000×gで15分間遠心分離を行う。
4)遠心分離後、前記遠心ボトル内の1−オクタノール相および水相を採取し、これらの相の各々について、分光光度計を使用して可視極大吸収波長における吸光度および660nmにおける吸光度を測定する。
5)1−オクタノール相の可視極大吸収波長における吸光度をO1、1−オクタノール相の660nmにおける吸光度をO2、水相の可視極大吸収波長における吸光度をW1、水相の660nmにおける吸光度をW2とし、次式に基づいて分配係数を計算する。
The beech mushroom dye used in the present invention is preferably a bemoji dye powder having a distribution coefficient of -2.0 to 1.5 when the following hydrophilicity discrimination test is performed, and the distribution coefficient is -1.5 to 0.7. Are more preferable, and a powdered beech powder having a partition coefficient of -1.2 to -0.1 is particularly preferable. When the distribution coefficient is in the range of -1.2 to -0.1, the stability of the food colored with the beige mushroom pigment preparation of the present invention to light is further improved.
<Hydrophilicity discrimination test>
1) Put 0.002 g of Benikouji pigment powder (converted to a color value of 1000) into a 50 ml capacitative colorimetric tube, add 15 ml of ion exchange water, and mix well to obtain a solution.
2) Add 15 ml of 1-octanol (special grade reagent; manufactured by Wako Pure Chemical Industries, Ltd.) to the solution of 1) and shake for 5 minutes while rotating the colorimetric tube 180 degrees up and down (rotation number 20 times / Min).
3) After shaking, the contents of the colorimetric tube are placed in a 50 ml centrifuge bottle and centrifuged for 15 minutes at a centrifugal acceleration of 12000 × g using a centrifuge.
4) After centrifugation, the 1-octanol phase and the aqueous phase in the centrifuge bottle are collected, and the absorbance at the visible maximum absorption wavelength and the absorbance at 660 nm are measured for each of these phases using a spectrophotometer.
5) The absorbance at the visible maximum absorption wavelength of the 1-octanol phase is O1, the absorbance at 660 nm of the 1-octanol phase is O2, the absorbance at 660 nm of the aqueous phase is W1, and the absorbance at 660 nm of the aqueous phase is W2. Calculate the distribution coefficient based on the formula.

Figure 0005317794
Figure 0005317794

尚、本発明のベニコウジ色素製剤の製造に用いられるベニコウジ色素の形態がベニコウジ色素粉末以外のもの(例えば、ベニコウジ色素水/アルコール溶液など)である場合、該ベニコウジ色素を自体公知の方法で粉末化することによりベニコウジ色素粉末を調製した上で、該ベニコウジ色素粉末について上記親水性判別試験を行うことができる。   In addition, when the form of the beige mushroom dye used in the production of the bemoji dye preparation of the present invention is something other than the bemoji dye powder (for example, bemoji dye water / alcohol solution), the bemoji dye is pulverized by a method known per se. In this way, after preparing a beige mushroom dye powder, the hydrophilicity discrimination test can be performed on the bemoji dye powder.

ここで、上記親水性判別試験における分配係数は、ベニコウジ色素の親水性の程度を示す指標である。この分配係数の値が大きい程、ベニコウジ色素の親水性が低いことを意味する。   Here, the distribution coefficient in the hydrophilicity discrimination test is an index indicating the degree of hydrophilicity of the beige mushroom dye. The larger the value of this distribution coefficient, the lower the hydrophilicity of the beige mushroom dye.

上記親水性判別試験における分配係数が−2.0〜1.5であるベニコウジ色素粉末としては、例えばリケカラーR−30(商品名;ベニコウジ色素水/アルコール溶液;理研ビタミン社製)を粉末化したもの(親水性判別試験での分配係数0.2)、リケカラーRPH−30(商品名;ベニコウジ色素水/アルコール溶液;理研ビタミン社製)を粉末化したもの(親水性判別試験での分配係数−0.3)、リケカラーRPH−60(商品名;ベニコウジ色素水/アルコール溶液;理研ビタミン社製)を粉末化したもの(親水性判別試験での分配係数−0.4)、リケカラーR−4200(SD)(商品名;理研ビタミン社製)(親水性判別試験での分配係数0.2)などが商業的に製造および販売されており、本発明のベニコウジ色素製剤の製造にはこれらを用いることができる。   Examples of Benikouji pigment powder having a distribution coefficient in the hydrophilicity discrimination test of −2.0 to 1.5 were powdered, for example, Riquecolor R-30 (trade name; Bencouge pigment water / alcohol solution; manufactured by Riken Vitamin Co., Ltd.). (Distribution coefficient 0.2 in the hydrophilicity discrimination test), Riquecolor RPH-30 (trade name; Benikouji pigment water / alcohol solution; manufactured by Riken Vitamin Co., Ltd.) powdered (Distribution coefficient in the hydrophilicity discrimination test- 0.3), Riquecolor RPH-60 (trade name: Benikouji pigment water / alcohol solution; manufactured by Riken Vitamin Co., Ltd.), powdered (partition coefficient -0.4 in hydrophilicity discrimination test), Riquecolor R-4200 ( SD) (trade name; manufactured by Riken Vitamin Co., Ltd.) (distribution coefficient 0.2 in the hydrophilicity discrimination test) and the like are commercially produced and sold. These can be used for production.

ポリグリセリン縮合リシノール酸エステル
本発明において用いられるポリグリセリン縮合リシノール酸エステルは、ポリグリセリンと縮合リシノール酸とのエステル化生成物であり、自体公知のエステル化反応等により製造される。該ポリグリセリンとしては、平均重合度が約2〜15程度のものが挙げられる。好ましくは平均重合度が約3〜10程度のものである。具体的には、例えば、トリグリセリン、テトラグリセリン又はヘキサグリセリン等が好ましく挙げられる。該縮合リシノール酸は、リシノール酸を加熱し、重縮合反応させて得られる混合物である。該縮合リシノール酸としては、平均重合度が約2〜10程度のものが挙げられる。好ましくは平均重合度が約3〜6程度のものである。
Polyglycerol condensed ricinoleic acid ester The polyglycerol condensed ricinoleic acid ester used in the present invention is an esterification product of polyglycerol and condensed ricinoleic acid, and is produced by a known esterification reaction or the like. Examples of the polyglycerin include those having an average degree of polymerization of about 2 to 15. The average degree of polymerization is preferably about 3 to 10. Specifically, for example, triglycerin, tetraglycerin, hexaglycerin and the like are preferable. The condensed ricinoleic acid is a mixture obtained by heating ricinoleic acid to cause a polycondensation reaction. Examples of the condensed ricinoleic acid include those having an average degree of polymerization of about 2 to 10. The average degree of polymerization is preferably about 3 to 6.

また、本発明ではポリグリセリン縮合リシノール酸エステルとして、後述する乳化力試験における乳化相の割合が81〜89%であるポリグリセリン縮合リシノール酸エステルを用いる。このようなポリグリセリン縮合リシノール酸エステルを使用することにより、本発明のベニコウジ色素製剤中のベニコウジ色素を含有する固体相微粒子のメジアン径がより小さくなり、これによりベニコウジ色素の光に対する安定性が向上し、更には該製剤を用いて着色した食品の光に対する安定性が向上するという効果が得られる。   Moreover, in this invention, the polyglycerol condensed ricinoleic acid ester whose ratio of the emulsification phase in the emulsification ability test mentioned later is 81-89% is used as a polyglycerol condensed ricinoleic acid ester. By using such a polyglycerin condensed ricinoleic acid ester, the median diameter of the solid phase fine particles containing the beige mushroom dye in the benichow dye preparation of the present invention becomes smaller, thereby improving the light stability of the bemoji dye. Moreover, the effect of improving the light stability of food colored using the preparation can be obtained.

本発明における乳化力試験とは、下記方法で行われる試験である。
<乳化力試験>
1)500ml容ビーカーに菜種白絞油(ボーソー油脂社製)200gおよびポリグリセリン縮合リシノール酸エステル0.80gを入れて混合し、60℃に加温して油相とする。
2)1)の油相をミキサー部と邪魔板との間隙を2.5cmに固定した乳化機(型式:T.K.ホモミクサーMARKII 2.5型;プライミクス社製)を用いて3000rpmで撹拌しながら、該油相に60℃に加温した精製水200gを90秒間かけて加える。
3)さらに、60℃に調温しながら10000rpmで3分間撹拌して油中水型乳化物を得る。
4)3)で得た油中水型乳化物を100ml容有栓メスシリンダーに100ml入れ37℃の恒温器で120時間保存する。保存後、油相、乳化相および水相に分離したメスシリンダーの内容物について乳化相の体積(ml)を測定し、次式に基づいて乳化相の割合(%)を計算する。
The emulsifying power test in the present invention is a test performed by the following method.
<Emulsifying power test>
1) In a 500 ml beaker, 200 g of rapeseed white squeezed oil (manufactured by Borso Oil & Fats Co., Ltd.) and 0.80 g of polyglycerin condensed ricinoleate are mixed and heated to 60 ° C. to obtain an oil phase.
2) The oil phase of 1) was stirred at 3000 rpm using an emulsifier (model: TK homomixer MARK II 2.5 type; manufactured by Primix Co., Ltd.) in which the gap between the mixer part and the baffle plate was fixed at 2.5 cm. Then, 200 g of purified water heated to 60 ° C. was added to the oil phase over 90 seconds.
3) Furthermore, stirring at 10000 rpm for 3 minutes while adjusting the temperature to 60 ° C., a water-in-oil emulsion is obtained.
4) Add 100 ml of the water-in-oil emulsion obtained in 3) to a 100 ml stoppered graduated cylinder and store it in a thermostat at 37 ° C. for 120 hours. After storage, the volume (ml) of the emulsified phase is measured for the contents of the graduated cylinder separated into an oil phase, an emulsified phase and an aqueous phase, and the proportion (%) of the emulsified phase is calculated based on the following formula.

