JP4961465B2 - Method for preventing precipitation in red radish pigment solution and red radish pigment solution - Google Patents

Method for preventing precipitation in red radish pigment solution and red radish pigment solution Download PDF

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JP4961465B2
JP4961465B2 JP2009237433A JP2009237433A JP4961465B2 JP 4961465 B2 JP4961465 B2 JP 4961465B2 JP 2009237433 A JP2009237433 A JP 2009237433A JP 2009237433 A JP2009237433 A JP 2009237433A JP 4961465 B2 JP4961465 B2 JP 4961465B2
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radish pigment
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出 得丸
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Description

本発明は、赤ダイコンから抽出した色素成分を含有する、低温保存安定性に優れた赤ダイコン色素液製剤に関する。   The present invention relates to a red radish pigment solution preparation that contains a pigment component extracted from red radish and has excellent low-temperature storage stability.

従来、天然物由来の色素成分の一種として、赤ダイコンから抽出された色素成分が知られており、食品,飲料,化粧品,保健・医薬品類等の着色剤として広く利用されている。   Conventionally, a pigment component extracted from red radish is known as a kind of pigment component derived from natural products, and is widely used as a colorant for foods, beverages, cosmetics, health / pharmaceuticals and the like.

赤ダイコンの色素成分は、通常、赤ダイコンから色素溶液として抽出される。赤ダイコン色素溶液はそのままでも使用できるが、一般には減圧蒸留等の常法により色価1500〜3000程度にまで濃縮され、或いは乾燥粉末化されて赤ダイコン色素原体となる。色素原体は長期保存には適するが、高粘度液体又は固体・粉体であるので、食品や飲料等の着色に使用する場合には希釈・溶解等の事前処理が必要となる。通常は、水及び必要に応じてエタノール等の適当な添加物を加え、色価が100〜1000程度となるように希釈又は溶解して、色素液製剤として使用する。   The pigment component of red radish is usually extracted as a pigment solution from red radish. Although the red radish dye solution can be used as it is, it is generally concentrated to a color value of about 1500 to 3000 by a conventional method such as distillation under reduced pressure, or dried to obtain a red radish dye base. Although the chromogen is suitable for long-term storage, it is a high-viscosity liquid or solid / powder. Therefore, when used for coloring foods, beverages, etc., pretreatment such as dilution / dissolution is required. Usually, water and appropriate additives such as ethanol are added as needed, diluted or dissolved so that the color value is about 100 to 1000, and used as a dye solution preparation.

特開平10−279825号公報JP-A-10-279825

しかしながら、天然物由来の色素成分を含有する色素液製剤は、低温で保存した場合に色素成分が結晶を形成してしまい、これが沈殿の発生を招き、色価が減少するという問題がある。例えば、色価100〜1000程度の赤ダイコン色素液製剤は、10℃以下の低温で色素成分が結晶し、沈殿を生じる場合がある。   However, a dye solution preparation containing a natural product-derived dye component has a problem that when the dye component is stored at a low temperature, the dye component forms crystals, which causes precipitation and reduces the color value. For example, in a red radish pigment solution preparation having a color value of about 100 to 1,000, the pigment component may crystallize and precipitate at a low temperature of 10 ° C. or lower.

これに対し、特開平10−279825号公報(上記特許文献1)には、赤キャベツや赤ダイコン等のアントシアニン含有植物を原料とするアントシアニン色素精製濃縮液に、ソルビトール、還元澱粉糖化物、デキストリン、及びトレハローズのうち少なくとも1種を添加することによって、色素結晶の形成による沈殿の発生及び色価の減少を防止することが記載されている。しかし、この方法を用いた場合でも僅かに沈殿の発生や色価の減少が見られることが記載されており、効果が不十分である。   In contrast, JP-A-10-279825 (Patent Document 1) discloses an anthocyanin pigment refining concentrate using an anthocyanin-containing plant such as red cabbage or red radish as a raw material, sorbitol, reduced starch saccharified product, dextrin, And the addition of at least one of trehalose is described to prevent the occurrence of precipitation and the decrease in color value due to the formation of dye crystals. However, it is described that even when this method is used, the occurrence of slight precipitation and a decrease in color value are observed, and the effect is insufficient.

本発明は、上記の課題に鑑みてなされたものである。即ち、本発明の目的は、低温下における沈殿の発生及び色価の減少が防止され、保存性及び安定性に優れた赤ダイコン色素液製剤を提供することに存する。   The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a red radish pigment solution preparation which is excellent in preservability and stability, in which the occurrence of precipitation and a decrease in color value are prevented at low temperatures.

