JP5019885B2 - Dispersion composition, cosmetic for skin care, and method for producing dispersion composition - Google Patents
Dispersion composition, cosmetic for skin care, and method for producing dispersion composition Download PDFInfo
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- JP5019885B2 JP5019885B2 JP2007000679A JP2007000679A JP5019885B2 JP 5019885 B2 JP5019885 B2 JP 5019885B2 JP 2007000679 A JP2007000679 A JP 2007000679A JP 2007000679 A JP2007000679 A JP 2007000679A JP 5019885 B2 JP5019885 B2 JP 5019885B2
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- 239000008158 vegetable oil Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000037373 wrinkle formation Effects 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 150000003735 xanthophylls Chemical class 0.000 description 1
- 235000010930 zeaxanthin Nutrition 0.000 description 1
- 239000001775 zeaxanthin Substances 0.000 description 1
- 229940043269 zeaxanthin Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- RZFHLOLGZPDCHJ-XZXLULOTSA-N α-Tocotrienol Chemical compound OC1=C(C)C(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1C RZFHLOLGZPDCHJ-XZXLULOTSA-N 0.000 description 1
- 235000019145 α-tocotrienol Nutrition 0.000 description 1
- 239000011730 α-tocotrienol Substances 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 1
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- FGYKUFVNYVMTAM-WAZJVIJMSA-N β-tocotrienol Chemical compound OC1=CC(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1C FGYKUFVNYVMTAM-WAZJVIJMSA-N 0.000 description 1
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- 239000011722 γ-tocotrienol Substances 0.000 description 1
- OTXNTMVVOOBZCV-WAZJVIJMSA-N γ-tocotrienol Chemical compound OC1=C(C)C(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 OTXNTMVVOOBZCV-WAZJVIJMSA-N 0.000 description 1
- 235000019144 δ-tocotrienol Nutrition 0.000 description 1
- 239000011729 δ-tocotrienol Substances 0.000 description 1
- ODADKLYLWWCHNB-LDYBVBFYSA-N δ-tocotrienol Chemical compound OC1=CC(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 ODADKLYLWWCHNB-LDYBVBFYSA-N 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Colloid Chemistry (AREA)
Description
本発明は、分散組成物及びスキンケア用化粧料並びにその製造方法に関し、特に、カロテノイド含有油溶性成分が水性組成物に分散している分散組成物及びこれを用いたスキンケア用化粧料並びにこの分散組成物の製造方法に関する。 The present invention relates to a dispersion composition, a skin care cosmetic, and a method for producing the same, and in particular, a dispersion composition in which a carotenoid-containing oil-soluble component is dispersed in an aqueous composition, a skin care cosmetic using the same, and the dispersion composition. The present invention relates to a method for manufacturing a product.
カロテノイド類は、天然に存在する黄色から赤のテルペノイド類の色素で、植物類、藻類、及びバクテリアに見つけることができる。カロテノイド類の一種であるアスタキサンチン類(アスタキサンチンおよびそのエステル等も含む)は、自然界では動植物界に広く分布しており、主として養殖魚や養鶏の色揚げ剤として使用されている。また、アスタキチンサンは、酸化防止効果、抗炎症効果(特許文献1)、皮膚老化防止効果(特許文献2)、シミやしわの形成予防効果(特許文献3)などの機能を有することも知られている。このため、アスタキチンサンを食品、化粧品、医薬品の原材料及びそれらの加工品等へ添加することが検討・実施されている。 Carotenoids are naturally occurring yellow to red terpenoid pigments that can be found in plants, algae, and bacteria. Astaxanthins (including astaxanthin and its esters), which are a kind of carotenoids, are widely distributed in the animal and plant kingdoms in nature, and are mainly used as coloring agents for farmed fish and poultry. It is also known that astaxanthin has functions such as an antioxidant effect, an anti-inflammatory effect (Patent Document 1), an anti-skin aging effect (Patent Document 2), and a stain and wrinkle formation preventing effect (Patent Document 3). It has been. For this reason, it has been studied and practiced to add astachitin sun to foods, cosmetics, raw materials for pharmaceuticals, processed products thereof, and the like.
このようにカロテノイド類は、食品、化粧品、医薬品及びその他の加工品等に添加使用される際、多くの場合、分散性の高いエマルジョン組成物として添加されるが、天然物由来のカロテノイドは、不安定な構造であり、その上、エマルジョン粒子の粒子径が満足できる範囲内で、比較的長期にわたって高い分散安定性を維持することが容易でなかった。
これを解消するために、例えば、特許文献4及び5には、カロテノイド系色素の分散安定性を検討した技術が記載されている。
Thus, when carotenoids are added to foods, cosmetics, pharmaceuticals, and other processed products, they are often added as highly dispersible emulsion compositions. However, carotenoids derived from natural products are not suitable. In addition, it was a stable structure, and it was not easy to maintain high dispersion stability for a relatively long period of time within a range where the particle diameter of the emulsion particles was satisfactory.
In order to solve this problem, for example, Patent Documents 4 and 5 describe techniques for examining the dispersion stability of carotenoid pigments.
しかしながら、上記の技術においても、カロテノイドを含む水分散物では、経時的に分散性や色味、性状が損なわれることがあり、カロテノイドを含む分散組成物の安定性を所望する期間にわたって維持することが困難であった。
本発明の目的は、カロテノイド含有油溶性成分を含み、保存安定性に優れた分散組成物及びこれを用いたスキンケア用化粧料を提供することである。
However, even in the above-described technique, the dispersion, color, and properties of the aqueous dispersion containing carotenoids may be impaired over time, and the stability of the dispersion composition containing carotenoids should be maintained over a desired period. It was difficult.
An object of the present invention is to provide a dispersion composition containing a carotenoid-containing oil-soluble component and excellent in storage stability, and a skin care cosmetic using the same.
本発明の分散組成物は、カロテノイド含有油溶性成分を含む分散組成物であって、カロテノイド含有油溶性成分及び、リン脂質又はその誘導体を含むエマルジョン粒子を有する水分散物と、アスコルビン酸又はその誘導体及び、分散組成物全体の質量に対して20質量%以下の油状成分を含む水性組成物と、を混合することによって得られ且つ平均粒子径200nm以下のエマルジョン粒子を有するものである。
本発明のスキンケア用化粧料は、上記分散組成物を含むことを特徴とするものである。
本発明の分散組成物の製造方法は、カロテノイド含有油溶性成分を含む分散組成物の製造方法であって、カロテノイド含有油溶性成分及びリン脂質又はその誘導体と、水相とを混合して、エマルジョン粒子を有する水分散物を得ること、前記水分散物と、アスコルビン酸又はその誘導体及び、分散組成物全体の質量に対して20質量%以下の油状成分を含む水性組成物とを混合して、平均粒子径200nm以下のエマルジョン粒子を有する分散組成物を得ることこと、を含むものである。
The dispersion composition of the present invention is a dispersion composition containing a carotenoid-containing oil-soluble component, an aqueous dispersion having emulsion particles containing a carotenoid-containing oil-soluble component and a phospholipid or a derivative thereof, and ascorbic acid or a derivative thereof. And it has emulsion particles with an average particle diameter of 200 nm or less obtained by mixing with an aqueous composition containing 20% by mass or less of an oily component with respect to the total mass of the dispersion composition.
The skin care cosmetic of the present invention is characterized by containing the above dispersion composition.
The method for producing a dispersion composition of the present invention is a method for producing a dispersion composition containing a carotenoid-containing oil-soluble component, wherein the emulsion is prepared by mixing a carotenoid-containing oil-soluble component and a phospholipid or a derivative thereof with an aqueous phase. Obtaining an aqueous dispersion having particles, mixing the aqueous dispersion with an aqueous composition containing ascorbic acid or a derivative thereof and an oily component of 20% by mass or less based on the total mass of the dispersion composition; Obtaining a dispersion composition having emulsion particles having an average particle diameter of 200 nm or less.
ここで、上記分散組成物では、前記カロテノイドが、アスタキサンチン及びそのエステルから選択された少なくとも1種であることが好ましく、また、前記カロテノイド含有油溶性成分が、ヘマトコッカス藻抽出物であることが好ましい。
また、上記分散組成物では、前記アスコルビン酸又はその誘導体が、リン酸アスコルビルマグネシウム、リン酸アスコルビルナトリウム、アスコルビル−2−グルコシド、アスコルビン酸ナトリウムから選択された少なくとも1種であることが好ましい。
上記分散組成物では、上記水分散組成物が更にトコフェロールを含むものであってもよい。
上記分散組成物では、前記リン脂質又はその誘導体が、前記水分散物全体の質量に対して0.001質量%〜20質量%であることが好ましい。
Here, in the dispersion composition, the carotenoid is preferably at least one selected from astaxanthin and esters thereof, and the carotenoid-containing oil-soluble component is preferably a Haematococcus alga extract. .