Figure 0005317794
Figure 0005317794

上記乳化力試験における乳化相の割合が81〜89%であるポリグリセリン縮合リシノール酸エステルとしては、例えばサンソフトNo.818SK(商品名;乳化力試験での乳化相の割合86%;太陽化学社製)、Palsgaard 4150(商品名;乳化力試験での乳化相の割合89%;パルスガード社製)、SYグリスターCR−ED(商品名;乳化力試験での乳化相の割合81%;阪本薬品工業社製)が商業的に製造および販売されており、本発明ではこれらをポリグリセリン縮合リシノール酸エステルとして用いることができる。   Examples of the polyglycerin condensed ricinoleic acid ester in which the proportion of the emulsified phase in the emulsifying power test is 81 to 89% include, for example, Sunsoft No. 818SK (trade name; 86% of emulsified phase in emulsifying power test; manufactured by Taiyo Kagaku Co., Ltd.), Palsgaard 4150 (trade name; 89% of the emulsified phase in emulsifying power test; manufactured by Pulseguard), SY Glister CR -ED (trade name; 81% of emulsified phase in emulsifying power test; manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) is commercially produced and sold. In the present invention, these are used as polyglycerin condensed ricinoleic acid esters. it can.

食用油脂
本発明において用いられる食用油脂としては、食用可能な油脂であれば特に制限はないが、例えばオリーブ油、ごま油、こめ油、サフラワー油、大豆油、とうもろこし油、菜種油、パーム油、パームオレイン、パーム核油、ひまわり油、ぶどう油、綿実油、やし油、落花生油などの植物油脂が好ましい。食用油脂の中でもごま油、こめ油、サフラワー油、大豆油、とうもろこし油、菜種油、ひまわり油、ぶどう油および綿実油からなる群より選択される一種以上の植物油脂のサラダ油がさらに好ましく、菜種サラダ油が特に好ましい。本発明においては、食用油脂を一種類で用いても良いし、二種類以上を任意に組み合わせて用いても良い。
Edible fats and oils The edible fats and oils used in the present invention are not particularly limited as long as they are edible fats and oils. For example, olive oil, sesame oil, sesame oil, safflower oil, soybean oil, corn oil, rapeseed oil, palm oil, palm olein Vegetable oils such as palm kernel oil, sunflower oil, grape oil, cottonseed oil, palm oil and peanut oil are preferred. Among the edible oils and fats, a salad oil of one or more vegetable oils selected from the group consisting of sesame oil, rice oil, safflower oil, soybean oil, corn oil, rapeseed oil, sunflower oil, grape oil and cottonseed oil is more preferred, and rapeseed salad oil is particularly preferred preferable. In the present invention, one type of edible oil or fat may be used, or two or more types may be used in any combination.

ベニコウジ色素製剤の製造方法
本発明のベニコウジ色素製剤は、(a)ベニコウジ色素を含有する水相と、(b)上記乳化力試験における乳化相の割合が81〜89%であるポリグリセリン縮合リシノール酸エステル(以下、単にポリグリセリン縮合リシノール酸エステルともいう)および(c)食用油脂を含有する油相とを乳化して油中水型乳化組成物を得る工程と、該油中水型乳化組成物を減圧乾燥する工程とを含む製造方法により製造することができる。このようなベニコウジ色素製剤の製造方法も、本発明の1つである。
Method for producing Benikouji pigment preparation Bencouge pigment formulation of the present invention comprises: (a) an aqueous phase containing Benikouji pigment; and (b) a polyglycerin condensed ricinoleic acid in which the proportion of the emulsion phase in the emulsifying power test is 81 to 89%. A step of emulsifying an ester (hereinafter, also simply referred to as polyglycerin condensed ricinoleic acid ester) and (c) an oil phase containing an edible oil and fat to obtain a water-in-oil emulsion composition, and the water-in-oil emulsion composition Can be manufactured by a manufacturing method including a step of drying under reduced pressure. Such a method for producing a beige mushroom pigment preparation is also one aspect of the present invention.

本発明では、先ずベニコウジ色素を含有する水相とポリグリセリン縮合リシノール酸エステルおよび食用油脂を含有する油相とを乳化して油中水型乳化組成物を得る。具体的には、食用油脂にポリグリセリン縮合リシノール酸エステルを加え、約50〜90℃、好ましくは約60〜80℃に加温して溶解し、油相とする。該油相を撹拌しながら、この中に約10〜70℃、好ましくは約20〜60℃で溶解したベニコウジ色素並びに水および/またはアルコールからなる水相をゆっくり加え、例えばクレアミックス(型式:CLM−0.8S;エム・テクニック社製)を用いて、回転数約6000〜20000rpm、撹拌時間約5〜60分間で乳化する方法により油中水型乳化組成物を得ることができる。   In the present invention, first, an aqueous phase containing a beige mushroom pigment and an oil phase containing a polyglycerin-condensed ricinoleic acid ester and an edible fat are emulsified to obtain a water-in-oil emulsion composition. Specifically, polyglycerin-condensed ricinoleic acid ester is added to edible fats and oils and dissolved by heating to about 50 to 90 ° C, preferably about 60 to 80 ° C. While stirring the oil phase, slowly add an aqueous phase consisting of Benicius dye and water and / or alcohol dissolved therein at about 10-70 ° C., preferably about 20-60 ° C., for example, Claremix (model: CLM A water-in-oil emulsion composition can be obtained by a method of emulsifying at a rotational speed of about 6000 to 20000 rpm and a stirring time of about 5 to 60 minutes.

上記水相100質量%中のベニコウジ色素の含有量に特に制限はないが、例えばベニコウジ色素粉末が通常約0.1〜50質量%、好ましくは約1〜35質量%であり、残余が水および/またはアルコールとなるように調整するのが好ましい。水相中のベニコウジ色素、並びに水および/またはアルコールの含有量がこのような範囲であると、十分な量のベニコウジ色素が溶解した水相を調製可能であるため好ましい。なお、上記水相の調製に用いられる水としては、例えば蒸留水、イオン交換樹脂処理水、逆浸透膜処理水および限外ろ過膜処理水などの精製水並びに水道水などの飲料水などが挙げられる。また、上記水相の調製に用いられるアルコールとしては、例えばエタノール、メタノール等の一価アルコールが挙げられる。水およびアルコールを使用する場合は、水:アルコール(体積比)を約99:1〜10:90とすることが好ましく、約95:5〜30:70とすることがより好ましい。   Although there is no particular limitation on the content of Benikouji pigment in 100% by mass of the aqueous phase, for example, Benikouji pigment powder is usually about 0.1 to 50% by mass, preferably about 1 to 35% by mass, with the balance being water and It is preferable to adjust so as to be alcohol. It is preferable that the content of Benikouji pigment and water and / or alcohol in the aqueous phase is in such a range because an aqueous phase in which a sufficient amount of Benikouji pigment is dissolved can be prepared. Examples of the water used for the preparation of the aqueous phase include purified water such as distilled water, ion exchange resin treated water, reverse osmosis membrane treated water and ultrafiltration membrane treated water, and drinking water such as tap water. It is done. Moreover, as alcohol used for preparation of the said water phase, monohydric alcohols, such as ethanol and methanol, are mentioned, for example. When water and alcohol are used, water: alcohol (volume ratio) is preferably about 99: 1 to 10:90, more preferably about 95: 5 to 30:70.

上記油相100質量%中の、ポリグリセリン縮合リシノール酸エステルおよび食用油脂の含有量に特に制限はないが、例えばポリグリセリン縮合リシノール酸エステルが通常約0.1〜70質量%、好ましくは約0.5〜60質量%、より好ましくは約1〜50質量%であり、残余が食用油脂となるように調整するのが好ましい。油相中のポリグリセリン縮合リシノール酸エステルおよび食用油脂の含有量がこのような範囲であると、乳化安定性が良好な油中水型乳化組成物が得られるため好ましい。   The content of polyglycerin condensed ricinoleic acid ester and edible oil / fat in 100% by mass of the oil phase is not particularly limited. For example, polyglycerin condensed ricinoleic acid ester is usually about 0.1 to 70% by mass, preferably about 0%. 0.5 to 60% by mass, more preferably about 1 to 50% by mass, and it is preferable to adjust the remainder to be edible fats and oils. It is preferable that the content of the polyglycerin condensed ricinoleic acid ester and the edible oil / fat in the oil phase is in such a range because a water-in-oil emulsion composition having good emulsion stability can be obtained.

上記油相に加える水相は、例えば、油相1に対して質量比で約0.01〜2とすることが好ましい。より好ましくは、油相1に対して水相を約0.05〜1(質量比)加える。このような範囲であると、乳化安定性が良好な油中水型乳化組成物が得られるため好ましい。   The aqueous phase added to the oil phase is preferably about 0.01 to 2 in terms of mass ratio with respect to the oil phase 1, for example. More preferably, about 0.05 to 1 (mass ratio) of the aqueous phase is added to the oil phase 1. Such a range is preferable because a water-in-oil emulsion composition having good emulsion stability can be obtained.

上記油中水型乳化組成物を製造するための装置としては特に限定されず、例えば、撹拌機、加熱用のジャケットおよび邪魔板等を備えた通常の撹拌・混合槽を用いることができる。装備する撹拌機としては、例えばTKホモミクサー(プライミクス社製)又はクレアミックス(エムテクニック社製)等の高速回転式ホモジナイザーが好ましく用いられる。また、これらの装置で乳化した液を高圧式均質化処理機を使用して、さらに均質化してもよい。ここで高圧式均質化処理機としては、例えばAPVゴーリンホモジナイザー(APV社製)、マイクロフルイダイザー(マイクロフルイデックス社製)、アルティマイザー(スギノマシン社製)又はナノマイザー(大和製罐社製)等を好ましく使用することができる。上記均質化処理機に代えて、例えば超音波乳化機等の均質化処理機を用いてもよい。   The apparatus for producing the water-in-oil emulsion composition is not particularly limited, and for example, a normal stirring / mixing tank equipped with a stirrer, a heating jacket, a baffle plate, and the like can be used. As a stirrer to be equipped, for example, a high-speed rotation type homogenizer such as TK homomixer (manufactured by Primics) or Claremix (manufactured by M Technique) is preferably used. Moreover, you may further homogenize the liquid emulsified with these apparatuses using a high-pressure type homogenizer. Here, examples of the high-pressure homogenizer include an APV gorin homogenizer (manufactured by APV), a microfluidizer (manufactured by Microfluidics), an optimizer (manufactured by Sugino Machine), or a nanomizer (manufactured by Daiwa Steel). Can be preferably used. Instead of the homogenizer, a homogenizer such as an ultrasonic emulsifier may be used.