本発明者らは鋭意検討の結果、赤ダイコン色素液製剤にクエン酸,リンゴ酸,又はリン酸を特定の濃度範囲となる様に加えることによって、上記課題が効果的に解決されることを見出し、本発明を完成するに至った。   As a result of intensive studies, the present inventors have found that the above problem can be effectively solved by adding citric acid, malic acid, or phosphoric acid to a red radish pigment solution so as to be in a specific concentration range. The present invention has been completed.

すなわち、本発明の要旨は、赤ダイコン色素液製剤の全重量に対して、クエン酸を4重量%以上12重量%以下,リンゴ酸を4重量%以上,又はリン酸を2重量%以上となるように添加することを特徴とする赤ダイコン色素液製剤における沈殿発生を防止する方法、並びに、クエン酸,リンゴ酸,及びリン酸からなる群より選ばれる2種以上の酸を含有し、且つこれらの酸の合計含有量が、赤ダイコン色素液製剤の全重量に対して、4重量%以上10重量%以下となるように添加することを特徴とする赤ダイコン色素液製剤における沈殿発生を防止する方法に存する。 That is, the gist of the present invention is that citric acid is 4 wt% or more, 12 wt% or less, malic acid is 4 wt% or more, or phosphoric acid is 2 wt% or more with respect to the total weight of the red radish pigment preparation. A method for preventing precipitation in a red radish pigment solution preparation characterized by being added , and two or more acids selected from the group consisting of citric acid, malic acid, and phosphoric acid, and these the total content of the acid, to prevent the total weight of the red radish pigment solution formulation, the precipitation occurs in the red radish pigment solution formulation, comprising adding to a 4 wt% to 10 wt% Lies in the way .

本発明によれば、赤ダイコン色素液製剤にクエン酸,リンゴ酸,又はリン酸を特定の濃度範囲となる様に加えることによって、低温下における沈殿の発生を防止するとともに、色価の減少を抑えることができ、色素としての保存安定性を向上させることが可能となる。加えて、色素液製剤の調製も容易である。   According to the present invention, by adding citric acid, malic acid, or phosphoric acid to a red radish pigment solution so as to be in a specific concentration range, the occurrence of precipitation at low temperatures can be prevented and the color value can be reduced. Therefore, the storage stability as a pigment can be improved. In addition, the preparation of the dye solution preparation is easy.

以下、本発明を詳細に説明する。
本発明の赤ダイコン色素液製剤に用いる赤ダイコン色素成分の形態は任意である。具体的には、例えばアブラナ科に属する赤ダイコンの色素抽出液を精製して得られる赤ダイコン色素溶液が挙げられる。原料として使用できる赤ダイコンの種類としては、アブラナ科ダイコン属(Raphanus sativus L.)に属する中国産赤大根(紅心赤大根など)や岩国赤等を挙げることができる。
Hereinafter, the present invention will be described in detail.
The form of the red radish pigment component used in the red radish pigment solution preparation of the present invention is arbitrary. Specific examples include a red radish pigment solution obtained by purifying a pigment extract of red radish belonging to the Brassicaceae family. Examples of red radish that can be used as a raw material include Chinese red radishes (such as red radish red radish) belonging to the genus Raphanus sativus L. and Iwakuni red.