In the dispersion composition, the ascorbic acid or a derivative thereof is preferably at least one selected from magnesium ascorbyl phosphate, sodium ascorbyl phosphate, ascorbyl-2-glucoside, and sodium ascorbate.
In the dispersion composition, the water dispersion composition may further contain tocopherol.
In the said dispersion composition, it is preferable that the said phospholipid or its derivative (s) is 0.001 mass%-20 mass% with respect to the mass of the said whole water dispersion.
本発明によれば、カロテノイド含有油溶性成分を含み、保存安定性に優れた分散組成物及びこれを用いたスキンケア用化粧品を提供することができる。 According to the present invention, it is possible to provide a dispersion composition containing a carotenoid-containing oil-soluble component and excellent in storage stability, and a skin care cosmetic using the same.
本発明の分散組成物は、カロテノイド含有油溶性成分及び、リン脂質又はその誘導体を含むエマルジョン粒子を有する水分散物と、アスコルビン酸又はその誘導体及び、分散組成物全体の質量に対して20質量%以下の油状成分を含む水性組成物と、を混合することによって得られ且つ平均粒子径200nm以下のエマルジョン粒子を有するものである。
本発明では、カロテノイド含有油溶性成分を含み、エマルジョン粒子を有するO/W型エマルジョンである水分散物と、アスコルビン酸又はその誘導体を含む水性組成物とを混合することにより、カロテノイド含有油溶性成分の分散安定性とカロテノイドの色味安定性とを共に良好に保つことができ、その結果、保存安定性に優れた分散組成物とすることができる。
The dispersion composition of the present invention comprises an aqueous dispersion having emulsion particles containing a carotenoid-containing oil-soluble component and phospholipid or a derivative thereof, ascorbic acid or a derivative thereof, and 20% by mass with respect to the total mass of the dispersion composition. The emulsion composition is obtained by mixing an aqueous composition containing the following oil component and has emulsion particles having an average particle diameter of 200 nm or less.
In the present invention, a carotenoid-containing oil-soluble component is mixed by mixing an aqueous dispersion that is an O / W emulsion having emulsion particles and containing a carotenoid-containing oil-soluble component and an aqueous composition containing ascorbic acid or a derivative thereof. The dispersion stability of the carotenoid and the color stability of the carotenoid can both be kept good, and as a result, a dispersion composition having excellent storage stability can be obtained.
本発明の分散組成物におけるカロテノイドとしては、植物類、藻類及びバクテリアのいずれのものも含まれる。また天然由来のものに限定されず、常法に従って得られるものであればいずれのものも本発明におけるカロテノイドに包含される。 The carotenoid in the dispersion composition of the present invention includes any of plants, algae and bacteria. Moreover, it is not limited to the thing of natural origin, Any thing will be included by the carotenoid in this invention if it can be obtained in accordance with a conventional method.
カロテノイドとしては、炭化水素類(カロテン類)及びこれらの酸化アルコール誘導体類(キサントフィル類)並びにこれらのエステルが挙げられる。本発明では特に断らない限り、これらの化合物を含めて「カロテノイド」と称する。
カロテノイドの例としては、アクチニオエリスロール、アスタキサンチン、ビキシン、カンタキサンチン、カプサンチン、カプソルビン、β−8’−アポ−カロテナール(アポカロテナール)、β−12’−アポ−カロテナール、α−カロテン、β−カロテン、”カロテン”(α−及びβ−カロテン類の混合物)、γ−カロテン、δ−カロテン、β−クリプトキサンチン、エキネノン、パーム油カロテン、ルテイン、リコピン、ビオレリトリン、ゼアキサンチン、及びそれらのうちヒドロキシル又はカルボキシルを含有するもののエステル類を挙げることができる。
Examples of carotenoids include hydrocarbons (carotenes), oxidized alcohol derivatives thereof (xanthophylls), and esters thereof. In the present invention, these compounds are referred to as “carotenoid” unless otherwise specified.
Examples of carotenoids include actinioerythrol, astaxanthin, bixin, canthaxanthin, capsanthin, capsorubin, β-8′-apo-carotenal (apocarotenal), β-12′-apo-carotenal, α-carotene, β-carotene , “Carotene” (a mixture of α- and β-carotenes), γ-carotene, δ-carotene, β-cryptoxanthin, echinone, palm oil carotene, lutein, lycopene, biorelithrin, zeaxanthin, and among them hydroxyl or carboxyl The ester of what contains is mentioned.
これらのカロテノイドの多くは、シス及びトランス異性体の形で天然に存在するが、合成物の場合にはラセミ混合物も含む。
カロテノイドは一般に植物素材から抽出することができる。これらのカロテノイド類は種々の機能を有しており、例えば、マリーゴールドの花弁から抽出するルテインは家禽の餌の原料として広く使用され、家禽の皮膚及び脂肪並びに家禽が産む卵に色を付ける機能がある。
本水分散物におけるカロテノイドの含有量は、分散組成物としたときにカロテノイド含有の機能的効果を良好に発揮させる観点から比較的高濃度であり、好ましくは0.1〜10質量%、より好ましくは0.2〜5質量%、更に好ましくは0.5〜2質量%である。
Many of these carotenoids occur naturally in the form of cis and trans isomers, but in the case of synthetics also include racemic mixtures.
Carotenoids can generally be extracted from plant material. These carotenoids have a variety of functions, for example, lutein extracted from marigold petals is widely used as a raw material for poultry food, and functions to color poultry skin and fat and eggs produced by poultry There is.
The content of the carotenoid in the aqueous dispersion is a relatively high concentration from the viewpoint of satisfactorily exerting the carotenoid-containing functional effect when the dispersion composition is formed, preferably 0.1 to 10% by mass, more preferably Is 0.2 to 5 mass%, more preferably 0.5 to 2 mass%.
本発明において用いられるカロテノイドとしては、分散時に用いる有機媒体を極力少なくする観点から、好ましくは常温で油状のものである。特に好ましい例としては、黄色から赤色の範囲の着色料として知られているアスタキサンチンである。
アスタキサンチンは、476nm(エタノール)、468nm(ヘキサン)に吸収極大を持つ赤色の色素でカロテノイドの一種キサントフィルに属している(Davies, B.H. : In “Chemistry and Biochemistry of Plant Pigments”, T. W. Goodwin ed., 2nd ed., 38-165, Academic Press, NY, 1976.)。アスタキサンチンの化学構造は3,3’−dihydroxy−β,β−carotene−4,4’−dione(C40H5204、分子量596.82)である。
本発明においては、特に断らない限り、上記のアスタキサンチン及びアスタキサンチンエステル等の誘導体を含めて「アスタキサンチン」と称する。
The carotenoid used in the present invention is preferably oily at normal temperature from the viewpoint of minimizing the organic medium used during dispersion. A particularly preferred example is astaxanthin, which is known as a colorant in the yellow to red range.
Astaxanthin is a red pigment with absorption maxima at 476 nm (ethanol) and 468 nm (hexane) and belongs to a kind of carotenoid xanthophyll (Davies, BH: In “Chemistry and Biochemistry of Plant Pigments”, TW Goodwin ed., 2nd. ed., 38-165, Academic Press, NY, 1976.). The chemical structure of astaxanthin is 3,3′-dihydroxy-β, β-carotene- 4 , 4′-dione (C 40 H 52 0 4 , molecular weight 596.82).
In the present invention, the term “astaxanthin” includes the above-mentioned derivatives such as astaxanthin and astaxanthin ester unless otherwise specified.
アスタキサンチンは、分子の両端に存在する環構造の3(3’)−位の水酸基の立体配置により異性体が存在する3S,3S’−体、3S,3R’−体(meso−体)、3R,3R’−体の三種で、さらに分子中央の共役二重結合のcis−、trans−の異性体も存在する。例えば全cis−、9−cis体と13−cis体などの如くである。 Astaxanthin is a 3S, 3S′-form, 3S, 3R′-form (meso-form), 3R in which isomers exist due to the configuration of the hydroxyl groups at the 3 (3 ′)-position of the ring structure present at both ends of the molecule. , 3R′-isomers, and cis- and trans-isomers of conjugated double bonds at the center of the molecule. For example, all cis-, 9-cis and 13-cis isomers.