次いで、上記油中水型乳化組成物を減圧乾燥することによりベニコウジ色素製剤が得られる。減圧乾燥では自体公知の減圧乾燥装置を使用することができ、減圧乾燥装置の使用条件に特に制限はないが、減圧乾燥時の密閉系内の真空度は、通常約100〜50000Pa、好ましくは約1000〜40000Paであり、減圧乾燥時の密閉系内の温度は、通常約30〜90℃、好ましくは約50〜75℃である。減圧乾燥する時間は、通常約10〜180分、好ましくは約30〜120分である。   Subsequently, the water-in-oil emulsion composition is dried under reduced pressure to obtain a beige mushroom pigment preparation. In vacuum drying, a known vacuum drying apparatus can be used, and there are no particular limitations on the use conditions of the vacuum drying apparatus, but the degree of vacuum in the sealed system during vacuum drying is usually about 100 to 50000 Pa, preferably about The temperature in the closed system at the time of drying under reduced pressure is usually about 30 to 90 ° C, preferably about 50 to 75 ° C. The time for drying under reduced pressure is usually about 10 to 180 minutes, preferably about 30 to 120 minutes.

本発明のベニコウジ色素製剤は、ベニコウジ色素を含有する固体相と、ポリグリセリン縮合リシノール酸エステルおよび食用油脂を含有する油相とからなる組成物であることが好ましい。また、該固体相が、メジアン径約0.01〜0.2μmの微粒子として油相中に分散したものであることがより好ましい。本発明においてベニコウジ色素を含有する固体相のメジアン径が上記範囲であると、ベニコウジ色素の光に対する安定性が顕著に向上する。該ベニコウジ色素を含有する固体相のメジアン径は、約0.02〜0.17μmであることがさらに好ましく、約0.03〜0.13μmであることが特に好ましい。   The Benikouji pigment preparation of the present invention is preferably a composition comprising a solid phase containing Bencouge pigment and an oil phase containing polyglycerin-condensed ricinoleic acid ester and edible fats and oils. More preferably, the solid phase is dispersed in the oil phase as fine particles having a median diameter of about 0.01 to 0.2 μm. In the present invention, when the median diameter of the solid phase containing a beige mushroom dye is in the above range, the stability of the bemoji dye to light is significantly improved. The median diameter of the solid phase containing the Benikouji pigment is more preferably about 0.02 to 0.17 μm, and particularly preferably about 0.03 to 0.13 μm.

本発明のベニコウジ色素製剤中の固体相のメジアン径は、例えば、ベニコウジ色素製剤をヘキサンに分散させて試験液を調製し、該試験液中の固体相微粒子のメジアン径を動的光散乱式粒径分布測定装置(型式:LB−500;堀場製作所社製)を用いて測定することにより求めることができる(粒子径基準:体積、試料屈折率:1.600、分散媒屈折率:1.376)。   The median diameter of the solid phase in the Benikouji pigment preparation of the present invention is prepared by, for example, preparing a test solution by dispersing the Benikouji pigment formulation in hexane, and determining the median size of the solid phase fine particles in the test solution using a dynamic light scattering type particle. It can be determined by measurement using a diameter distribution measuring device (model: LB-500; manufactured by HORIBA, Ltd.) (particle diameter standard: volume, sample refractive index: 1.600, dispersion medium refractive index: 1.376). ).

本発明のベニコウジ色素製剤の水分含有量は、約5質量%以下であることが好ましい。本発明において製剤中の水分含有量が上記範囲であると、ベニコウジ色素の光に対する安定性が向上し、また、該ベニコウジ色素製剤を暗所で保存する場合のベニコウジ色素の経時的退色および変色が抑制される。該ベニコウジ色素製剤の水分含有量は、約2質量%以下であることがさらに好ましく、約0.5質量%以下であることが特に好ましく、約0.2質量%以下であることが一層好ましい。   It is preferable that the water content of the beech mushroom pigment preparation of the present invention is about 5% by mass or less. In the present invention, when the water content in the preparation is in the above range, the stability of the beige mushroom pigment to light is improved, and the time-lapse fading and discoloration of the beech mushroom pigment in the case of storing the beige mushroom pigment preparation in a dark place. It is suppressed. The water content of the beige mushroom pigment preparation is more preferably about 2% by mass or less, particularly preferably about 0.5% by mass or less, and further preferably about 0.2% by mass or less.

尚、本発明により得られるベニコウジ色素製剤中の水分含有量は、『第8版 食品添加物公定書』に記載の「19.水分測定法(カールフィッシャー法)」に基づいて測定することができる。   The water content in the beech mushroom pigment preparation obtained by the present invention can be measured based on “19. Moisture determination method (Karl Fischer method)” described in “8th Edition Food Additives Official Specification”. .

本発明のベニコウジ色素製剤100質量%中のベニコウジ色素、ポリグリセリン縮合リシノール酸エステルおよび食用油脂の含有量に特に制限はないが、例えばベニコウジ色素が通常約0.05〜35質量%、好ましくは約0.1〜20質量%、ポリグリセリン縮合リシノール酸エステルが通常約0.5〜70質量%、好ましくは約1〜50質量%、食用油脂が通常20〜99質量%、好ましくは約40〜95質量%となるように調整するのが好ましい。ベニコウジ色素、ポリグリセリン縮合リシノール酸エステルおよび食用油脂の含有量が上記範囲であると、加工食品等にベニコウジ色素製剤が添加された状態において、該製剤に含まれるベニコウジ色素の光に対する安定性が顕著に向上するため好ましい。   Although there are no particular restrictions on the content of the beech powder, polyglycerin-condensed ricinoleic acid ester, and edible oil in 100% by weight of the present Bencow dye preparation, for example, the amount of the beech powder is usually about 0.05 to 35% by weight, preferably about 0.1 to 20% by mass, polyglycerin condensed ricinoleic acid ester is usually about 0.5 to 70% by mass, preferably about 1 to 50% by mass, and edible oil / fat is usually 20 to 99% by mass, preferably about 40 to 95%. It is preferable to adjust so that it may become mass%. When the content of the beech mushroom pigment, polyglycerin condensed ricinoleate and edible oil and fat is within the above-mentioned range, the stability of the beech mushroom pigment contained in the drug product to light is remarkable in the state where the beech mushroom pigment formulation is added to processed foods, etc. Therefore, it is preferable.

本発明のベニコウジ色素製剤中には、本発明の目的および効果を阻害しない範囲で、例えば、ベニコウジ色素以外の色素や酸化防止剤(例えば、抽出トコフェロール、アスコルビン酸パルミチン酸エステルなど)などを添加してもよい。   In the beconic dye preparation of the present invention, for example, a dye other than the becouge dye or an antioxidant (for example, extracted tocopherol, ascorbyl palmitate, etc.) and the like are added within a range not inhibiting the purpose and effect of the present invention. May be.

本発明のベニコウジ色素製剤は、例えば、パン・焼き菓子類、カマボコ、珍味類などの水産加工品、焼き豚、ハム・ソーセージ、鮭フレーク、ラー油、チョコレート、粉末調味料など赤色色素が使用される各種の加工食品および口紅などの化粧品の着色に使用でき、とりわけカマボコの着色に好適に用いることができる。   Benikouji pigment preparation of the present invention, for example, various processed foods such as bread and baked confectionery, rice cakes, delicacies, baked pork, ham sausage, salmon flakes, chili oil, chocolate, powdered seasoning, etc. It can be used for coloring processed foods and cosmetics such as lipsticks, and can be used particularly favorably for coloring of sea urchins.

本発明のベニコウジ色素製剤を用いて食品を着色する方法に特に制限はなく、自体公知の方法により実施することができる。ベニコウジ色素製剤の食品に対する添加量は、その色価や食品の種類などにより異なるが、食品100質量%に対して、好ましくは約0.01〜5.0質量%、より好ましくは約0.02〜3.0質量%である。   There is no restriction | limiting in particular in the method of coloring a foodstuff using the beech mushroom pigment | dye formulation of this invention, It can implement by a publicly known method. Although the amount of the beige mushroom pigment preparation added to the food varies depending on the color value, the kind of the food, and the like, it is preferably about 0.01 to 5.0% by mass, more preferably about 0.02% with respect to 100% by mass of the food. It is -3.0 mass%.

(a)ベニコウジ色素を、(b)上記乳化力試験における乳化相の割合が81〜89%であるポリグリセリン縮合リシノール酸エステルおよび(c)食用油脂を含有する油相中に分散させることにより、ベニコウジ色素の光に対する安定性を向上させることができる。このような、(a)ベニコウジ色素を、(b)乳化力試験における乳化相の割合が81〜89%であるポリグリセリン縮合リシノール酸エステルおよび(c)食用油脂を含有する油相中に分散させる工程を含むベニコウジ色素の光安定化方法も、本発明の1つである。   By dispersing (a) Benikouji pigment in an oil phase containing (b) a polyglycerin condensed ricinoleic acid ester in which the proportion of the emulsified phase in the emulsifying power test is 81 to 89% and (c) edible fats and oils, It is possible to improve the stability of the beige moji pigment to light. Such a (a) bemoji dye is dispersed in an oil phase containing (b) a polyglycerin-condensed ricinoleic acid ester in which the proportion of the emulsified phase in the emulsifying power test is 81 to 89% and (c) edible fats and oils. A method for stabilizing the light of a beige mushroom dye including the steps is also one aspect of the present invention.

ベニコウジ色素を上記油相中に分散させる方法としては、上述したベニコウジ色素製剤の製造方法において油中水型乳化組成物を製造する方法と同様である。また、上述したようにベニコウジ色素を含有する固体相を油相中に分散させることが好ましく、該固体相をメジアン径約0.01〜0.2μmの微粒子として油相中に分散させることがより好ましい。ベニコウジ色素を含有する固体相のメジアン径は、約0.02〜0.17μmであることがさらに好ましく、約0.03〜0.13μmであることが特に好ましい。   The method for dispersing the beech powder dye in the oil phase is the same as the method for producing the water-in-oil emulsion composition in the above-described method for producing the bemoji dye preparation. Further, as described above, it is preferable to disperse a solid phase containing a beige powder pigment in an oil phase, and it is more preferable to disperse the solid phase as fine particles having a median diameter of about 0.01 to 0.2 μm in the oil phase. preferable. The median diameter of the solid phase containing Benikouji pigment is more preferably about 0.02 to 0.17 μm, and particularly preferably about 0.03 to 0.13 μm.

以下に本発明を実施例、比較例および試験例に基づいて、より具体的に説明するが、本発明はこれらに限定されるものではない。   Hereinafter, the present invention will be described more specifically based on Examples, Comparative Examples, and Test Examples, but the present invention is not limited to these.