赤ダイコン色素の抽出液は、例えば上記植物を色素成分が抽出可能な程度に裁断し、適量の水及びpH調整剤等を加えて室温にて浸漬し、所望により攪拌して該植物に含まれる色素成分を抽出し、これを濾過することにより得られる。この場合、溶媒のpHを酸性側に保持して抽出することが望ましい。溶媒のpHは通常4以下が好ましく、中でも1以上4以下の範囲がより好ましい。pHの調整に使用できる酸としては、例えばクエン酸、酒石酸、リンゴ酸、酢酸などの有機酸、或いは塩酸、硫酸、リン酸などの無機酸を挙げることができる。水の使用量は任意であるが、抽出対象となる赤ダイコンの1〜10重量倍程度の量が取り扱い易く好ましい。また、水にアルコールを添加して、これを抽出に用いても良い。アルコールを添加する場合、添加するアルコールの種類は特に限定されず、エタノール,プロパノール等の様々なアルコールが使用できるが、中でもエタノール等が好ましい。添加するアルコールの濃度は任意であるが、例えばエタノールの場合、約1〜50重量%程度が好ましい。かくして得られる赤ダイコン色素の粗抽出液は、一般に、原料由来の独特の臭気を有する。   The extract of red radish pigment is included in the plant by, for example, cutting the plant to such an extent that the pigment component can be extracted, adding an appropriate amount of water and a pH adjuster, and soaking at room temperature, and stirring as desired. It is obtained by extracting the pigment component and filtering it. In this case, it is desirable to perform extraction while maintaining the pH of the solvent on the acidic side. The pH of the solvent is usually preferably 4 or less, more preferably 1 or more and 4 or less. Examples of the acid that can be used for adjusting the pH include organic acids such as citric acid, tartaric acid, malic acid, and acetic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. The amount of water used is arbitrary, but an amount of about 1 to 10 times the amount of red radish to be extracted is preferable because it is easy to handle. Moreover, you may add alcohol to water and use this for extraction. When adding alcohol, the kind of alcohol to add is not specifically limited, Although various alcohol, such as ethanol and propanol, can be used, Ethanol etc. are especially preferable. The concentration of the alcohol to be added is arbitrary. For example, in the case of ethanol, about 1 to 50% by weight is preferable. The crude extract of red radish pigment thus obtained generally has a unique odor derived from the raw material.

続いて、この赤ダイコン色素の抽出液を精製処理に供する。精製処理の方法としては、水蒸気蒸留法、分子蒸留法、有機溶剤や超臨界流体による抽出法、膜濾過法、吸着法など、一般に知られる精製処理方法であれば何でも適用可能である。中でも、合成吸着樹脂カラムを用いる方法が好ましく、特に、カラムに色素成分と不純物とを含む赤ダイコン色素抽出液を通液し、先ず樹脂に赤ダイコン色素成分を吸着させ、その後、水或いは低濃度のアルコール水溶液で樹脂を洗浄して親水性の不純物を溶出させ、その後、30〜70体積%のエタノール水溶液で赤ダイコン色素成分を回収する方法が好ましい。   Subsequently, this red radish pigment extract is subjected to a purification treatment. As a purification method, any generally known purification method such as a steam distillation method, a molecular distillation method, an extraction method using an organic solvent or a supercritical fluid, a membrane filtration method, or an adsorption method can be applied. Among them, a method using a synthetic adsorption resin column is preferable, and in particular, a red radish dye extract containing a dye component and impurities is passed through the column, first the red radish dye component is adsorbed on the resin, and then water or a low concentration The resin is washed with an aqueous alcohol solution to elute hydrophilic impurities, and then the red radish pigment component is recovered with a 30 to 70% by volume aqueous ethanol solution.

精製処理に用いる合成吸着樹脂は、特に限定されないが、例えば、比表面積が約300〜約1500m2/g程度、最頻度半径が20〜700Å程度の無極性の多孔質吸着樹脂が好ましい。このような合成吸着剤の具体例としては、ダイヤイオン(登録商標)HP20SS、HP20、HP21等のHP樹脂、セパピーズ(登録商標)SP825、SP850、SP207等のSP樹脂(以上、三菱化学(株)製)、アンバーライトXAD−2、XAD−4、XAD−16(以上、ローム アンド ハース社製)等のスチレン−ジビニルベンゼン系樹脂;ダイヤイオン(登録商標)HP2MG(三菱化学(株)製)、アンバーライトXAD−7、XAD−8(以上、ローム アンド ハース社製)等のアクリル系樹脂などが挙げられる。 The synthetic adsorption resin used for the purification treatment is not particularly limited. For example, a nonpolar porous adsorption resin having a specific surface area of about 300 to about 1500 m 2 / g and a most frequent radius of about 20 to 700 mm is preferable. Specific examples of such a synthetic adsorbent include HP resins such as Diaion (registered trademark) HP20SS, HP20, and HP21, and SP resins such as Sepapies (registered trademark) SP825, SP850, and SP207 (hereinafter, Mitsubishi Chemical Corporation). Styrene-divinylbenzene resin such as Amberlite XAD-2, XAD-4, XAD-16 (above, manufactured by Rohm and Haas); Diaion (registered trademark) HP2MG (manufactured by Mitsubishi Chemical Corporation), Examples thereof include acrylic resins such as Amberlite XAD-7 and XAD-8 (manufactured by Rohm and Haas).