前記3(3’)−位の水酸基は脂肪酸とエステルを形成することができる。オキアミから得られるアスタキサンチンは、脂肪酸二個結合したジエステル(Yamaguchi,K., Miki,W., Toriu, N., Kondo,Y., Murakami,M., Konosu,S., Satake,M., Fujita,T. : The composition of carotenoid pigments in the antarctic krill Euphausia superba, Bull. Jap. Sos. Sci. Fish., 1983, 49, p.1411-1415.)、H. pluvialisから得られるものは3S,3S’−体で、脂肪酸一個結合したモノエステル体が多く含まれている(Renstrom, B., Liaaen-Jensen, S. : Fatty acids of some esterified carotenols, Comp. Biochem. Physiol. B, Comp. Biochem., 1981, 69, p.625-627.)。 The hydroxyl group at the 3 (3 ')-position can form an ester with a fatty acid. Astaxanthin obtained from krill is a diester (Yamaguchi, K., Miki, W., Toriu, N., Kondo, Y., Murakami, M., Konosu, S., Satake, M., Fujita). , T .: The composition of carotenoid pigments in the antarctic krill Euphausia superba, Bull. Jap. Sos. Sci. Fish., 1983, 49, p.1411-1415.), H. pluvialis can be obtained from 3S, 3S '-Body, which contains many monoesters with one fatty acid (Renstrom, B., Liaaen-Jensen, S .: Fatty acids of some esterified carotenols, Comp. Biochem. Physiol. B, Comp. Biochem. , 1981, 69, p.625-627.).
また、Phaffia Rhodozymaより得られるアスタキサンチンは、3R,3R’−体(Andrewes, A.G., Starr, M.P. : (3R,3’R)-Asttaxanthin from the yeast Phaffa rhodozyma, Phytochem., 1976, 15, p.1009-1011.)であり、通常天然に見出される3S,3S’−体と反対の構造を持っている。また、これは脂肪酸とエステル形成していないフリー体で存在している(Andrewes, A.G., Phaffia, H.J., Starr, M.P. : Carotenids of Phaffia rhodozyma, a red pigmented fermenting yeast, Phytochem., 1976, 15, p.1003-1007.)。 Astaxanthin obtained from Phaffia Rhodozyma is a 3R, 3R′-form (Andrewes, AG, Starr, MP: (3R, 3′R) -Asttaxanthin from the yeast Phaffa rhodozyma, Phytochem., 1976, 15, p.1009. -1011.) And has the opposite structure to the 3S, 3S′-form normally found in nature. It also exists in free form that does not form esters with fatty acids (Andrewes, AG, Phaffia, HJ, Starr, MP: Carotenids of Phaffia rhodozyma, a red pigmented fermenting yeast, Phytochem., 1976, 15, p. .1003-1007.)
アスタキサンチンおよび同エステル体はR.Kuhnらによってロブスター(Astacus gammarus L.)から初めて分離され、その推定構造が開示された(Kuhn, R., Soerensen, N.A. : The coloring matters of the lobster (Astacus gammarus L.), Z. Angew. Chem.,1938, 51, p.465-466.)。それ以来、アスタキサンチンが自然界に広く分布し、通常アスタキサンチン脂肪酸エステル体として存在すること、甲殻類などでたんぱく質と結合したアスタキサンチン蛋白(オボルビン、クラスタシアニン)としても存在することが明らかにされている(Cheesman, D.F. : Ovorubin, a chromoprotein from the eggs of the gastropod mollusc Pomacea canaliculata, Proc. Roy. Soc. B, 1958, 149, p.571-587.)。 Astaxanthin and its ester are R.I. Kuhn et al. First isolated from lobster (Astacus gammarus L.) and disclosed its putative structure (Kuhn, R., Soerensen, NA: The coloring matters of the lobster (Astacus gammarus L.), Z. Angew. Chem. , 1938, 51, p.465-466.). Since then, it has been clarified that astaxanthin is widely distributed in nature and usually exists as an astaxanthin fatty acid ester, and also exists as an astaxanthin protein (oborbin, cluster cyanine) bound to proteins in crustaceans (Cheesman , DF: Ovorubin, a chromoprotein from the eggs of the gastropod mollusc Pomacea canaliculata, Proc. Roy. Soc. B, 1958, 149, p.571-587.).
前記アスタキサンチン及びアスタキサンチンのエステル(アスタキサンチン類)は、アスタキサンチン及び/又はそのエステルを含有する天然物から分離・抽出したアスタキサンチン含有オイルとして、本発明の水分散物及び分散組成物に含まれてもよい。このようなアスタキサンチン含有オイルとしては、例えば、赤色酵母ファフィア、緑藻ヘマトコッカス、海洋性細菌等を培養し、その培養物からの抽出物、ナンキョクオキアミ等からの抽出物を挙げることができる。
アスタキサンチンは分子内に2個の水酸基を有するが、ヘマトコッカス藻抽出物(ヘマトコッカス藻由来色素)はモノエステル体が主成分であり、オキアミ由来の色素は、ジエステル体が主成分である点で異なることが知られている。
The astaxanthin and the ester of astaxanthin (astaxanthins) may be contained in the aqueous dispersion and the dispersion composition of the present invention as an astaxanthin-containing oil separated and extracted from a natural product containing astaxanthin and / or its ester. Examples of such astaxanthin-containing oils include red yeast Phaffia, green algae hematococcus, marine bacteria, and the like, and extracts from the culture, extracts from Antarctic krill, and the like.
Astaxanthin has two hydroxyl groups in the molecule, Haematococcus alga extract (Haematococcus alga-derived dye) is monoester is the main component, krill-derived dyes, in terms diester as a main component It is known to be different.
本発明において用いることができるアスタキサンチンは、前記抽出物、またさらにこの抽出物を必要に応じて適宜精製したものでもよく、また合成品であってもよい。前記アスタキサンチンとしては、ヘマトコッカス藻から抽出されたもの(以下、ヘマトコッカス藻抽出物ともいう)が、品質、生産性の点から特に好ましい。 Astaxanthin that can be used in the present invention may be the above-described extract, a product obtained by appropriately purifying the extract as necessary, or a synthetic product. As the astaxanthin, those extracted from Haematococcus alga (hereinafter also referred to as Haematococcus alga extract) are particularly preferred from the viewpoint of quality and productivity.
本発明に使用できるヘマトコッカス藻抽出物の由来としては、具体的には、ヘマトコッカス・プルビアリス(Haematococcus pluvialis)、ヘマトコッカス・ラキュストリス(Haematococcus lacustris)、ヘマトコッカス・カペンシス(Haematococcus capensis)、ヘマトコッカス・ドロエバゲンシス(Haematococcus droebakensis)、ヘマトコッカス・ジンバビエンシス(Haematococcus zimbabwiensis)等が挙げられる。 Specific examples of the origin of the Haematococcus alga extract usable in the present invention include Haematococcus pluvialis, Haematococcus lacustris, Haematococcus capensis, Haematococcus capensis, Examples thereof include Haematococcus droebakensis and Haematococcus zimbabwiensis.
本発明に使用できるヘマトコッカス藻の培養方法は、特開平8−103288号公報等に開示された様々な方法を採用することができ、特に限定されるものではなく、栄養細胞から休眠細胞であるシスト細胞に形態変化していればよい。
本発明に使用できるヘマトコッカス藻抽出物は、上記の原料を、必要に応じて、例えば特開平5−68585号公報等に開示された方法により細胞壁を破砕して、アセトン、エーテル、クロロホルム及びアルコール(エタノール、メタノール等)等の有機溶剤や、超臨界状態の二酸化炭素等の抽出溶剤を加えて抽出することによって得られる。
The method for culturing Haematococcus algae that can be used in the present invention can employ various methods disclosed in JP-A-8-103288 and the like, and is not particularly limited. What is necessary is just to change the form to cyst cells.
The Haematococcus alga extract that can be used in the present invention is prepared by using the above-mentioned raw materials, if necessary, by crushing the cell wall by a method disclosed in, for example, JP-A-5-68585, etc., and adding acetone, ether, chloroform, and alcohol. It can be obtained by adding an organic solvent such as (ethanol, methanol, etc.) or an extraction solvent such as supercritical carbon dioxide.