以下の実施例および比較例で用いるポリグリセリン縮合リシノール酸エステル、および該ポリグリセリン縮合リシノール酸エステルについての下記乳化力試験における乳化相の割合を表1に示す。   Table 1 shows the proportion of the emulsified phase in the following emulsification test for the polyglycerol condensed ricinoleic acid ester used in the following Examples and Comparative Examples, and the polyglycerol condensed ricinoleic acid ester.

Figure 0005317794
Figure 0005317794

<乳化力試験>
1)500ml容ビーカーに菜種白絞油(ボーソー油脂社製)200gおよびポリグリセリン縮合リシノール酸エステル0.80gを入れて混合し、60℃に加温して油相とした。
2)1)の油相をミキサー部と邪魔板との間隙を2.5cmに固定した乳化機(型式:T.K.ホモミクサーMARKII 2.5型;プライミクス社製)を用いて3000rpmで撹拌しながら、該油相に60℃に加温した精製水200gを90秒間かけて加えた。
3)さらに60℃に調温しながら10000rpmで3分間撹拌して油中水型乳化物を得た。
4)3)の油中水型乳化物を100ml容有栓メスシリンダーに100ml入れ37℃の恒温器で120時間保存した。保存後、油相、乳化相および水相に分離したメスシリンダーの内容物について乳化相の体積(ml)を測定し、次式に基づいて乳化相の割合(%)を計算した。
<Emulsifying power test>
1) 200 g of rapeseed white squeezed oil (manufactured by Borso Oil & Fats) and 0.80 g of polyglycerin condensed ricinoleate were mixed in a 500 ml beaker and heated to 60 ° C. to obtain an oil phase.
2) The oil phase of 1) was stirred at 3000 rpm using an emulsifier (model: TK homomixer MARK II 2.5 type; manufactured by Primix Co., Ltd.) in which the gap between the mixer part and the baffle plate was fixed at 2.5 cm. Then, 200 g of purified water heated to 60 ° C. was added to the oil phase over 90 seconds.
3) The mixture was further stirred at 10,000 rpm for 3 minutes while adjusting the temperature to 60 ° C. to obtain a water-in-oil emulsion.
4) 100 ml of the water-in-oil emulsion of 3) was placed in a 100 ml stoppered graduated cylinder and stored in a 37 ° C. incubator for 120 hours. After storage, the volume (ml) of the emulsified phase was measured for the contents of the graduated cylinder separated into an oil phase, an emulsified phase and an aqueous phase, and the proportion (%) of the emulsified phase was calculated based on the following formula.

Figure 0005317794
Figure 0005317794

以下の実施例および比較例で用いるベニコウジ色素粉末についての下記親水性判別試験における分配係数を表2に示す。   Table 2 shows the distribution coefficient in the following hydrophilicity discrimination test for the powdered beech powder used in the following Examples and Comparative Examples.

Figure 0005317794
<親水性判別試験>
1)ベニコウジ色素粉末(色価1000換算)0.002gを50ml容共栓付比色管に入れ、イオン交換水15mlを加え、よく混合して溶解液を得た。
2)1)の溶解液に1−オクタノール(試薬特級;和光純薬工業社製)15mlを加え、前記比色管を上下に180度づつ回転させながら5分間振とうした(回転数20回/分)。
3)振とう後、前記比色管の内容物を50ml容遠心ボトルに入れ、遠心分離機を使用して遠心加速度12000×gで15分間遠心分離を行った。
4)遠心分離後、前記遠心ボトル内の1−オクタノール相および水相を採取し、これらの相の各々について、分光光度計を使用して可視極大吸収波長における吸光度および660nmにおける吸光度を測定した。
5)1−オクタノール相の可視極大吸収波長における吸光度をO1、1−オクタノール相の660nmにおける吸光度をO2、水相の可視極大吸収波長における吸光度をW1、水相の660nmにおける吸光度をW2とし、次式に基づいて分配係数を計算した。
Figure 0005317794
<Hydrophilicity discrimination test>
1) 0.002 g of Benikouji dye powder (color value 1000 conversion) was put into a 50 ml capacitative colorimetric tube, and 15 ml of ion exchange water was added and mixed well to obtain a solution.
2) 15 ml of 1-octanol (special grade reagent; manufactured by Wako Pure Chemical Industries, Ltd.) was added to the solution of 1) and shaken for 5 minutes while rotating the colorimetric tube up and down 180 degrees (rotation number 20 times / Min).
3) After shaking, the contents of the colorimetric tube were placed in a 50 ml centrifuge bottle and centrifuged at 12000 × g for 15 minutes using a centrifuge.
4) After centrifugation, the 1-octanol phase and the aqueous phase in the centrifuge bottle were collected, and for each of these phases, the absorbance at the visible maximum absorption wavelength and the absorbance at 660 nm were measured using a spectrophotometer.
5) The absorbance at the visible maximum absorption wavelength of the 1-octanol phase is O1, the absorbance at 660 nm of the 1-octanol phase is O2, the absorbance at 660 nm of the aqueous phase is W1, and the absorbance at 660 nm of the aqueous phase is W2. The distribution coefficient was calculated based on the formula.

Figure 0005317794
Figure 0005317794

[実施例1]
1)菜種サラダ油(岡村製油社製)128gおよびポリグリセリン縮合リシノール酸エステル(市販品A)16gを300ml容トールビーカーに入れて70℃に加温し、スパーテルで撹拌して溶解して油相とした。
2)ベニコウジ色素粉末a(商品名:リケカラーR−4200(SD);色価2000;理研ビタミン社製)4gをイオン交換水12gに溶解して60℃に加温して水相とした。
3)1)で得た油相をクレアミックス(型式:CLM−0.8S;エム・テクニック社製)を用いて4500rpmで撹拌しながら、2)で得た水相を該油相中に加え、更に該クレアミックスにて70℃、17000rpmの条件で10分間撹拌し、油中水型乳化組成物を得た。
4)3)で得た油中水型乳化組成物のうち50gを500ml容ナス型フラスコに入れ、ダイヤフラム真空ポンプ(型式:V−700;日本ビュッヒ社製)を用いて、温度65℃の条件で該フラスコ内の真空度を30000Paから徐々に2000Paとし、さらに2000Paで30分間減圧乾燥し、ベニコウジ色素製剤(実施品1)46gを得た。
5)該製剤中の水分を上記カールフィッシャー法(機器名:カールフィッシャー水分計 MKA−610;京都電子工業社製、滴定試薬:アクアミクロン滴定剤SS;三菱化学社製、脱水溶剤:アクアミクロン脱水溶剤CM;三菱化学社製)で測定した結果、0.2質量%であった。
[Example 1]
1) 128 g of rapeseed salad oil (manufactured by Okamura Oil Co., Ltd.) and 16 g of polyglycerin condensed ricinoleic acid ester (commercially available product A) are placed in a 300 ml tall beaker, heated to 70 ° C., stirred and dissolved with a spatula to dissolve the oil phase did.
2) 4 g of Benikouji pigment powder a (trade name: Riquecolor R-4200 (SD); color value 2000; manufactured by Riken Vitamin Co., Ltd.) was dissolved in 12 g of ion-exchanged water and heated to 60 ° C. to obtain an aqueous phase.
3) While stirring the oil phase obtained in 1) at 4500 rpm using Claremix (model: CLM-0.8S; manufactured by M Technique Co., Ltd.), the aqueous phase obtained in 2) was added to the oil phase. Further, the mixture was stirred for 10 minutes under the conditions of 70 ° C. and 17000 rpm with the Clare mix to obtain a water-in-oil emulsion composition.
4) 50 g of the water-in-oil emulsified composition obtained in 3) was placed in a 500 ml eggplant type flask, and the temperature was 65 ° C. using a diaphragm vacuum pump (model: V-700; manufactured by Nihon Büch). The vacuum in the flask was gradually increased from 30000 Pa to 2000 Pa, and further dried under reduced pressure at 2000 Pa for 30 minutes, to obtain 46 g of Benikouji pigment preparation (Example product 1).
5) Water in the preparation was clarified by the above Karl Fischer method (device name: Karl Fischer moisture meter MKA-610; manufactured by Kyoto Electronics Industry Co., Ltd., titration reagent: Aquamicron titrant SS; manufactured by Mitsubishi Chemical Corporation, dehydrated solvent: Aquamicron dehydration It was 0.2 mass% as a result of measuring with Solvent CM;

[実施例2]
実施例1のポリグリセリン縮合リシノール酸エステル(市販品A)16gに替えて、ポリグリセリン縮合リシノール酸エステル(市販品B)16gを使用したこと以外は、実施例1と同様に実施し、ベニコウジ色素製剤(実施品2)46gを得た。該製剤中の水分含有量を同様に測定した結果、0.2質量%であった。
[Example 2]
The same procedure as in Example 1 was carried out except that 16 g of polyglycerin condensed ricinoleic acid ester (commercial product B) was used instead of 16 g of polyglycerin condensed ricinoleic acid ester (commercial product A) of Example 1, Benikouji dye 46 g of the preparation (work product 2) was obtained. It was 0.2 mass% as a result of measuring the water content in this formulation similarly.

[実施例3]
実施例1のポリグリセリン縮合リシノール酸エステル(市販品A)16gに替えて、ポリグリセリン縮合リシノール酸エステル(市販品C)16gを使用したこと以外は、実施例1と同様に実施し、ベニコウジ色素製剤(実施品3)46gを得た。該製剤中の水分含有量を同様に測定した結果、0.2質量%であった。
[Example 3]
The same procedure as in Example 1 was carried out except that 16 g of polyglycerin condensed ricinoleic acid ester (commercial product C) was used instead of 16 g of polyglycerin condensed ricinoleic acid ester (commercial product A) of Example 1, Benikouji dye 46 g of the preparation (Example 3) was obtained. It was 0.2 mass% as a result of measuring the water content in this formulation similarly.