精製処理の際の合成吸着樹脂への赤ダイコン色素溶液の通過速度は特に限定されない。通過速度が速いほど単位時間当たりの処理量を確保できるが、色素成分のロスが多くなったり精製が不十分となったりする場合がある。また、通過速度が遅いほど色素成分と不純物との分離性を向上させることができるが、逆に単位時間当たりの処理量が低下する。従って、通過速度としては、SV値が通常0.1以上、中でも0.5以上が好ましく、また、通常10以下、中でも5以下が好ましい。   The passing speed of the red radish dye solution through the synthetic adsorption resin during the purification treatment is not particularly limited. The faster the passage speed is, the more the processing amount per unit time can be secured, but the loss of the pigment component may increase or the purification may be insufficient. In addition, the lower the passing speed, the more the separation between the pigment component and the impurity can be improved, but conversely, the throughput per unit time decreases. Therefore, as the passing speed, the SV value is usually 0.1 or more, preferably 0.5 or more, and usually 10 or less, particularly preferably 5 or less.

この様にして精製された赤ダイコン色素溶液は、そのままの形態で使用しても良いが、保存時の安定性や流通時・使用時の取り扱いの容易性の観点から、好ましくは濃縮又は乾燥粉末化して色素原体の形態とした上で、本発明の赤ダイコン色素液製剤の原料として使用する。色素原体とする場合には、減圧蒸留等の常法によりその色価が通常1500以上,好ましくは1800以上、また、通常6000以下程度になるように、濃縮又は乾燥粉末化を行なうことが好ましい。   The red radish pigment solution purified in this way may be used as it is, but it is preferably a concentrated or dry powder from the viewpoint of stability during storage and ease of handling during distribution and use. It is used as a raw material for the red radish pigment solution preparation of the present invention after being converted into a chromogen form. When the chromogen is used, it is preferably concentrated or dried into a powder by a conventional method such as vacuum distillation so that the color value is usually 1500 or more, preferably 1800 or more and usually 6000 or less. .

なお、赤ダイコン色素成分を含む試料(色素溶液,色素原体,色素液製剤等)の色価は、下記式(I)により定義されるE100% 1cmの値とする。

Figure 0004961465
The color value of a sample containing a red radish pigment component (a pigment solution, a chromogen, a pigment solution preparation, etc.) is a value of E 100% 1 cm defined by the following formula (I).
Figure 0004961465

上記色価の具体的な評価方法としては、例えば、約0.1gの赤ダイコン色素溶液試料を秤量し、これにpH3の緩衝液、例えばMcIlvaine緩衝液(0.2Mリン酸水素二ナトリウム−0.1Mクエン酸)を加えて全量を100mLとし、光路長1cmで極大吸収波長512nmにおける吸光度A512を測定する。この測定値を用いて、下式で色価を算出できる。

Figure 0004961465
As a specific method for evaluating the color value, for example, about 0.1 g of a red radish dye solution sample was weighed, and a pH 3 buffer solution such as McIlvaine buffer solution (0.2 M disodium hydrogen phosphate-0 .1M citric acid) is added to make a total volume of 100 mL, and the absorbance A 512 at an optical path length of 1 cm and a maximum absorption wavelength of 512 nm is measured. Using this measured value, the color value can be calculated by the following equation.
Figure 0004961465

本発明の赤ダイコン色素液製剤は、上述の赤ダイコン色素溶液又は赤ダイコン色素原体と、クエン酸,リンゴ酸,リン酸のうち少なくとも何れか一種の酸と、必要に応じて各種の添加物とを、溶解槽の中で溶媒に加えて溶解させることにより得ることができる。   The red radish pigment solution preparation of the present invention comprises the above-mentioned red radish pigment solution or red radish chromogen, at least one acid selected from citric acid, malic acid, and phosphoric acid, and various additives as necessary. Can be obtained by dissolving in a dissolution tank in addition to the solvent.

溶媒としては、水,水と各種アルコールとの混合溶液等を挙げることができる。後者の場合、水との混合で用いるアルコールの種類としては、エタノールが好ましい。また、水に対するアルコールの混合割合としては、1〜50重量%程度が好ましい。   Examples of the solvent include water, a mixed solution of water and various alcohols, and the like. In the latter case, ethanol is preferred as the type of alcohol used for mixing with water. The mixing ratio of alcohol to water is preferably about 1 to 50% by weight.