前記ヘマトコッカス藻抽出物は、特開平2−49091号公報記載の色素同様、色素純分としてはアスタキサンチンもしくはそのエステル体を含み、エステル体を、一般的には50モル%以上、好ましくは75モル%以上、より好ましくは90モル%以上含むものである。
また、本発明において、広く市販されているヘマトコッカス藻抽出物を用いることができ、例えば、武田紙器(株)製のASTOTS−S、同−2.5O、同−5O、同−10O等、富士化学工業(株)製のアスタリールオイル50F、同5F等、東洋酵素化学(株)製のBioAstinSCE7等が挙げられる。
本発明において、ヘマトコッカス藻抽出物中のアスタキサチンの色素純分としての含有量は、好ましくは0.001質量%〜50質量%が好ましく、より好ましくは0.01質量%〜25質量%である。
また水分散物におけるアスタキサンチン含有オイルとしての配合量は、分散物の安定性の観点から0.001質量%〜20質量%が好ましく、0.1質量%〜10質量%であることが更に好ましい。
The Haematococcus alga extract contains astaxanthin or an ester thereof as the pure pigment, as in the dye described in JP-A-2-49091, and the ester is generally at least 50 mol%, preferably 75 mol. % Or more, more preferably 90 mol% or more.
In addition, in the present invention, commercially available Haematococcus alga extract can be used, for example, ASTOTS-S, -2.5O, -5O, -10O, etc., manufactured by Takeda Shiki Co., Ltd. Examples include Asteryl Oil 50F and 5F manufactured by Fuji Chemical Industry Co., Ltd., BioAstin SCE7 manufactured by Toyo Enzyme Chemical Co., Ltd., and the like.
In the present invention, the content of astaxanthin in the Haematococcus alga extract as a pure pigment content is preferably 0.001% by mass to 50% by mass, more preferably 0.01% by mass to 25% by mass. .
Moreover, 0.001 mass%-20 mass% are preferable from a viewpoint of the stability of a dispersion, and, as for the compounding quantity as an astaxanthin containing oil in an aqueous dispersion, it is still more preferable that it is 0.1 mass%-10 mass%.
本発明におけるリン脂質とは、複合脂質の内、脂肪酸、アルコール、燐酸、窒素化合物からなるエステルで、リン酸エステル及び脂肪酸エステルを有する一群であり、グリセリンを含まないグリセロリン脂質、スフィンドシンを含むスフィンゴリン脂質をいう。
本発明で使用するリン脂質としては、具体的にはホスファチジン酸、ビスホスファチジン酸、レシチン(ホスファチジルコリン)、ホスファチジルエタノールアミン、ホスファチジルメチルエタノールアミン、ホスファチジルセリン、ホスファチジルイノシトール、ホスファチジルグリセロール、ジホスファチジルグリセロール、スフィンゴミエリン等を例示でき、これらの成分を含む大豆、トウモロコシ、落花生、ナタネ、麦等の植物由来のものや、卵黄、牛等の動物由来のもの及び大腸菌等の微生物等由来の各種レシチンも挙げることができる。これらの混合物であるレシチンや水素添加レシチンを用いることもできる。またこれらリン脂質の由来は特に限定されず、例えばダイズ油等の植物油、卵黄等の動物由来のもの等が用いられ、特に精製したものが好適である。
The phospholipid in the present invention is an ester composed of fatty acid, alcohol, phosphoric acid and nitrogen compound among complex lipids, and is a group having phosphate ester and fatty acid ester, glycerophospholipid not containing glycerin, sphingoline containing sphingosine It refers to lipid.
Specific examples of the phospholipid used in the present invention include phosphatidic acid, bisphosphatidic acid, lecithin (phosphatidylcholine), phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol, phosphatidylglycerol, diphosphatidylglycerol, and sphingomyelin. Examples thereof include those derived from plants such as soybeans, corn, peanuts, rapeseed, and wheat, those derived from animals such as egg yolk and cows, and various lecithins derived from microorganisms such as E. coli. it can. A mixture of these, lecithin and hydrogenated lecithin can also be used. The origin of these phospholipids is not particularly limited. For example, vegetable oils such as soybean oil, those derived from animals such as egg yolk, etc. are used, and particularly purified ones are preferred.
また、本発明においては、グリセロリン脂質として、酵素分解した結果、1分子内に1つの脂肪酸残基を有するグリセロリン脂質、即ちリゾレシチンも含まれる。
このようなリゾレシチンは、酸、又はアルカリ触媒によるレシチンの加水分解により得られるが、ホスホリパーゼA1又はA2によるレシチンの加水分解により得ることもできる。
このようなリゾレシチンとしては、リゾホスファチジン酸、リゾホスファチジルグリセリン、リゾホスファチジルイノシトール、リゾホスファチジルエタノールアミン、リゾホスファチジルメチルエタノールアミン、リゾホスファチジルコリン(リゾレシチン)、リゾホスファチジルセリン等が挙げられる。
In the present invention, the glycerophospholipid includes glycerophospholipid having one fatty acid residue in one molecule, that is, lysolecithin as a result of enzymatic degradation.
Such lysolecithin can be obtained by hydrolysis of lecithin with an acid or alkali catalyst, but can also be obtained by hydrolysis of lecithin with phospholipase A 1 or A 2 .
Examples of such lysolecithin include lysophosphatidic acid, lysophosphatidylglycerin, lysophosphatidylinositol, lysophosphatidylethanolamine, lysophosphatidylmethylethanolamine, lysophosphatidylcholine (lysolecithin), lysophosphatidylserine and the like.
また更に、上記のレシチンに代表されるグリセロリン脂としては、水素添加又はヒドロキシル化されたものも、本発明において用いることができ、例えば水素添加レシチン、酵素分解レシチン、酵素分解水素添加レシチン、ヒドロキシレシチン等を使用することができる。
前記水素添加は、例えば、レシチンを触媒の存在下に水素と反応させることにより行われ、脂肪酸部分の不飽和結合が水素添加される。水素添加により、レシチンの酸化安定性が向上する。
また、前記ヒドロキシル化は、レシチンを高濃度の過酸化水素と酢酸、酒石酸、酪酸などの有機酸と共に加熱することにより、脂肪酸部分の不飽和結合が、ヒドロキシル化される。ヒドロキシル化により、レシチンの親水性が改良される。
Furthermore, as glycerophospholipid represented by the above lecithin, hydrogenated or hydroxylated one can also be used in the present invention. For example, hydrogenated lecithin, enzymatically decomposed lecithin, enzymatically decomposed hydrogenated lecithin, hydroxylecithin Etc. can be used.
The hydrogenation is performed, for example, by reacting lecithin with hydrogen in the presence of a catalyst, and the unsaturated bond of the fatty acid moiety is hydrogenated. Hydrogenation improves the oxidation stability of lecithin.
Moreover, the said hydroxylation heats a lecithin with high concentration hydrogen peroxide and organic acids, such as an acetic acid, tartaric acid, and butyric acid, and the unsaturated bond of a fatty-acid part is hydroxylated. Hydroxylation improves the hydrophilicity of lecithin.
本発明においては、乳化安定性の観点から、レシチンが特に好ましい。
市販品のレシチンとしては、理研ビタミン(株)製レシオンシリーズや、レシマールELなどを挙げることができる。
In the present invention, lecithin is particularly preferable from the viewpoint of emulsion stability.
Examples of commercially available lecithins include the Riken series manufactured by Riken Vitamin Co., Ltd. and Recimar EL.
前記レシチンの純度60質量%以上のものが産業的にはレシチンとして利用されているが、本発明においては、一般に「高純度レシチン」と称されるレシチン純度80質量%以上のものが好ましく、より好ましくは90質量%以上のものである。
このレシチン純度(質量%)は、レシチンがトルエンに溶解しやすくアセトンに溶解しない性質を利用して、トルエン不溶物とアセトン可溶物の重量を差し引くことにより求められる。高純度レシチンは、リゾレシチンに比べて親油性が高く、そのためレシチンと油性成分との相溶性が高くなり、乳化安定性を向上させ得るため好ましい。
本発明で用いるリン脂質は、単独又は複数種の混合物の形態で用いることができる。
Although the lecithin having a purity of 60% by mass or more is industrially used as lecithin, in the present invention, a lecithin having a purity of 80% by mass or more generally called “high purity lecithin” is preferable. Preferably it is 90 mass% or more.
The lecithin purity (mass%) is determined by subtracting the weight of the toluene insoluble matter and the acetone soluble matter by utilizing the property that lecithin is easily dissolved in toluene and not dissolved in acetone. High purity lecithin, high lipophilicity compared to lysolecithin, therefore increases the compatibility of the lecithin and the oily component is preferable since capable of improving emulsion stability.
The phospholipid used in the present invention can be used alone or in the form of a mixture of plural kinds.