[実施例4]
1)菜種サラダ油(岡村製油社製)80gおよびポリグリセリン縮合リシノール酸エステル(市販品B)48gを300ml容トールビーカーに入れて65℃に加温し、スパーテルで撹拌して溶解して油相とした。
2)ベニコウジ色素粉末a(商品名:リケカラーR−4200(SD);色価2000;理研ビタミン社製)4gをイオン交換水14gおよびエタノール(試薬1級、和光純薬工業社製)14gに溶解して65℃に加温して水相とした。
3)1)で得た油相をクレアミックス(型式:CLM−0.8S;エム・テクニック社製)を用いて4500rpmで撹拌しながら、2)で得た水相を該油相中に加え、更に該クレアミックスにて60℃、10000rpmの条件で20分間撹拌し、油中水型乳化組成物を得た。
4)3)で得た油中水型乳化組成物のうち50gを500ml容ナス型フラスコに入れ、ダイヤフラム真空ポンプ(型式:V−700;日本ビュッヒ社製)を用いて、温度65℃の条件で該フラスコ内の真空度を30000Paから徐々に2000Paとし、さらに2000Paで30分間減圧乾燥し、ベニコウジ色素製剤(実施品4)41gを得た。該製剤中の水分含有量を同様に測定した結果、0.1質量%であった。
[Example 4]
1) 80 g of rapeseed salad oil (manufactured by Okamura Oil Co., Ltd.) and 48 g of polyglycerin condensed ricinoleic acid ester (commercial product B) are placed in a 300 ml tall beaker, heated to 65 ° C., stirred and dissolved with a spatula to dissolve the oil phase did.
2) 4 g of Benikouji pigment powder a (trade name: Riquecolor R-4200 (SD); color value 2000; manufactured by Riken Vitamin Co., Ltd.) is dissolved in 14 g of ion-exchanged water and 14 g of ethanol (reagent grade 1, manufactured by Wako Pure Chemical Industries, Ltd.). And heated to 65 ° C. to obtain an aqueous phase.
3) While stirring the oil phase obtained in 1) at 4500 rpm using Claremix (model: CLM-0.8S; manufactured by M Technique Co., Ltd.), the aqueous phase obtained in 2) was added to the oil phase. Further, the mixture was stirred for 20 minutes at 60 ° C. and 10000 rpm with the CLEARMIX to obtain a water-in-oil emulsion composition.
4) 50 g of the water-in-oil emulsified composition obtained in 3) was placed in a 500 ml eggplant type flask, and the temperature was 65 ° C. using a diaphragm vacuum pump (model: V-700; manufactured by Nihon Büch). The vacuum in the flask was gradually increased from 30000 Pa to 2000 Pa, and further dried under reduced pressure at 2000 Pa for 30 minutes to obtain 41 g of Benikouji pigment preparation (Example product 4). It was 0.1 mass% as a result of measuring the water content in this formulation similarly.

[実施例5]
1)ベニコウジ色素水/エタノール溶液(商品名:リケカラーRPH−30;色価63;理研ビタミン社製)200gを1000ml容ナス型フラスコに入れ、ダイヤフラム真空ポンプ(型式:V−500;日本ビュッヒ社製)を用いて、温度45℃の条件で該フラスコ内の真空度を13000Paから徐々に6000Paとし、ベニコウジ色素溶液の量が90gになるまで減圧乾燥し、ベニコウジ色素水/エタノール溶液の濃縮液を得た。
2)1)の濃縮液を500ml容ビーカーに入れ、−80℃で凍結し、凍結乾燥機(型式:DC500;ヤマト科学社製)を用いて、真空度5Paの条件で凍結乾燥を行い、ベニコウジ色素粉末b(色価1200)10.5gを得た。
3)菜種サラダ油(岡村製油社製)88gおよびポリグリセリン縮合リシノール酸エステル(市販品B)48gを300ml容トールビーカーに入れて70℃に加温し、スパーテルで撹拌して溶解して油相とした。
4)2)のベニコウジ色素粉末b7gをイオン交換水17gに溶解して60℃に加温して水相とした。
5)3)で得た油相をクレアミックス(型式:CLM−0.8S;エム・テクニック社製)を用いて4500rpmで撹拌しながら、2)で得た水相を該油相中に加え、更に該クレアミックスにて70℃、17000rpmの条件で10分間撹拌し、油中水型乳化組成物を得た。
6)5)で得た油中水型乳化組成物のうち50gを500ml容ナス型フラスコに入れ、ダイヤフラム真空ポンプ(型式:V−700;日本ビュッヒ社製)を用いて、温度65℃の条件で該フラスコ内の真空度を30000Paから徐々に2000Paとし、さらに2000Paで30分間減圧乾燥し、ベニコウジ色素製剤(実施品5)45gを得た。
7)該製剤中の水分を上記カールフィッシャー法(機器名:カールフィッシャー水分計MKA−610;京都電子工業社製、滴定試薬:アクアミクロン滴定剤SS;三菱化学社製、脱水溶剤:アクアミクロン脱水溶剤CM;三菱化学社製)で測定した結果、0.2質量%であった。
[Example 5]
1) 200 g of Benikouji pigment water / ethanol solution (trade name: Riquecolor RPH-30; color value 63; manufactured by Riken Vitamin Co., Ltd.) is placed in a 1000 ml eggplant type flask, and a diaphragm vacuum pump (model: V-500; manufactured by Nihon Büch) ), The vacuum in the flask was gradually changed from 13000 Pa to 6000 Pa under the condition of a temperature of 45 ° C., and dried under reduced pressure until the amount of Benikouji dye solution reached 90 g, to obtain a concentrated solution of Benikouji dye water / ethanol solution. It was.
2) Put the concentrated solution of 1) into a 500 ml beaker, freeze at −80 ° C., and freeze-dry using a freeze-dryer (model: DC500; manufactured by Yamato Kagaku Co., Ltd.) at a vacuum degree of 5 Pa. 10.5 g of pigment powder b (color value 1200) was obtained.
3) 88 g of rapeseed salad oil (manufactured by Okamura Oil Co., Ltd.) and 48 g of polyglycerin condensed ricinoleic acid ester (commercial product B) are placed in a 300 ml tall beaker, heated to 70 ° C., stirred and dissolved with a spatula to dissolve the oil phase did.
4) 7 g of the beech powder pigment b of 2) was dissolved in 17 g of ion-exchanged water and heated to 60 ° C. to obtain an aqueous phase.
5) While stirring the oil phase obtained in 3) at 4500 rpm using CLEARMIX (model: CLM-0.8S; manufactured by M Technique Co., Ltd.), the aqueous phase obtained in 2) was added to the oil phase. Further, the mixture was stirred for 10 minutes under the conditions of 70 ° C. and 17000 rpm with the Clare mix to obtain a water-in-oil emulsion composition.
6) 50 g of the water-in-oil emulsion composition obtained in 5) was placed in a 500 ml eggplant type flask, and the temperature was 65 ° C. using a diaphragm vacuum pump (model: V-700; manufactured by Nihon Büch). The vacuum in the flask was gradually increased from 30000 Pa to 2000 Pa, and further dried under reduced pressure at 2000 Pa for 30 minutes to obtain 45 g of Benikouji pigment preparation (Example product 5).
7) The water content in the preparation was determined by the Karl Fischer method (equipment name: Karl Fischer moisture meter MKA-610; manufactured by Kyoto Denki Kogyo Co., Ltd., titration reagent: Aquamicron titrant SS; manufactured by Mitsubishi Chemical Corporation, dehydrated solvent: Aquamicron dehydration) It was 0.2 mass% as a result of measuring with Solvent CM;

[実施例6]
1)ベニコウジ色素水/エタノール溶液(商品名:リケカラーRPH−60;色価63;理研ビタミン社製)200gを1000ml容ナス型フラスコに入れ、ダイヤフラム真空ポンプ(型式:V−500;日本ビュッヒ社製)を用いて、温度45℃の条件で該フラスコ内の真空度を13000Paから徐々に6000Paとし、ベニコウジ色素溶液の量が90gになるまで減圧乾燥し、ベニコウジ色素水/エタノール溶液の濃縮液を得た。
2)1)の濃縮液を500ml容ビーカーに入れ、−80℃で凍結し、凍結乾燥機(型式:DC500;ヤマト科学社製)を用いて、真空度5Paの条件で凍結乾燥を行い、ベニコウジ色素粉末c(色価1150)10.9gを得た。
3)菜種サラダ油(岡村製油社製)88gおよびポリグリセリン縮合リシノール酸エステル(市販品B)48gを300ml容トールビーカーに入れて70℃に加温し、スパーテルで撹拌して溶解して油相とした。
4)2)のベニコウジ色素粉末c7gをイオン交換水17gに溶解して60℃に加温して水相とした。
5)3)で得た油相をクレアミックス(型式:CLM−0.8S;エム・テクニック社製)を用いて4500rpmで撹拌しながら、4)で得た水相を該油相中に加え、更に該クレアミックスにて70℃、17000rpmの条件で10分間撹拌し、油中水型乳化組成物を得た。
6)5)で得た油中水型乳化組成物のうち50gを500ml容ナス型フラスコに入れ、ダイヤフラム真空ポンプ(型式:V−700;日本ビュッヒ社製)を用いて、温度65℃の条件で該フラスコ内の真空度を30000Paから徐々に2000Paとし、さらに2000Paで30分間減圧乾燥し、ベニコウジ色素製剤(実施品6)45gを得た。
7)該製剤中の水分を上記カールフィッシャー法(機器名:カールフィッシャー水分計MKA−610;京都電子工業社製、滴定試薬:アクアミクロン滴定剤SS;三菱化学社製、脱水溶剤:アクアミクロン脱水溶剤CM;三菱化学社製)で測定した結果、0.2質量%であった。
[Example 6]
1) 200 g of Benikouji pigment water / ethanol solution (trade name: Riquecolor RPH-60; color value 63; manufactured by Riken Vitamin Co., Ltd.) is placed in a 1000 ml eggplant type flask, and a diaphragm vacuum pump (model: V-500; manufactured by Nihon Büch) ), The vacuum in the flask was gradually changed from 13000 Pa to 6000 Pa under the condition of a temperature of 45 ° C., and dried under reduced pressure until the amount of Benikouji dye solution reached 90 g, to obtain a concentrated solution of Benikouji dye water / ethanol solution. It was.
2) Put the concentrated solution of 1) into a 500 ml beaker, freeze at −80 ° C., and freeze-dry using a freeze-dryer (model: DC500; manufactured by Yamato Kagaku Co., Ltd.) at a vacuum degree of 5 Pa. 10.9 g of pigment powder c (color value 1150) was obtained.
3) 88 g of rapeseed salad oil (manufactured by Okamura Oil Co., Ltd.) and 48 g of polyglycerin condensed ricinoleic acid ester (commercial product B) are placed in a 300 ml tall beaker, heated to 70 ° C., stirred and dissolved with a spatula to dissolve the oil phase did.
4) 7 g of the beech powder pigment c of 2) was dissolved in 17 g of ion-exchanged water and heated to 60 ° C. to obtain an aqueous phase.
5) While stirring the oil phase obtained in 3) at 4500 rpm using CLEARMIX (model: CLM-0.8S; manufactured by M Technique Co., Ltd.), the aqueous phase obtained in 4) was added to the oil phase. Further, the mixture was stirred for 10 minutes under the conditions of 70 ° C. and 17000 rpm with the Clare mix to obtain a water-in-oil emulsion composition.
6) 50 g of the water-in-oil emulsion composition obtained in 5) was placed in a 500 ml eggplant type flask, and the temperature was 65 ° C. using a diaphragm vacuum pump (model: V-700; manufactured by Nihon Büch). The vacuum in the flask was gradually increased from 30000 Pa to 2000 Pa, and further dried under reduced pressure at 2000 Pa for 30 minutes to obtain 45 g of Benikouji pigment preparation (Example 6).
7) The water content in the preparation was determined by the Karl Fischer method (equipment name: Karl Fischer moisture meter MKA-610; manufactured by Kyoto Denki Kogyo Co., Ltd., titration reagent: Aquamicron titrant SS; manufactured by Mitsubishi Chemical Corporation, dehydrated solvent: Aquamicron dehydration) It was 0.2 mass% as a result of measuring with Solvent CM;