酸としてクエン酸を添加する場合、その添加割合は、最終的に得られる色素液製剤の全重量に対して、通常4重量%以上、好ましくは5重量%以上であり、また、通常12重量%以下、好ましくは10重量%以下が適当である。   When citric acid is added as an acid, the addition ratio is usually 4% by weight or more, preferably 5% by weight or more, and usually 12% by weight, based on the total weight of the dye solution preparation finally obtained. Hereinafter, it is preferably 10% by weight or less.

なお、一般に「クエン酸」と呼ばれる化合物としては、クエン酸無水物(分子量192)とクエン酸一水和物(分子量210)とがあるが、これらは水分子の結合の有無のみの違いであり、何れを使用しても分子数さえ同じであれば同等の効果が得られると考えられる。従って、本明細書では、クエン酸無水物とクエン酸一水和物の双方を総称して、クエン酸と呼ぶことにする。なお、本明細書におけるクエン酸の濃度はクエン酸無水物を基準として記載しているが、この濃度に210/192を乗じることによりクエン酸一水和物の濃度に換算できる。   In addition, as a compound generally called “citric acid”, there are citric acid anhydride (molecular weight 192) and citric acid monohydrate (molecular weight 210), which are different only in the presence or absence of water molecule bonding. Even if any of them is used, it is considered that an equivalent effect can be obtained as long as the number of molecules is the same. Therefore, in this specification, both citric acid anhydride and citric acid monohydrate are collectively referred to as citric acid. In addition, although the density | concentration of the citric acid in this specification is described on the basis of a citric acid anhydride, it can convert into the density | concentration of a citric acid monohydrate by multiplying this concentration by 210/192.

リンゴ酸を添加する場合、その添加割合は、最終的に得られる色素液製剤の全重量に対して、通常4重量%以上、好ましくは5重量%以上、より好ましくは7重量%以上であり、また、上限は特に制限は無いが、好ましくは15重量%以下、より好ましくは12重量%以下が適当である。   When malic acid is added, the addition ratio is usually 4% by weight or more, preferably 5% by weight or more, more preferably 7% by weight or more, with respect to the total weight of the finally obtained pigment solution preparation, The upper limit is not particularly limited, but is preferably 15% by weight or less, more preferably 12% by weight or less.

リン酸を添加する場合、その添加割合は、最終的に得られる色素液製剤の全重量に対して、通常2重量%以上、好ましくは3重量%以上であり、また、上限は特に制限は無いが、好ましくは15重量%以下、より好ましくは10重量%以下が適当である。   When phosphoric acid is added, the addition ratio is usually 2% by weight or more, preferably 3% by weight or more, with respect to the total weight of the dye solution preparation finally obtained, and the upper limit is not particularly limited. However, it is preferably 15% by weight or less, more preferably 10% by weight or less.

なお、一般に「リン酸」と呼ばれる化合物として、狭義のリン酸であるオルトメタリン酸(H3PO4)の他に、鎖状のポリリン酸(ピロリン酸,トリリン酸、テトラリン酸など)や環状のメタリン酸が挙げられる。これらの化合物のうち何れを加えても本発明の効果を得ることができると考えられるので、本明細書ではこれらの化合物全てを総称してリン酸と呼ぶことにする。なお、これらの化合物の中でも本発明の効果が特に顕著に得られるのは、オルトメタリン酸である。 In addition, as a compound generally called “phosphoric acid”, in addition to orthometaphosphoric acid (H 3 PO 4 ), which is a narrowly defined phosphoric acid, chain polyphosphoric acid (eg, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid) or cyclic Metaphosphoric acid is mentioned. Since it is considered that the effects of the present invention can be obtained by adding any of these compounds, all of these compounds are collectively referred to as phosphoric acid in this specification. Of these compounds, orthometaphosphoric acid has a particularly remarkable effect of the present invention.

クエン酸,リンゴ酸及びリン酸は、それぞれ単独で添加しても良いが、これらのうち任意の二種、又は三種全てを併用しても良い。二種又は三種を併用する場合、これらの添加割合の合計は、通常4重量%以上、好ましくは5重量%以上であり、また、上限は特に制限は無いが、好ましくは12重量%以下、より好ましくは10重量%以下が適当である。   Citric acid, malic acid and phosphoric acid may be added singly, but any two or all three of them may be used in combination. When two or three types are used in combination, the total of these addition ratios is usually 4% by weight or more, preferably 5% by weight or more, and the upper limit is not particularly limited, but is preferably 12% by weight or less. 10% by weight or less is preferable.