本発明における水分散物におけるリン脂質の含有量は、乳化安定性の観点から、水分散物に対して0.001質量%〜20質量%であることが好ましく、より好ましくは0.001〜10質量%である。 The phospholipid content in the aqueous dispersion in the present invention is preferably from 0.001% by mass to 20% by mass, more preferably from 0.001 to 10%, based on the aqueous dispersion, from the viewpoint of emulsion stability. % By mass.
本発明にかかる水分散物に使用することができる水溶性乳化剤としては、水性媒体に溶解する乳化剤であれば特に限定は無いが、例えばHLBが10以上、好ましくは12以上のノニオン界面活性剤が好ましい。HLBが10未満の場合には、乳化力が不十分となることがある。また乳化安定性の観点からHLBは16以下であることが好ましい。 The water-soluble emulsifier that can be used in the aqueous dispersion according to the present invention is not particularly limited as long as it is an emulsifier that dissolves in an aqueous medium. For example, a nonionic surfactant having an HLB of 10 or more, preferably 12 or more. preferable. If the HLB is less than 10, the emulsifying power may be insufficient. From the viewpoint of emulsion stability, the HLB is preferably 16 or less.
ここで、HLBは、通常界面活性剤の分野で使用される親水性−疎水性のバランスであり、通常用いる計算式、例えば川上式等が使用できる。本発明においては、川上式を採用する。
HLB=7+11.7log(Mw/Mo)
ここで、Mwは親水基の分子量、Moは疎水基の分子量である。
また、カタログ等に記載されているHLBの数値を使用してもよい。
また、上記の式からも分かるように、HLBの加成性を利用して、任意のHLB値の乳化剤を得ることができる。
Here, HLB is a hydrophilic-hydrophobic balance that is usually used in the field of surfactants, and a commonly used calculation formula such as the Kawakami formula can be used. In the present invention, the Kawakami equation is adopted.
HLB = 7 + 11.7log (Mw / Mo)
Here, Mw is the molecular weight of the hydrophilic group, and Mo is the molecular weight of the hydrophobic group.
Moreover, you may use the numerical value of HLB described in the catalog etc.
Further, as can be seen from the above formula, an emulsifier having an arbitrary HLB value can be obtained by utilizing the additivity of HLB.
本発明で使用することのできる乳化剤は、特に制限は無いが、ノニオン性乳化剤が好ましい。ノニオン性乳化剤の例としては、グリセリン脂肪酸エステル、有機酸モノグリセリド、ポリグリセリン脂肪酸エステル、プロピレングリコール脂肪酸エステル、ポリグリセリン縮合リシノレイン酸エステル、ソルビタン脂肪酸エステル、およびショ糖脂肪酸エステルなどが挙げられる。より好ましくは、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ショ糖脂肪酸エステルである。また、上記の乳化剤は蒸留などで高度に精製されたものであることは必ずしも必要ではなく、反応混合物であってもよい。 The emulsifier that can be used in the present invention is not particularly limited, but a nonionic emulsifier is preferable. Examples of nonionic emulsifiers include glycerin fatty acid esters, organic acid monoglycerides, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyglycerin condensed ricinoleic acid esters, sorbitan fatty acid esters, and sucrose fatty acid esters. More preferred are polyglycerin fatty acid esters, sorbitan fatty acid esters, and sucrose fatty acid esters. The emulsifier is not necessarily highly purified by distillation or the like, and may be a reaction mixture.
本発明に用いられる、ポリグリセリン脂肪酸エステルとしては、平均重合度が2以上、好ましくは6〜15、より好ましくは8〜10のポリグリセリンと、炭素数8〜18の脂肪酸、例えばカプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、およびリノール酸とのエステルである。ポリグリセリン脂肪酸エステルの好ましい例としては、ヘキサグリセリンモノオレイン酸エステル、ヘキサグリセリンモノステアリン酸エステル、ヘキサグリセリンモノパルミチン酸エステル、ヘキサグリセリンモノミリスチン酸エステル、ヘキサグリセリンモノラウリン酸エステル、デカグリセリンモノオレイン酸エステル、デカグリセリンモノステアリン酸エステル、デカグリセリンモノパルミチン酸エステル、デカグリセリンモノミリスチン酸エステル、デカグリセリンモノラウリン酸エステル等が挙げられる。これらのポリグリセリン脂肪酸エステルを、単独又は混合して用いることができる。市販品としては、例えば、日光ケミカルズ(株)社製、NIKKOL DGMS,NIKKOL DGMO-CV,NIKKOL DGMO-90V,NIKKOL DGDO,NIKKOL DGMIS,NIKKOL DGTIS,NIKKOL Tetraglyn 1−SV,NIKKOL Tetraglyn 1−O,NIKKOL Tetraglyn 3−S,NIKKOL Tetraglyn 5−S,NIKKOL Tetraglyn 5−O,NIKKOL Hexaglyn 1−L,NIKKOL Hexaglyn 1−M,NIKKOL Hexaglyn 1−SV,NIKKOL Hexaglyn 1−O,NIKKOL Hexaglyn 3−S,NIKKOL Hexaglyn 4−B,NIKKOL Hexaglyn 5−S,NIKKOL Hexaglyn 5−O,NIKKOL Hexaglyn PR−15,NIKKOL Decaglyn 1−L,NIKKOL Decaglyn 1−M,NIKKOL Decaglyn 1−SV,NIKKOL Decaglyn 1−50SV,NIKKOL Decaglyn 1−ISV,NIKKOL Decaglyn 1−O,NIKKOL Decaglyn 1−OV,NIKKOL Decaglyn 1−LN,NIKKOL Decaglyn 2−SV,NIKKOL Decaglyn 2−ISV,NIKKOL Decaglyn 3−SV,NIKKOL Decaglyn 3−OV,NIKKOL Decaglyn 5−SV,NIKKOL Decaglyn 5−HS,NIKKOL Decaglyn 5−IS,NIKKOL Decaglyn 5−OV,NIKKOL Decaglyn 5−O−R,NIKKOL Decaglyn 7−S,NIKKOL Decaglyn 7−O,NIKKOL Decaglyn 10−SV,NIKKOL Decaglyn 10−IS,NIKKOL Decaglyn 10−OV,NIKKOL Decaglyn 10−MAC,NIKKOL Decaglyn PR−20,三菱化学フーズ(株)社製リョートーポリグリエステル L−10D、L−7D、M−10D、M−7D、P−8D、S−28D、S−24D、SWA−20D、SWA−15D、SWA−10D、O−50D、O−15D、B−100D、B−70D、ER−60D、太陽化学(株)社製サンソフトQ−17UL、サンソフトQ−14S、サンソフトA−141C、理研ビタミン(株)社製ポエムDO−100、ポエムJ−0021などが挙げられる。 The polyglycerin fatty acid ester used in the present invention has an average degree of polymerization of 2 or more, preferably 6 to 15, more preferably 8 to 10 and fatty acid having 8 to 18 carbon atoms, such as caprylic acid and caprin. Esters with acids, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid. Preferred examples of polyglycerol fatty acid esters include hexaglycerol monooleate, hexaglycerol monostearate, hexaglycerol monopalmitate, hexaglycerol monomyristate, hexaglycerol monolaurate, decaglycerol monooleate , Decaglycerin monostearic acid ester, decaglycerin monopalmitic acid ester, decaglycerin monomyristic acid ester, decaglycerin monolauric acid ester and the like. These polyglycerin fatty acid esters can be used alone or in combination. Commercially available products include, for example, Nikko Chemicals Co., Ltd., NIKKOL DGMS, NIKKOL DGMO-CV, NIKOL DGMO-90V, NIKKOL DGDO, NIKKOL DGMIS, NIKKOL DGTI, NIKKOL DGTIS, NIKKOL DGTI Tetraglyn 3-S, NIKKOL Tetraglyn 5-S, NIKKOL Tetraglyn 5-O, NIKKOL Hexaglyn 1-L, NIKKOL Hexaglyn 1-M, NIKKOL Hexaglyn 1-SV, NIKKOL Hexaglyn 1-O, NIKKOL Hexaglyn 3-S, NIKKOL Hexaglyn 4 -B, NIKKOL Hexa lyn 5-S, NIKKOL Hexaglyn 5-O, NIKKOL Hexaglyn PR-15, NIKKOL Decaglyn 1-L, NIKKOL Decaglyn 1-M, NIKKOL Decaglyn 1-SV, NIKKOL Decaglyn 1-50SV, NIKKOL Decaglyn 1-ISV, NIKKOL Decaglyn 1 -O, NIKKOL Decaglyn 1-OV, NIKKOL Decaglyn 1-LN, NIKKOL Decaglyn 2-SV, NIKKOL Decaglyn 2-ISV, NIKKOL Decaglyn 3-SV, NIKKOL Decaglyn 3-OV, NIKKOL Decaglyn 5-SV, NIKKOL Decaglyn 5-H , NIKKOL Decaglyn 5-IS, NIKKOL Decaglyn 5-OV, NIKKOL Decaglyn 5-O-R, NIKKOL Decaglyn 7-S, NIKKOL Decaglyn 7-O, NIKKOL Decaglyn 10-SV, NIKKOL Decaglyn 10-IS, NIKKOL Decaglyn 10-OV , NIKKOL Decaglyn 10-MAC, NIKKOL Decaglyn PR-20, Ryoto polyglycerate L-10D, L-7D, M-10D, M-7D, P-8D, S-28D, S, manufactured by Mitsubishi Chemical Foods Co., Ltd. -24D, SWA-20D, SWA-15D, SWA-10D, O-50D, O-15D, B-100D, B-70D, ER-60D, solarization Examples include Sunsoft Q-17UL, Sunsoft Q-14S, Sunsoft A-141C, and Poem DO-100, Poem J-0021 manufactured by Riken Vitamin Co., Ltd.