[実施例7]
1)ベニコウジ色素水/エタノール溶液(商品名:リケカラーRPH−30;色価63;理研ビタミン社製)400gを2000ml容ナス型フラスコに入れ、ダイヤフラム真空ポンプ(型式:V−500;日本ビュッヒ社製)を用いて、温度45℃の条件で該フラスコ内の真空度を13000Paから徐々に6000Paとし、ベニコウジ色素溶液の量が180gになるまで減圧乾燥し、ベニコウジ色素水/エタノール溶液の濃縮液を得た。
2)1)の濃縮液を500ml容ビーカーに入れ、−80℃で凍結し、凍結乾燥機(型式:DC500;ヤマト科学社製)を用いて、真空度5Paの条件で凍結乾燥を行い、ベニコウジ色素粉末(色価1200)21.0gを得た。
3)2)のベニコウジ色素粉末13.0gを500ml容ビーカーに入れ、イオン交換水42gおよびエタノール(試薬1級、和光純薬工業社製)45gを加えて溶解させ、これにアセトン(試薬特級、和光純薬工業社製)200gを徐々に(10g/分)加え、さらに15分間撹拌した。
4)攪拌後、ビーカー内の沈殿画分をデカンテーションにて回収し、500ml容ナス型フラスコに入れ、ダイヤフラム真空ポンプ(型式:V−500;日本ビュッヒ社製)を用いて該フラスコ内の真空度を500Paとして減圧乾燥し、ベニコウジ色素粉末d(色価960)8.2gを得た。
5)菜種サラダ油(岡村製油社製)88gおよびポリグリセリン縮合リシノール酸エステル(市販品B)48gを300ml容トールビーカーに入れて70℃に加温し、スパーテルで撹拌して溶解して油相とした。
6)4)のベニコウジ色素粉末d7gをイオン交換水17gに溶解して60℃に加温して水相とした。
7)5)で得た油相をクレアミックス(型式:CLM−0.8S;エム・テクニック社製)を用いて4500rpmで撹拌しながら、2)で得た水相を該油相中に加え、更に該クレアミックスにて70℃、17000rpmの条件で10分間撹拌し、油中水型乳化組成物を得た。
8)7)で得た油中水型乳化組成物のうち50gを500ml容ナス型フラスコに入れ、ダイヤフラム真空ポンプ(型式:V−700;日本ビュッヒ社製)を用いて、温度65℃の条件で該フラスコ内の真空度を30000Paから徐々に2000Paとし、さらに2000Paで30分間減圧乾燥し、ベニコウジ色素製剤(実施品7)45gを得た。
9)該製剤中の水分を上記カールフィッシャー法(機器名:カールフィッシャー水分計 MKA−610;京都電子工業社製、滴定試薬:アクアミクロン滴定剤SS;三菱化学社製、脱水溶剤:アクアミクロン脱水溶剤CM;三菱化学社製)で測定した結果、0.2質量%であった。
[Example 7]
1) 400 g of Benikouji pigment water / ethanol solution (trade name: Riquecolor RPH-30; color value 63; manufactured by Riken Vitamin Co., Ltd.) is placed in a 2000 ml eggplant type flask, and a diaphragm vacuum pump (model: V-500; manufactured by Nihon Büch) ), The vacuum degree in the flask is gradually changed from 13000 Pa to 6000 Pa under the condition of a temperature of 45 ° C., and dried under reduced pressure until the amount of Benikouji dye solution reaches 180 g, thereby obtaining a concentrated solution of Benikouji dye water / ethanol solution. It was.
2) Put the concentrated solution of 1) into a 500 ml beaker, freeze at −80 ° C., and freeze-dry using a freeze-dryer (model: DC500; manufactured by Yamato Kagaku Co., Ltd.) at a vacuum degree of 5 Pa. 21.0 g of dye powder (color value 1200) was obtained.
3) Place 13.0 g of the beige powder pigment powder of 2) into a 500 ml beaker, add 42 g of ion exchange water and 45 g of ethanol (reagent grade 1, Wako Pure Chemical Industries, Ltd.) and dissolve it in acetone (reagent grade, 200 g (manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added (10 g / min), and the mixture was further stirred for 15 minutes.
4) After stirring, the precipitate fraction in the beaker was collected by decantation, put into a 500 ml eggplant type flask, and vacuumed in the flask using a diaphragm vacuum pump (model: V-500; manufactured by Nihon Büch). The pressure was reduced to 500 Pa and dried under reduced pressure to obtain 8.2 g of Benikouji pigment powder d (color value 960).
5) 88 g of rapeseed salad oil (manufactured by Okamura Oil Co., Ltd.) and 48 g of polyglycerin condensed ricinoleic acid ester (commercial product B) are placed in a 300 ml tall beaker, heated to 70 ° C., stirred and dissolved with a spatula to dissolve the oil phase did.
6) The beech powder pigment d7g of 4) was dissolved in 17 g of ion-exchanged water and heated to 60 ° C. to obtain an aqueous phase.
7) While stirring the oil phase obtained in 5) at 4500 rpm using CLEARMIX (model: CLM-0.8S; manufactured by M Technique Co., Ltd.), the aqueous phase obtained in 2) was added to the oil phase. Further, the mixture was stirred for 10 minutes under the conditions of 70 ° C. and 17000 rpm with the Clare mix to obtain a water-in-oil emulsion composition.
8) 50 g of the water-in-oil emulsified composition obtained in 7) is put into a 500 ml eggplant type flask, and the temperature is 65 ° C. using a diaphragm vacuum pump (model: V-700; manufactured by Nihon Büch). The vacuum inside the flask was gradually increased from 30000 Pa to 2000 Pa, and further dried under reduced pressure at 2000 Pa for 30 minutes to obtain 45 g of Benikouji pigment preparation (Example product 7).
9) The water in the preparation was clarified by the Karl Fischer method (equipment name: Karl Fischer moisture meter MKA-610; manufactured by Kyoto Electronics Industry Co., Ltd., titration reagent: Aquamicron titrant SS; manufactured by Mitsubishi Chemical Corporation, dehydrated solvent: Aquamicron dehydration) It was 0.2 mass% as a result of measuring with Solvent CM;

[比較例1]
実施例1のポリグリセリン縮合リシノール酸エステル(市販品A)16gに替えて、ポリグリセリン縮合リシノール酸エステル(市販品D)16gを使用したこと以外は、実施例1と同様に実施し、ベニコウジ色素製剤(比較品1)46gを得た。該製剤中の水分を同様に測定した結果、0.2質量%であった。
[Comparative Example 1]
The same procedure as in Example 1 was carried out except that 16 g of polyglycerin condensed ricinoleic acid ester (commercial product D) was used instead of 16 g of polyglycerin condensed ricinoleic acid ester (commercial product A) of Example 1, Benikouji dye 46 g of the preparation (Comparative product 1) was obtained. It was 0.2 mass% as a result of measuring the water | moisture content in this formulation similarly.

[比較例2]
実施例1のポリグリセリン縮合リシノール酸エステル(市販品A)16gに替えて、ポリグリセリン縮合リシノール酸エステル(市販品E)16gを使用したこと以外は、実施例1と同様に実施し、ベニコウジ色素製剤(比較品2)46gを得た。該製剤中の水分を同様に測定した結果、0.2質量%であった。
[Comparative Example 2]
The same procedure as in Example 1 was carried out except that 16 g of polyglycerin condensed ricinoleic acid ester (commercial product E) was used instead of 16 g of polyglycerin condensed ricinoleic acid ester (commercial product A) of Example 1, Benikouji dye 46 g of the preparation (Comparative product 2) was obtained. It was 0.2 mass% as a result of measuring the water | moisture content in this formulation similarly.

[試験例1]製剤中のベニコウジ色素の粒子径測定
実施例1〜7並びに比較例1および2で製造したベニコウジ色素製剤(実施品1〜7並びに比較品1および2)それぞれについて、該製剤中のベニコウジ色素を含有する固体相微粒子のメジアン径を測定した。具体的には、ベニコウジ色素製剤(実施品1〜7並びに比較品1および2)を各々ヘキサンに分散させて試験液を調製し、該試験液中の固体相微粒子のメジアン径を動的光散乱式粒径分布測定装置(型式:LB−500;堀場製作所社製)を用いて測定した(粒子径基準:体積、試料屈折率:1.600、分散媒屈折率:1.376)。
結果を表3に示す。
[Test Example 1] Particle size measurement of Benikouji pigment in the formulation Examples 1-7 and Benikouji pigment formulations produced in Comparative Examples 1 and 2 (Examples 1-7 and Comparative products 1 and 2), respectively, in the formulation The median diameter of the solid phase microparticles containing the benichouji dye was measured. Specifically, a test liquid is prepared by dispersing Benikouji pigment preparations (Examples 1 to 7 and Comparative products 1 and 2) in hexane, and the median diameter of solid phase fine particles in the test liquid is dynamically scattered. It was measured using a formula particle size distribution measuring apparatus (model: LB-500; manufactured by HORIBA, Ltd.) (particle diameter standard: volume, sample refractive index: 1.600, dispersion medium refractive index: 1.376).
The results are shown in Table 3.