クエン酸,リンゴ酸,及びリン酸をそれぞれ単独で用いる場合、並びに、数種を組み合わせて用いる場合ともに、これらの酸の添加割合が低過ぎると、充分な沈殿防止効果を得ることができないので好ましくない。一方、これらの酸の添加割合が高過ぎると、効果が頭打ちとなる上にコストが嵩み、着色対象物の味やpH等の特性に影響を及ぼす可能性もある。また、特にクエン酸の場合、溶解処理の際にクエン酸の結晶と色素原体とが塊状になってしまい、溶媒中に均一に溶解し難くなったり、溶解槽の凹部分などに入り込んでライン閉塞などの問題を起こしたりする可能性があるのに加えて、調製後の溶解槽の洗浄が困難となり非効率となるので、やはり好ましくない。   When citric acid, malic acid, and phosphoric acid are used alone or in combination of several kinds, if the addition ratio of these acids is too low, a sufficient precipitation preventing effect cannot be obtained. Absent. On the other hand, when the addition ratio of these acids is too high, the effect reaches a peak and the cost increases, and there is a possibility that the coloring object has characteristics such as taste and pH. In particular, in the case of citric acid, the citric acid crystals and the chromogen are agglomerated during the dissolution process, making it difficult to dissolve uniformly in the solvent, or entering the concave portion of the dissolution tank. In addition to the possibility of causing problems such as clogging, cleaning of the dissolution tank after preparation becomes difficult and inefficient, which is also not preferable.

添加物の使用は任意であるが、具体例としては防腐剤等が挙げられる。防腐剤としては、例えばエタノール等が使用できる。   The use of additives is optional, but specific examples include preservatives. As the preservative, for example, ethanol can be used.

なお、赤ダイコン色素液製剤の色価は、赤ダイコン色素溶液又は赤ダイコン色素原体と溶媒との分量比を調節することにより、容易に調整することができる。具体的な色価の値は、色素液製剤の使用目的に応じて適宜選択すれば良いが、通常100以上、好ましくは200以上、より好ましくは300以上とすることが適当であり、また、通常1000以下、好ましくは800以下、より好ましくは700以下とすることが適当である。   In addition, the color value of a red radish pigment solution preparation can be easily adjusted by adjusting the quantity ratio between the red radish pigment solution or the red radish pigment raw material and the solvent. The specific color value may be appropriately selected according to the intended use of the dye liquid preparation, but is usually 100 or more, preferably 200 or more, more preferably 300 or more, and usually It is appropriate to set it to 1000 or less, preferably 800 or less, more preferably 700 or less.

このようにして得られた本発明の赤ダイコン色素液製剤は、色調に優れ、また長期間にわたって安定であり、食品、飲料や香粧品、保健・医薬品類等の着色剤として広く利用できる。   The red radish pigment solution preparation of the present invention thus obtained is excellent in color tone and stable over a long period of time, and can be widely used as a colorant for foods, beverages, cosmetics, health / pharmaceuticals and the like.

例えば、ドロップ、キャンディー、チョコレート、アイスクリーム、シャーベット、ゼリー、清涼飲料、乳飲料、飴、畜肉加工食品、焼き肉のたれ、漬物などの如き飲食品、嗜好品類への天然着色料;錠剤、液状経口薬、湿布薬などの如き保健・医薬品類への天然着色料;或いは、石鹸、洗剤、シャンプーの着色の如き香粧品類への天然着色料などとして有用である。   For example, natural coloring agents for foods and drinks such as drops, candy, chocolate, ice cream, sorbet, jelly, soft drinks, milk drinks, rice cakes, processed meat, grilled meat, pickles, etc .; tablets, liquid oral It is useful as a natural colorant for health and pharmaceuticals such as medicines and poultices; or as a natural colorant for cosmetics such as soaps, detergents and shampoos.

上記した如き飲食品等に添加する場合の添加量は、得られる製品の種類、要求される消費者の嗜好等によって左右されるが、通常は製品に対して約0.005〜10重量%の範囲、好ましくは約0.01〜0.1重量%の範囲を例示することができる。   The amount of addition to foods and beverages as described above depends on the type of product obtained, the consumer preference required, etc., but is usually about 0.005 to 10% by weight based on the product. A range, preferably a range of about 0.01 to 0.1% by weight, can be exemplified.