本発明に用いられるソルビタン脂肪酸エステルは、脂肪酸の炭素数が8以上のものが好ましく、12以上のものがより好ましい。ソルビタン脂肪酸エステルの好ましい例としては、モノカプリル酸ソルビタン、モノラウリン酸ソルビタン、モノステアリン酸ソルビタン、セキステアリン酸ソルビタン、トリステアリン酸ソルビタン、イソステアリン酸ソルビタン、セスキイソステアリン酸ソルビタン、オレイン酸ソルビタン、セスキオレイン酸ソルビタン、トリオレイン酸ソルビタン等が挙げられる。これらのソルビタン脂肪酸エステルを、単独又は混合して用いることができる。市販品としては、例えば、日光ケミカルズ(株)社製、NIKKOL SL−10,SP−10V,SS−10V,SS−10MV,SS−15V,SS−30V,SI−10RV,SI−15RV,SO−10V,SO−15MV,SO−15V,SO−30V,SO−10R,SO−15R,SO−30R,SO−15EX,第一工業製薬(株)社製の、ソルゲン30V、40V、50V、90、110などが挙げられる。 The sorbitan fatty acid ester used in the present invention preferably has 8 or more carbon atoms, more preferably 12 or more. Preferable examples of sorbitan fatty acid esters include sorbitan monocaprylate, sorbitan monolaurate, sorbitan monostearate, sorbitan tristearate, sorbitan tristearate, sorbitan isostearate, sorbitan sesquiisostearate, sorbitan oleate, sorbitan sesquioleate And sorbitan trioleate. These sorbitan fatty acid esters can be used alone or in combination. As a commercial item, Nikko Chemicals Co., Ltd. make, NIKKOL SL-10, SP-10V, SS-10V, SS-10MV, SS-15V, SS-30V, SI-10RV, SI-15RV, SO-15 10V, SO-15MV, SO-15V, SO-30V, SO-10R, SO-15R, SO-30R, SO-15EX, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Sorgen 30V, 40V, 50V, 90, 110 or the like.
本発明に用いられるショ糖脂肪酸エステルは、脂肪酸の炭素数が12以上のものが好ましく、12〜20のものがより好ましい。ショ糖脂肪酸エステルの好ましい例としては、ショ糖ジオレイン酸エステル、ショ糖ジステアリン酸エステル、ショ糖ジパルミチン酸エステル、ショ糖ジミリスチン酸エステル、ショ糖ジラウリン酸エステル、ショ糖モノオレイン酸エステル、ショ糖モノステアリン酸エステル、ショ糖モノパルミチン酸エステル、ショ糖モノミリスチン酸エステル、ショ糖モノラウリン酸エステル等が挙げられる。本発明においては、これらのショ糖脂肪酸エステルを、単独又は混合して用いることができる。市販品としては、例えば、三菱化学フーズ(株)社製リョートーシュガーエステル S−070、S−170、S−270、S−370、S−370F、S−570、S−770、S−970、S−1170、S−1170F、S−1570、S−1670、P−070、P−170、P−1570、P−1670、M−1695、O−170、O−1570、OWA−1570、L−195、L−595、L−1695、LWA−1570、B−370、B−370F、ER−190、ER−290、POS−135、第一工業製薬(株)社製の、DKエステルSS、F160、F140、F110、F90、F70、F50、F−A50、F−20W、F−10、F−A10E、コスメライクB−30、S−10、S−50、S−70、S−110、S−160、S−190、SA−10、SA−50、P−10、P−160、M−160、L−10、L−50、L−160、L−150A、L−160A、R−10、R−20、O−10、O−150等が挙げられる。 The sucrose fatty acid ester used in the present invention preferably has a fatty acid having 12 or more carbon atoms, more preferably 12-20. Preferred examples of sucrose fatty acid esters include sucrose dioleate, sucrose distearate, sucrose dipalmitate, sucrose dimyristic ester, sucrose dilaurate, sucrose monooleate, sucrose Examples thereof include sugar monostearate, sucrose monopalmitate, sucrose monomyristate, and sucrose monolaurate. In the present invention, these sucrose fatty acid esters can be used alone or in combination. Examples of commercially available products include Ryoto Sugar Esters S-070, S-170, S-270, S-370, S-370F, S-570, S-770, and S-970 manufactured by Mitsubishi Chemical Foods Corporation. , S-1170, S-1170F, S-1570, S-1670, P-070, P-170, P-1570, P-1670, M-1695, O-170, O-1570, OWA-1570, L -195, L-595, L-1695, LWA-1570, B-370, B-370F, ER-190, ER-290, POS-135, DK ester SS manufactured by Daiichi Kogyo Seiyaku Co., Ltd., F160, F140, F110, F90, F70, F50, F-A50, F-20W, F-10, F-A10E, Cosmelike B-30, S-10, S-50, S-70, -110, S-160, S-190, SA-10, SA-50, P-10, P-160, M-160, L-10, L-50, L-160, L-150A, L-160A , R-10, R-20, O-10, O-150 and the like.
これら乳化剤の添加量は、水分散物に対して、好ましくは0.1〜50質量%、より好ましくは0.5〜20質量%、更に好ましくは1〜15質量%である。0.1質量%以上の添加量とすることによって、より微細な粒子径の乳化物を得ることができると共に乳化物の安定性を充分に確保することができ、また、50質量%以下の添加量とすることによって、乳化物の泡立ちを適切な範囲に調整することができる。 The amount of these emulsifiers added is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 15% by mass with respect to the aqueous dispersion. By setting the addition amount to 0.1% by mass or more, it is possible to obtain an emulsion having a finer particle size and to sufficiently ensure the stability of the emulsion, and to add 50% by mass or less. By setting the amount, foaming of the emulsion can be adjusted to an appropriate range.
水分散物には、カロテノイド類の酸化防止の観点から油溶性成分として更にトコフェロールを含有することが好ましい。
使用可能なトコフェロールとしては、特に限定されず、トコフェロールまたはその誘導体からなる化合物群から選ばれるものである。
トコフェロールまたはその誘導体からなる化合物群としては、dl−α−トコフェロール、dl−β−トコフェロール、dl−γ−トコフェロール、dl−δ−トコフェロール、酢酸dl−α−トコフェロール、ニコチン酸−dl−α−トコフェロール、リノール酸−dl−α−トコフェロール、コハク酸dl−α−トコフェロール等のトコフェロール及びその誘導体、α−トコトリエノール、β−トコトリエノール、γ−トコトリエノール、δ−トコトリエノール等が挙げられる。これらは、混合物の状態で使用する場合が多く、抽出トコフェロール、ミックストコフェロールなどと呼ばれる状態で使用できる。
本水分散物におけるトコフェロールの含有量としては、特に限定されないが、カロテノイド類の酸化防止に有効な量の観点から、カロテノイド量に対して0.1〜5の比率であることが好ましく、より好ましくは0.2〜3、更に好ましくは0.5〜2の比率である。
The aqueous dispersion preferably further contains tocopherol as an oil-soluble component from the viewpoint of preventing carotenoids from being oxidized.
Usable tocopherols are not particularly limited and are selected from the group of compounds consisting of tocopherols or derivatives thereof.