Figure 0005317794
Figure 0005317794

表1および表3の結果から、上記乳化力試験における乳化相の割合が81〜89%の範囲内にあるポリグリセリン縮合リシノール酸エステルを用いた場合には、該範囲外のものを用いた場合に比べ、ベニコウジ色素を含有する固体相微粒子のメジアン径が顕著に小さいベニコウジ色素製剤が得られることが明らかであった。   From the results of Table 1 and Table 3, when using a polyglycerin condensed ricinoleic acid ester in which the proportion of the emulsified phase in the emulsifying power test is within the range of 81 to 89%, a case outside this range is used. Compared to the above, it was clear that a beige mushroom dye preparation having a remarkably small median diameter of the solid phase fine particles containing the bemoji dye can be obtained.

[試験例2]着色カマボコの光安定性試験(1)
冷凍調理すり身(大冷社製)を解凍し、フードプロセッサー(型式:MK−K48;松下電器産業社製)を用いて均一になるまで破砕した。破砕した該調理すり身120gに、実施例1〜3並びに比較例1および2で製造したベニコウジ色素製剤(実施品1〜3並びに比較品1および2)2.6gまたは実施例4で製造したベニコウジ色素製剤(実施品4)2.3gを加え、スパーテルで均一になるまで混合し、着色すり身を得た。得られた着色すり身90gをナイロン製の耐熱袋(15×24cm)に入れて真空包装し、該袋内の着色すり身を厚さ約10mmに均一に整えた。真空包装された着色すり身を88℃の温水浴下で30分間加熱し、着色カマボコ試料を調製した。また、対照として、従来からカマボコの着色に使用されているベニコウジ色素水/エタノール溶液(対照品A;商品名:リケカラーR−30;色価63;理研ビタミン社製)2.3gを用いて同様に着色すり身を調製した。
[Test Example 2] Light stability test of colored sea urchin (1)
The frozen cooked surimi (manufactured by Daihyo Co., Ltd.) was thawed and crushed until uniform using a food processor (model: MK-K48; manufactured by Matsushita Electric Industrial Co., Ltd.). To 120 g of the crushed cooked surimi, 2.6 g of Benikouji pigment preparations produced in Examples 1 to 3 and Comparative Examples 1 and 2 (Examples 1 to 3 and Comparative Products 1 and 2) or Benikouji pigment produced in Example 4 2.3 g of the preparation (practical product 4) was added and mixed with a spatula until uniform to obtain a colored surimi. 90 g of the obtained colored surimi was placed in a heat-resistant bag made of nylon (15 × 24 cm) and vacuum-packed, and the colored surimi in the bag was uniformly arranged to a thickness of about 10 mm. The colored surimi packed in a vacuum package was heated in a warm water bath at 88 ° C. for 30 minutes to prepare a colored sea urchin sample. In addition, as a control, the same was used with 2.3 g of an aqueous solution of Benikomiji dye / ethanol (control product A: trade name: Riquecolor R-30; color value 63; manufactured by Riken Vitamin Co., Ltd.), which has been conventionally used for coloring of sea urchins. A colored surimi was prepared.

真空包装された着色カマボコ試料の半分を包装の外側からアルミ箔で覆って遮光し、10℃、6700ルクスの条件で、光安定性試験機(型式:PT−400NC;日本医化器械製作所社製)内で6時間保存した。保存後、着色カマボコ試料を、包装の外側から黒色試料押さえを用いて固定し、分光式色彩計(型式:SE−2000、日本電色工業社製)で光照射部分および遮光部分の色調(L*a*b*値)を各々測定し(測定径:直径10mm)、測定された色調および次式に基づいて、光照射部分と遮光部分のL*a*b*色差(ΔE*(ab))を算出した。結果を表4に示す。   Half of the vacuum-packed colored sea urchin sample is covered with aluminum foil from the outside of the package and shielded from light. Under the conditions of 10 ° C. and 6700 lux, the light stability tester (model: PT-400NC; manufactured by Nippon Medical Chemical Co., Ltd.) ) For 6 hours. After storage, the colored sea urchin sample is fixed from the outside of the package using a black sample holder, and the color tone (L of the light-irradiated part and light-shielded part) is measured with a spectroscopic colorimeter (model: SE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.). * A * b * value) (measured diameter: diameter 10 mm), and based on the measured color tone and the following formula, L * a * b * color difference (ΔE * (ab)) ) Was calculated. The results are shown in Table 4.

Figure 0005317794
Figure 0005317794

上記式中、L*は、明度を表す。a*は、赤方向の色度を表す。b*は、黄方向の色度を表す。ΔE*(ab)は変色の程度を表す。   In the above formula, L * represents lightness. a * represents the chromaticity in the red direction. b * represents chromaticity in the yellow direction. ΔE * (ab) represents the degree of discoloration.

Figure 0005317794
Figure 0005317794

表1および表4の結果から、上記乳化力試験における乳化相の割合が81〜89%の範囲内にあるポリグリセリン縮合リシノール酸エステルを用いて製造したベニコウジ色素製剤(実施品1〜5)により着色したカマボコは、該範囲外のポリグリセリン縮合リシノール酸エステルを用いて製造したベニコウジ色素製剤(比較品1〜2、および対照品A)により着色したカマボコに比べ、光照射による色差が小さく、相対的に光に対する安定性が改善されたものであった。また、上記乳化力試験における乳化相の割合が81〜89%の範囲内にあるポリグリセリン縮合リシノール酸エステルを用いて製造したベニコウジ色素製剤により着色したカマボコは、従来からカマボコの着色に使用されているベニコウジ色素水/エタノール溶液で着色したカマボコとの比較においても、相対的に光に対する安定性が改善されたものであった。   From the results shown in Tables 1 and 4, according to Benicowian dye preparations (practical products 1 to 5) produced using polyglycerin condensed ricinoleic acid ester in which the proportion of the emulsified phase in the emulsifying power test is in the range of 81 to 89%. The colored sea urchin has a smaller color difference due to light irradiation compared to the sea urchin colored by a beige mushroom pigment preparation (Comparative products 1 and 2 and Control product A) produced using a polyglycerin condensed ricinoleic acid ester outside the above range. In particular, the stability to light was improved. In addition, the kamaboko colored by the beige mushroom pigment preparation produced by using the polyglycerin condensed ricinoleic acid ester in the range of 81 to 89% of the emulsified phase in the emulsifying power test has been conventionally used for coloring kamaboko. In comparison with the eelworm pigmented water / ethanol solution, the stability to light was relatively improved.

[試験例3]着色カマボコの光安定性試験(2)
冷凍調理すり身(大冷社製)を解凍し、フードプロセッサー(型式:MK−K48;松下電器産業社製)を用いて均一になるまで破砕した。破砕した該調理すり身120gに、実施例4で製造したベニコウジ色素製剤(実施品4)1.0g、実施例5で製造したベニコウジ色素製剤(実施品5)1.0g、実施例6で製造したベニコウジ色素製剤(実施品6)1.1gまたは実施例7で製造したベニコウジ色素製剤(実施品7)1.3gを加え、スパーテルで均一になるまで混合し、着色すり身を得た。得られた着色すり身90gをナイロン製の耐熱袋(15×24cm)に入れて真空包装し、該袋内の着色すり身を厚さ約10mmに均一に整えた。真空包装された着色すり身を88℃の温水浴下で30分間加熱し、着色カマボコ試料を調製した。また、対照として、従来からカマボコの着色に使用されているベニコウジ色素水/エタノール溶液(対照品A;商品名:リケカラーR−30;色価63;理研ビタミン社製)1.0gまたはベニコウジ色素水/エタノール溶液(対照品B;商品名:リケカラーRPH−30;色価63;理研ビタミン社製)1.0gを用いて同様に着色すり身を調製した。
[Test Example 3] Light stability test of colored sea urchin (2)
The frozen cooked surimi (manufactured by Daihyo Co., Ltd.) was thawed and crushed until uniform using a food processor (model: MK-K48; manufactured by Matsushita Electric Industrial Co., Ltd.). To 120 g of the crushed cooked surimi, 1.0 g of Benikouji pigment preparation (Example 4) produced in Example 4 and 1.0 g of Benikouji pigment preparation (Example 5) produced in Example 5 were produced in Example 6. 1.1 g of Benikouji pigment preparation (Example 6) or 1.3 g of Benikouji pigment preparation (Example 7) produced in Example 7 were added and mixed with a spatula until uniform to obtain a colored surimi. 90 g of the obtained colored surimi was placed in a heat-resistant bag made of nylon (15 × 24 cm) and vacuum-packed, and the colored surimi in the bag was uniformly arranged to a thickness of about 10 mm. The colored surimi packed in a vacuum package was heated in a warm water bath at 88 ° C. for 30 minutes to prepare a colored sea urchin sample. As a control, 1.0 g of Benikouji pigment water / ethanol solution (control product A: trade name: Riquet color R-30; color value 63; manufactured by Riken Vitamin Co., Ltd.) or Benikouji pigment water, which has been conventionally used for coloring of sea urchins. A colored surimi was similarly prepared using 1.0 g of an ethanol solution (control product B; trade name: Riquecolor RPH-30; color value 63; manufactured by Riken Vitamin Co., Ltd.).

真空包装された着色カマボコ試料の半分を包装の外側からアルミ箔で覆って遮光し、10℃、3300ルクスの条件で、光安定性試験機(型式:PT−400NC;日本医化器械製作所社製)内で5時間保存した。保存後、着色カマボコ試料を、包装の外側から黒色試料押さえを用いて固定し、分光式色彩計(型式:SE−2000、日本電色工業社製)で光照射部分および遮光部分の色調(L*a*b*値)を各々測定し(測定径:直径10mm)、測定された色調および次式に基づいて、光照射部分と遮光部分のL*a*b*色差(ΔE*(ab))を算出した。結果を表5に示す。   Half of the vacuum-packed colored sea urchin sample is covered with aluminum foil from the outside of the package, shielded from light, and subjected to a light stability tester (model: PT-400NC; manufactured by Nippon Medical Instruments Co., Ltd.) at 10 ° C and 3300 lux. ) For 5 hours. After storage, the colored sea urchin sample is fixed from the outside of the package using a black sample holder, and the color tone (L of the light-irradiated part and light-shielded part) is measured with a spectroscopic colorimeter (model: SE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.). * A * b * value) (measured diameter: diameter 10 mm), and based on the measured color tone and the following formula, L * a * b * color difference (ΔE * (ab)) ) Was calculated. The results are shown in Table 5.