以下、本発明を実施例により更に詳細に説明するが、本発明はその要旨を超えない限り以下の実施例に制約されるものではなく、種々変形して実施することが可能である。   EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not restrict | limited to a following example, unless it exceeds the summary, It can implement in various deformation | transformation.

赤ダイコンを破砕し、赤ダイコンの重量に対して5倍量の1%クエン酸水溶液中に浸漬し、常温下で8時間抽出処理を行ない、抽出液を得る操作を3回繰り返した。3回の抽出液を合わせて、濾紙で濾過して不溶成分を除去した後、55℃にて減圧蒸留により濃縮し、赤ダイコン色素の粗抽出液を得た。この色素粗抽出液の色価は550であった。   Red radish was crushed, immersed in a 1% aqueous citric acid solution 5 times the weight of red radish, subjected to extraction treatment at room temperature for 8 hours, and the operation of obtaining an extract was repeated three times. The three extracts were combined, filtered through filter paper to remove insoluble components, and then concentrated by distillation under reduced pressure at 55 ° C. to obtain a red radish pigment crude extract. The color value of this crude pigment extract was 550.

次に、該色素粗抽出液1Lを、合成吸着樹脂ダイヤイオンHP20(三菱化学(株)製)2Lを充填したカラムにSV=3の通過速度で通液させ、赤ダイコン色素成分を樹脂に吸着させた。続いて、2Lの水を流して樹脂を洗浄し、その後60体積%のエタノール水を4L通液させて、樹脂に吸着している赤ダイコン色素成分を回収した。得られた赤ダイコン色素成分の回収液を減圧濃縮してエタノールを留去し、160gの赤ダイコン色素濃縮液を得た。該色素濃縮液の色価は1950であった。該色素濃縮液を赤ダイコン色素原体として、以下の試験に供した。   Next, 1 L of the crude dye extract is passed through a column packed with 2 L of synthetic adsorption resin Diaion HP20 (Mitsubishi Chemical Corporation) at a passing speed of SV = 3 to adsorb the red radish dye component to the resin. I let you. Subsequently, 2 L of water was allowed to flow to wash the resin, and then 4 L of 60 vol% ethanol water was passed through to collect the red radish pigment component adsorbed on the resin. The obtained red radish pigment component recovered liquid was concentrated under reduced pressure to distill off ethanol, thereby obtaining 160 g of a red radish pigment concentrate. The color value of the dye concentrate was 1950. The dye concentrate was used for the following test as a red radish chromogen.

[実施例1]
上記色素原体36g及びエタノール10g、並びに下記表−1記載の添加物それぞれ5gを容器に入れ、水を添加して最終的に100gになる様に調整し、十分に撹拌混合して色素液製剤を調製した。得られた色素液製剤の色価は約700であった。この色素液製剤を−3℃で3日間保存した後、沈殿発生の有無を目視にて確認した。その結果を下記表−1に示す。
[Example 1]
36 g of the chromogen, 10 g of ethanol, and 5 g of each of the additives listed in Table 1 below are placed in a container, adjusted to a final concentration of 100 g by adding water, and thoroughly stirred and mixed to prepare a dye solution formulation Was prepared. The color value of the resulting dye solution preparation was about 700. After this dye solution preparation was stored at -3 ° C for 3 days, the presence or absence of precipitation was visually confirmed. The results are shown in Table 1 below.

Figure 0004961465
Figure 0004961465

[実施例2]
上記色素原体36g及びエタノール10g、並びに下記表−2記載の添加物それぞれ同表記載の添加量を容器に入れ、水を添加して最終的に100gとなる様に調整し、十分に撹拌混合して色素液製剤を調製した。得られた色素液製剤の色価は約700であった。この色素液製剤を−3℃で3日間保存した後、沈殿発生の有無を目視にて確認した。また、この色素液製剤を40℃で2週間後保存した後、色価の残存率を測定した。それらの結果を下記表−2に示す。
[Example 2]
36 g of the chromogen, 10 g of ethanol, and the additives listed in Table 2 below are added to the containers, adjusted to a final volume of 100 g by adding water, and mixed thoroughly. Thus, a dye solution preparation was prepared. The color value of the resulting dye solution preparation was about 700. After this dye solution preparation was stored at -3 ° C for 3 days, the presence or absence of precipitation was visually confirmed. Further, after this dye solution preparation was stored at 40 ° C. for 2 weeks, the residual ratio of the color value was measured. The results are shown in Table 2 below.