The compound group consisting of tocopherol or its derivatives includes dl-α-tocopherol, dl-β-tocopherol, dl-γ-tocopherol, dl-δ-tocopherol, dl-α-tocopherol acetate, nicotinic acid-dl-α-tocopherol. , Linoleic acid-dl-α-tocopherol, tocopherols such as dl-α-tocopherol succinate and derivatives thereof, α-tocotrienol, β-tocotrienol, γ-tocotrienol, δ-tocotrienol and the like. These are often used in the form of a mixture, and can be used in a state called extracted tocopherol, mixed tocopherol or the like.
The content of tocopherol in the present aqueous dispersion is not particularly limited, but is preferably a ratio of 0.1 to 5 with respect to the amount of carotenoid, more preferably from the viewpoint of an amount effective for preventing carotenoids from being oxidized. Is a ratio of 0.2 to 3, more preferably 0.5 to 2.
本発明にかかる水分散物においては、グリセリンを含有することが、水分散物におけるエマルジョン粒子の平均粒子径をより小さくし、かつ該粒子径を小さいまま長期に亘り安定して保持できるため、好ましい。
この場合、グリセリンの含有量は、本水分散物の全質量に対して、分散安定性、防腐性の観点から10質量%〜60質量%が好ましく、好ましくは20質量%〜55質量%、さらに好ましくは30質量%〜50質量%である。
In the aqueous dispersion according to the present invention, it is preferable that glycerin is contained because the average particle diameter of the emulsion particles in the aqueous dispersion can be further reduced, and the particle diameter can be stably maintained over a long period of time. .
In this case, the content of glycerin is preferably 10% by mass to 60% by mass, preferably 20% by mass to 55% by mass, more preferably 20% by mass to 55% by mass with respect to the total mass of the aqueous dispersion. Preferably they are 30 mass%-50 mass%.
また、本水分散物は、酸化防止剤を含むことが好ましい。
使用可能な酸化防止剤としては、特に限定されないが、例えば、ポリフェノール類からなる化合物群、ラジカル補足剤、前述のトコフェロール類等を挙げることができる。
本発明で使用可能な酸化防止剤は、親水性の酸化防止剤、及び/又は、油溶性の酸化防止剤を、単独又は併用して使用することができる。
本発明のカロテノイド含有エマルジョン組成物における酸化防止剤の含有量は、一般的には0.1質量%〜10質量%であり、好ましくは0.2質量%〜5質量%、より好ましくは0.5質量%〜2質量%である。
なお、一般に酸化防止剤等として使用可能なアスコルビン酸又はアスコルビン酸誘導体は、本水分散物には含まれない。これらの化合物は、後述するように、本水分散物と混合するための水性組成物中に含まれる。
Moreover, it is preferable that this water dispersion contains antioxidant.
Examples of usable antioxidants include, but are not limited to, compounds including polyphenols, radical scavengers, the aforementioned tocopherols, and the like.
As the antioxidant that can be used in the present invention, a hydrophilic antioxidant and / or an oil-soluble antioxidant can be used alone or in combination.
The content of the antioxidant in the carotenoid-containing emulsion composition of the present invention is generally 0.1% by mass to 10% by mass, preferably 0.2% by mass to 5% by mass, and more preferably 0.8%. It is 5 mass%-2 mass%.
In addition, ascorbic acid or an ascorbic acid derivative that can generally be used as an antioxidant or the like is not included in the aqueous dispersion. These compounds are contained in the aqueous composition for mixing with the aqueous dispersion as described later.
水分散物において使用可能な酸化防止剤であるポリフェノール類からなる化合物群としては、フラボノイド類(カテキン、アントシアニン、フラボン、イソフラボン、フラバン、フラバノン、ルチン)、フェノール酸類(クロロゲン酸、エラグ酸、没食子酸、没食子酸プロピル)、リグナン類、クルクミン類、クマリン類などを挙げることができる。また、これらの化合物は、以下のような天然物由来の抽出物中に多く含まれるため、抽出物という状態で利用することができる。 Compound groups consisting of polyphenols that are antioxidants that can be used in aqueous dispersions include flavonoids (catechin, anthocyanin, flavone, isoflavone, flavan, flavanone, rutin), phenolic acids (chlorogenic acid, ellagic acid, gallic acid Propyl gallate), lignans, curcumins, and coumarins. Moreover, since these compounds are contained in a large amount in the following natural product-derived extracts, they can be used in the form of extracts.
例えば、カンゾウ抽出物、キュウリ抽出物、ケイケットウ抽出物、ゲンチアナ(リンドウ)抽出物、ゲンノショウコ抽出物、コレステロール及びその誘導体、サンザシ抽出物、シャクヤク抽出物、イチョウ抽出物、コガネバナ(オウゴン)抽出物、ニンジン抽出物、マイカイカ(マイカイ、ハマナス)抽出物、サンペンズ(カワラケツメイ)抽出物、トルメンチラ抽出物、パセリ抽出物、ボタン(ボタンピ)抽出物、モッカ(ボケ)抽出物、メリッサ抽出物、ヤシャジツ(ヤシャ)抽出物、ユキノシタ抽出物、ローズマリー(マンネンロウ)抽出物、レタス抽出物、茶抽出物(烏龍茶、紅茶、緑茶等)、微生物醗酵代謝産物、羅漢果抽出物等が挙げられる(かっこ内は、植物の別名、生薬名等を記載した。)。これらのポリフェノール類のうち、特に好ましいものとしては、カテキン、ローズマリー抽出物、グルコシルルチン、エラグ酸、没食子酸を挙げることができる。 For example, licorice extract, cucumber extract, caquette extract, gentian (gentian) extract, Gentian extract, cholesterol and its derivatives, hawthorn extract, peonies extract, ginkgo biloba extract, scallop (Ogon) extract, carrot Extract, Maika (Maika, Hamanasu) extract, Sunpens (Kawara-Ketsumei) extract, Tormentilla extract, Parsley extract, Button (buttonpi) extract, Mokka (bokeh) extract, Melissa extract, Yashajitsu (Yasha) extract , Yukinoshita extract, Rosemary (mannenrou) extract, lettuce extract, tea extract (Oolong tea, black tea, green tea, etc.), microbial fermentation metabolites, Rakan fruit extract, etc. (in parentheses are plant aliases) , Herbal medicine name etc. were described.) Among these polyphenols, catechin, rosemary extract, glucosyl rutin, ellagic acid, and gallic acid are particularly preferable.
本発明に用いる酸化防止剤は、一般に市販されているものを適宜用いることができる。例えば、エラグ酸(和光純薬ほか)、ローズマリー抽出物(商品名RM−21A,RM−21E:三菱化学フーズほか)、カテキン(商品名:サンカトールW−5、No.1:太陽化学、ほか)、没食子酸Na(商品名:サンカトール:太陽化学、ほか)、ルチン・グルコシルルチン・酵素分解ルチン(商品名:ルチンK−2、P−10:キリヤ化学、商品名αGルチン:林原生物化学研究所ほか)等が挙げられる。 What is generally marketed can be used suitably for the antioxidant used for this invention. For example, ellagic acid (Wako Pure Chemicals, etc.), rosemary extract (trade names RM-21A, RM-21E: Mitsubishi Chemical Foods, etc.), catechin (trade names: Sankatol W-5, No. 1: Taiyo Kagaku, etc. ), Na gallate (trade name: Sankatol: Taiyo Kagaku, etc.), rutin / glucosylrutin / enzymatic degradation rutin (trade name: rutin K-2, P-10: Kiriya Chemical, trade name αG rutin: Hayashibara Biochemical Research) Etc.).
水分散物において使用可能なラジカル捕捉剤からなる群は、ラジカルの発生を抑えるとともに、生成したラジカルをできる限り速やかに捕捉し、連鎖反応を断つ役割を担う添加剤である。(出典:「油化学便覧第4版」、日本油化学会編、2001)ラジカル捕捉剤としての機能を確認する直接的な方法としては、試薬と混合して、ラジカルを捕捉する様子を分光光度計やESR(電子スピン共鳴装置)によって測定する方法が知られている。これらの方法では、試薬として、DPPH(1,1−ジフェニル−2−ピクリルヒドラジル)や、ガルビノキシルラジカルが使用される。
本発明では、油脂の自動酸化反応を利用して、以下の実験条件下で、油脂の過酸化物価(POV値)を60meq/kgに引き上げるまでに要する時間が、ブランクに対し2倍以上である化合物をラジカル捕捉剤とする。より好ましくは、5倍以上である。
油脂:オリーブ油
添加量:油脂に対し0.1質量%
試験条件:試料を190℃にて加熱し、時間を追ってPOV値を測定し、60meq/kgとなる時間を算出した。
The group of radical scavengers that can be used in the aqueous dispersion is an additive that suppresses the generation of radicals, captures the generated radicals as quickly as possible, and interrupts the chain reaction. (Source: “Oil Chemistry Handbook 4th Edition”, edited by Japan Oil Chemists' Society, 2001) As a direct method of confirming the function as a radical scavenger, it can be mixed with a reagent to capture radicals by spectrophotometry. A method of measuring by a meter or an ESR (electron spin resonance apparatus) is known. In these methods, DPPH (1,1-diphenyl-2-picrylhydrazyl) or galvinoxyl radical is used as a reagent.