Figure 0005317794
Figure 0005317794

上記式中、L*は、明度を表す。a*は、赤方向の色度を表す。b*は、黄方向の色度を表す。ΔE*(ab)は変色の程度を表す。   In the above formula, L * represents lightness. a * represents the chromaticity in the red direction. b * represents chromaticity in the yellow direction. ΔE * (ab) represents the degree of discoloration.

Figure 0005317794
Figure 0005317794

表1、表2および表5の結果から、上記乳化力試験における乳化相の割合が81〜89%の範囲内にあるポリグリセリン縮合リシノール酸エステルを用いて製造したベニコウジ色素製剤(実施品4〜7)のうち、上記親水性判別試験におけるベニコウジ色素粉末の分配係数が、−1.2〜−0.1の範囲内にあるベニコウジ色素粉末を用いて製造したベニコウジ色素製剤(実施品5〜7)により着色したカマボコは、ベニコウジ色素粉末の分配係数が該範囲外にあるベニコウジ色素粉末を用いて製造したベニコウジ色素製剤(実施品4)により着色したカマボコに比べ、光照射による色差がより小さく、相対的に光に対する安定性がさらに改善されたものであった。   From the results of Table 1, Table 2 and Table 5, Benikouji pigment preparations manufactured using polyglycerin condensed ricinoleic acid esters in which the proportion of the emulsified phase in the emulsifying power test is in the range of 81 to 89% (practical products 4 to 4). 7), a Benikouji pigment preparation produced by using Benikouji pigment powder in which the distribution coefficient of Benikouji pigment powder is in the range of -1.2 to -0.1 in the hydrophilicity discrimination test (Examples 5 to 7) ), The color difference due to light irradiation is smaller than that of the sea bream colored by the bene moji pigment preparation (practical product 4) produced using the beni moji pigment powder whose distribution coefficient is outside the range. The stability against light was further improved.

Claims (3)

(a)ベニコウジ色素、(b)下記乳化力試験における乳化相の割合が81〜89%であるポリグリセリン縮合リシノール酸エステルおよび(c)食用油脂を含有するベニコウジ色素製剤。
<乳化力試験>
1)500ml容ビーカーに菜種白絞油(ボーソー油脂社製)200gおよびポリグリセリン縮合リシノール酸エステル0.80gを入れて混合し、60℃に加温して油相とする。
2)1)の油相をミキサー部と邪魔板との間隙を2.5cmに固定した乳化機(型式:T.K.ホモミクサーMARKII 2.5型;プライミクス社製)を用いて3000rpmで撹拌しながら、該油相に60℃に加温した精製水200gを90秒間かけて加える。
3)さらに、60℃に調温しながら10000rpmで3分間撹拌して油中水型乳化物を得る。
4)3)で得た油中水型乳化物を100ml容有栓メスシリンダーに100ml入れ37℃の恒温器で120時間保存する。保存後、油相、乳化相および水相に分離したメスシリンダーの内容物について乳化相の体積(ml)を測定し、次式に基づいて乳化相の割合(%)を計算する。
Figure 0005317794
(A) Benikouji pigment preparation, (b) Benikouji pigment preparation containing polyglycerin condensed ricinoleic acid ester having an emulsified phase ratio of 81 to 89% in the following emulsifying power test and (c) edible oil and fat.
<Emulsifying power test>
1) In a 500 ml beaker, 200 g of rapeseed white squeezed oil (manufactured by Borso Oil & Fats Co., Ltd.) and 0.80 g of polyglycerin condensed ricinoleate are mixed and heated to 60 ° C. to obtain an oil phase.
2) The oil phase of 1) was stirred at 3000 rpm using an emulsifier (model: TK homomixer MARK II 2.5 type; manufactured by Primix Co., Ltd.) in which the gap between the mixer part and the baffle plate was fixed at 2.5 cm. Then, 200 g of purified water heated to 60 ° C. was added to the oil phase over 90 seconds.
3) Furthermore, stirring at 10000 rpm for 3 minutes while adjusting the temperature to 60 ° C., a water-in-oil emulsion is obtained.
4) Add 100 ml of the water-in-oil emulsion obtained in 3) to a 100 ml stoppered graduated cylinder and store it in a thermostat at 37 ° C. for 120 hours. After storage, the volume (ml) of the emulsified phase is measured for the contents of the graduated cylinder separated into an oil phase, an emulsified phase and an aqueous phase, and the proportion (%) of the emulsified phase is calculated based on the following formula.
Figure 0005317794
ベニコウジ色素がベニコウジ色素粉末であり、該ベニコウジ色素粉末について下記親水性判別試験を実施した場合の分配係数が−1.2〜−0.1である、請求項1のベニコウジ色素製剤。
<親水性判別試験>
1)ベニコウジ色素粉末(色価1000換算)0.002gを50ml容共栓付比色管に入れ、イオン交換水15mlを加え、よく混合して溶解液を得る。
2)1)の溶解液に1−オクタノール(試薬特級;和光純薬工業社製)15mlを加え、前記比色管を上下に180度づつ回転させながら5分間振とうする(回転数20回/分)。
3)振とう後、前記比色管の内容物を50ml容遠心ボトルに入れ、遠心分離機を使用して遠心加速度12000×gで15分間遠心分離を行う。
4)遠心分離後、前記遠心ボトル内の1−オクタノール相および水相を採取し、これらの相の各々について、分光光度計を使用して可視極大吸収波長における吸光度および660nmにおける吸光度を測定する。
5)1−オクタノール相の可視極大吸収波長における吸光度をO1、1−オクタノール相の660nmにおける吸光度をO2、水相の可視極大吸収波長における吸光度をW1、水相の660nmにおける吸光度をW2とし、次式に基づいて分配係数を計算する。
Figure 0005317794
The beige mushroom dye preparation according to claim 1, wherein the beige mushroom dye is a bemoji dye powder, and the partition coefficient when the following hydrophilicity discrimination test is performed on the bemoji dye powder is −1.2 to −0.1.
<Hydrophilicity discrimination test>
1) Put 0.002 g of Benikouji pigment powder (converted to a color value of 1000) into a 50 ml capacitative colorimetric tube, add 15 ml of ion exchange water, and mix well to obtain a solution.
2) Add 15 ml of 1-octanol (special grade reagent; manufactured by Wako Pure Chemical Industries, Ltd.) to the solution of 1) and shake for 5 minutes while rotating the colorimetric tube 180 degrees up and down (rotation number 20 times / Min).
3) After shaking, the contents of the colorimetric tube are placed in a 50 ml centrifuge bottle and centrifuged for 15 minutes at a centrifugal acceleration of 12000 × g using a centrifuge.
4) After centrifugation, the 1-octanol phase and the aqueous phase in the centrifuge bottle are collected, and the absorbance at the visible maximum absorption wavelength and the absorbance at 660 nm are measured for each of these phases using a spectrophotometer.
5) The absorbance at the visible maximum absorption wavelength of the 1-octanol phase is O1, the absorbance at 660 nm of the 1-octanol phase is O2, the absorbance at 660 nm of the aqueous phase is W1, and the absorbance at 660 nm of the aqueous phase is W2. Calculate the distribution coefficient based on the formula.
Figure 0005317794
(a)ベニコウジ色素を含有する水相と、(b)下記乳化力試験における乳化相の割合が81〜89%であるポリグリセリン縮合リシノール酸エステルおよび(c)食用油脂を含有する油相とを乳化して油中水型乳化組成物を得る工程と、該油中水型乳化組成物を減圧乾燥する工程とを含むことを特徴とするベニコウジ色素製剤の製造方法。
<乳化力試験>
1)500ml容ビーカーに菜種白絞油(ボーソー油脂社製)200gおよびポリグリセリン縮合リシノール酸エステル0.80gを入れて混合し、60℃に加温して油相とする。
2)1)の油相をミキサー部と邪魔板との間隙を2.5cmに固定した乳化機(型式:T.K.ホモミクサーMARKII 2.5型;プライミクス社製)を用いて3000rpmで撹拌しながら、該油相に60℃に加温した精製水200gを90秒間かけて加える。
3)さらに、60℃に調温しながら10000rpmで3分間撹拌して油中水型乳化物を得る。
4)3)で得た油中水型乳化物を100ml容有栓メスシリンダーに100ml入れ37℃の恒温器で120時間保存する。保存後、油相、乳化相および水相に分離したメスシリンダーの内容物について乳化相の体積(ml)を測定し、次式に基づいて乳化相の割合(%)を計算する。
Figure 0005317794
(A) an aqueous phase containing Benikouji pigment, and (b) a polyglycerin condensed ricinoleic acid ester in which the proportion of the emulsified phase in the following emulsifying power test is 81 to 89% and (c) an oil phase containing edible fats and oils. A method for producing a beige mushroom pigment preparation, comprising a step of emulsifying to obtain a water-in-oil emulsion composition and a step of drying the water-in-oil emulsion composition under reduced pressure.
<Emulsifying power test>
1) In a 500 ml beaker, 200 g of rapeseed white squeezed oil (manufactured by Borso Oil & Fats Co., Ltd.) and 0.80 g of polyglycerin condensed ricinoleate are mixed and heated to 60 ° C. to obtain an oil phase.
2) The oil phase of 1) was stirred at 3000 rpm using an emulsifier (model: TK homomixer MARK II 2.5 type; manufactured by Primix Co., Ltd.) in which the gap between the mixer part and the baffle plate was fixed at 2.5 cm. Then, 200 g of purified water heated to 60 ° C. was added to the oil phase over 90 seconds.
3) Furthermore, stirring at 10000 rpm for 3 minutes while adjusting the temperature to 60 ° C., a water-in-oil emulsion is obtained.
4) Add 100 ml of the water-in-oil emulsion obtained in 3) to a 100 ml stoppered graduated cylinder and store it in a thermostat at 37 ° C. for 120 hours. After storage, the volume (ml) of the emulsified phase is measured for the contents of the graduated cylinder separated into an oil phase, an emulsified phase and an aqueous phase, and the proportion (%) of the emulsified phase is calculated based on the following formula.
Figure 0005317794
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