Figure 0004961465
Figure 0004961465

[実施例3]
上記色素原体36g及びエタノール10g、並びに下記表−3記載の添加物それぞれ同表記載の添加量を容器に入れて、水を添加して最終的に100gとなる様に調整し、室温にてマグネティックスターラーを用いて5分間撹拌した。攪拌後の液を濾紙で濾過し、濾紙上及び容器中に溶け残って残留した残渣(塊状物)の量を目視にて観察した。その結果を下記表−3に示す。
[Example 3]
36 g of the chromogen and 10 g of ethanol, and the additives listed in Table 3 below are added to the container, and adjusted to 100 g by adding water and finally at room temperature. It stirred for 5 minutes using the magnetic stirrer. The liquid after stirring was filtered with a filter paper, and the amount of residue (lumps) remaining undissolved on the filter paper and in the container was visually observed. The results are shown in Table 3 below.

Figure 0004961465
Figure 0004961465

Claims (6)

色価が100以上1000以下の赤ダイコン色素液製剤における沈殿発生を防止する方法であって、  A method for preventing precipitation in a red radish pigment preparation having a color value of 100 or more and 1000 or less,
クエン酸を、該赤ダイコン色素液製剤の全重量に対して、4重量%以上12重量%以下となるように該赤ダイコン色素液製剤に添加する  Citric acid is added to the red radish pigment solution so as to be 4% by weight to 12% by weight with respect to the total weight of the red radish pigment solution
ことを特徴とする、赤ダイコン色素液製剤における沈殿発生を防止する方法。A method for preventing the occurrence of precipitation in a red radish dye solution.
色価が100以上1000以下の赤ダイコン色素液製剤における沈殿発生を防止する方法であって、  A method for preventing precipitation in a red radish pigment preparation having a color value of 100 or more and 1000 or less,
リンゴ酸を、該赤ダイコン色素液製剤の全重量に対して、4重量%以上となるように該赤ダイコン色素液製剤に添加する  Malic acid is added to the red radish pigment solution so as to be 4% by weight or more based on the total weight of the red radish pigment solution
ことを特徴とする、赤ダイコン色素液製剤における沈殿発生を防止する方法。A method for preventing the occurrence of precipitation in a red radish dye solution.
色価が100以上1000以下の赤ダイコン色素液製剤における沈殿発生を防止する方法であって、  A method for preventing precipitation in a red radish pigment preparation having a color value of 100 or more and 1000 or less,
リン酸を、該赤ダイコン色素液製剤の全重量に対して、2重量%以上となるように該赤ダイコン色素液製剤に添加する  Phosphoric acid is added to the red radish pigment solution so as to be 2% by weight or more based on the total weight of the red radish pigment solution
ことを特徴とする、赤ダイコン色素液製剤における沈殿発生を防止する方法。A method for preventing the occurrence of precipitation in a red radish dye solution.
色価が100以上1000以下の赤ダイコン色素液製剤における沈殿発生を防止する方法であって、  A method for preventing precipitation in a red radish pigment preparation having a color value of 100 or more and 1000 or less,
クエン酸、リンゴ酸及びリン酸からなる群より選ばれる2種以上の酸を、該赤ダイコン色素液製剤の全重量に対して、4重量%以上10重量%以下となるように該赤ダイコン色素液製剤に添加する  The red radish pigment such that two or more acids selected from the group consisting of citric acid, malic acid and phosphoric acid are 4% by weight or more and 10% by weight or less based on the total weight of the red radish pigment solution preparation Add to liquid formulation
ことを特徴とする、赤ダイコン色素液製剤における沈殿発生を防止する方法。A method for preventing the occurrence of precipitation in a red radish dye solution.
請求項1〜4の何れか1項に記載の赤ダイコン色素液製剤における沈殿発生を防止する方法を含む工程を有する  It has the process including the method of preventing precipitation generation | occurrence | production in the red radish pigment solution formulation of any one of Claims 1-4.
ことを特徴とする、赤ダイコン色素液製剤の製造方法。A method for producing a red radish pigment preparation characterized by the above.
請求項5に記載の赤ダイコン色素液製剤の製造方法により製造された  It was manufactured by the manufacturing method of the red radish pigment solution preparation according to claim 5.
ことを特徴とする、赤ダイコン色素液製剤。A red radish pigment solution preparation characterized by the above.
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