In the present invention, the time required to raise the peroxide value (POV value) of fats and oils to 60 meq / kg under the following experimental conditions using the autoxidation reaction of fats and oils is twice or more that of the blank. The compound is a radical scavenger. More preferably, it is 5 times or more.
Fat and oil: Olive oil Addition amount: 0.1% by mass with respect to fat and oil
Test conditions: The sample was heated at 190 ° C., the POV value was measured over time, and the time for 60 meq / kg was calculated.
本発明のラジカル捕捉剤として使用できる化合物は、「抗酸化剤の理論と実際」(梶本著、三書房、1984)や、「酸化防止剤ハンドブック」(猿渡、西野、田端著、大成社、1976)に記載の各種酸化防止剤のうち、ラジカル捕捉剤として機能するものであれば良く、具体的には、フェノール性OHを有する化合物、フェニレンジアミン等のアミン系酸化防止剤、また、アスコルビン酸、エリソルビン酸の油溶化誘導体等を挙げることができる。
以下に好ましい化合物を例示するが本発明はこれらに限定されるものではない。
前記フェノール性OHを有する化合物として、グアヤク脂、ノルジヒドログアヤレチック酸(NDGA)、没食子酸エステル類、BHT(ブチルヒドロキシトルエン)、BHA(ブチルヒドロキシアニソール)、トコフェロール類およびビスフェノール類等が挙げられる。没食子酸エステル類として、没食子酸プロピル、没食子酸ブチルおよび没食子酸オクチルが挙げられる。
アミン系化合物としてフェニレンジアミンが挙げられ、ジフェニル−p−フェニレンジアミンまたは4−アミノ−p−ジフェニルアミンがより好ましい。
The compounds that can be used as the radical scavenger of the present invention include “theory and practice of antioxidants” (Enomoto, Sanshobo, 1984) and “Antioxidant Handbook” (Saruwatari, Nishino, Tabata, Taiseisha, 1976). Among the various antioxidants described in (1), any compound that functions as a radical scavenger may be used. Specifically, compounds having phenolic OH, amine-based antioxidants such as phenylenediamine, ascorbic acid, Examples include oil-solubilized derivatives of erythorbic acid.
Although the preferable compound is illustrated below, this invention is not limited to these.
Examples of the compound having phenolic OH include guaiac fat, nordihydroguaiaretic acid (NDGA), gallic acid esters, BHT (butylhydroxytoluene), BHA (butylhydroxyanisole), tocopherols and bisphenols. . Examples of gallic acid esters include propyl gallate, butyl gallate, and octyl gallate.
Examples of the amine compound include phenylenediamine, and diphenyl-p-phenylenediamine or 4-amino-p-diphenylamine is more preferable.
また他の油溶性成分として、通常、紫外線吸収剤、抗酸化剤、抗炎症剤、保湿剤、毛髪保護剤、分散剤、溶剤、美白剤、抗シミ剤、細胞賦活剤、エモリエント剤、角質溶解剤、帯電防止剤、ビタミン類、メタボリックシンドローム改善剤、降圧剤、鎮静剤などとして使用されている他の成分も使用することができ、例えば、オリーブ油、ツバキ油、マカデミアナッツ油、ヒマシ油などの油脂類、流動パラフィン、パラフィン、ワセリン、セレシン、マイクロクリスタリンワックス、スクワランなどの炭化水素、カルナウバロウ、キャンデリラロウ、ホホバ油、ミツロウ、ラノリンなどのロウ類、ミリスチン酸イソプロピル、ミリスチン酸2−オクチルドデシル、2−エチルヘキサン酸セチル、リンゴ酸ジイソステアリルなどのエステル類、パルミチン酸、ステアリン酸、イソステアリン酸などの脂肪酸類、セチルアルコール、ステアリルアルコール、イソステアリルアルコール、2−オクチルドデカノールなどの高級アルコール類、メチルポリシロキサン、メチルフェニルポリシロキサンなどのシリコーン油、グリセリンの脂肪酸エステル類、その他、高分子類、油溶性色素類、油溶性蛋白質などを挙げることができる。また、それらの混合物である各種の植物由来油、動物由来油も含まれる。本発明に用いられる好ましい他の油性成分としては、ビタミンE類(上述したトコフェロールの他として、トコトリエノール等)、コエンザイムQ類、ω−3油脂類(EPA、DHA、リノレン酸等を含む油脂)などを挙げることができる。 Other oil-soluble ingredients are usually UV absorbers, antioxidants, anti-inflammatory agents, moisturizers, hair protectants, dispersants, solvents, whitening agents, anti-staining agents, cell activators, emollients, keratolytics. Other ingredients used as agents, antistatic agents, vitamins, metabolic syndrome improving agents, antihypertensives, sedatives, etc. can be used, for example, oils such as olive oil, camellia oil, macadamia nut oil, castor oil , Hydrocarbons such as liquid paraffin, paraffin, petrolatum, ceresin, microcrystalline wax, squalane, carnauba wax, candelilla wax, jojoba oil, beeswax, lanolin and other waxes, isopropyl myristate, 2-octyldodecyl myristate, 2 -Esters such as cetyl ethylhexanoate and diisostearyl malate, Fatty acids such as mitic acid, stearic acid and isostearic acid, higher alcohols such as cetyl alcohol, stearyl alcohol, isostearyl alcohol and 2-octyldodecanol, silicone oils such as methylpolysiloxane and methylphenylpolysiloxane, fatty acids of glycerin Examples include esters, other polymers, oil-soluble pigments, and oil-soluble proteins. In addition, various plant-derived oils and animal-derived oils that are mixtures thereof are also included. Other preferable oily components used in the present invention include vitamin Es (in addition to the above-mentioned tocopherol, tocotrienol, etc.), coenzyme Qs, omega-3 oils (oils and fats containing EPA, DHA, linolenic acid, etc.), etc. Can be mentioned.
また、本発明における水分散物には、上述した種々の油性成分及びその他の成分を溶解するために、また、水分散物におけるエマルジョン粒子の平均粒径をより微細化するために有機溶媒を添加することが好ましい。
このような有機溶媒としては水溶性であることが好ましく、例えば、メタノール、エタノール、イソプロパノール、アセトン、テトラヒドロフラン、アセトニトリル等及びそれらの混合物を挙げられる。これらの中でも、食品、化粧品等への用途を考慮したとき、エタノールが好ましい。
この有機溶媒の水分散物に対する含有量は、例えば、0.1質量%〜20質量%、好ましくは0.5質量%〜10質量%とすることができる。
In addition, an organic solvent is added to the aqueous dispersion in the present invention in order to dissolve the various oily components and other components described above and to further refine the average particle size of the emulsion particles in the aqueous dispersion. It is preferable to do.
Such an organic solvent is preferably water-soluble, and examples thereof include methanol, ethanol, isopropanol, acetone, tetrahydrofuran, acetonitrile and a mixture thereof. Among these, ethanol is preferred when considering use for foods, cosmetics and the like.
Content with respect to the aqueous dispersion of this organic solvent can be 0.1 mass%-20 mass%, for example, Preferably it can be 0.5 mass%-10 mass%.
本水分散物におけるエマルジョン粒子の粒子径は、透明性の観点から、体積平均粒子径(メジアン径)として200nm以下であり、好ましくは150nm以下、更に好ましくは100nm以下である。このような平均粒子径の粒子は、上記水分散物の成分を上述したような量比で混合することによって、容易に得ることができる。
粒子径は、添加成分の種類及び使用量、製造方法における乳化条件(せん断力・温度・圧力)や、添加剤の使用量、油相と水相比率、界面活性剤の使用量などの要因によって変動するが、本発明の粒子径であれば、実用上問題ない。
From the viewpoint of transparency, the particle diameter of the emulsion particles in the aqueous dispersion is 200 nm or less, preferably 150 nm or less, more preferably 100 nm or less, as a volume average particle diameter (median diameter). The particles having such an average particle diameter can be easily obtained by mixing the components of the aqueous dispersion in the above-described quantitative ratio.
The particle size depends on factors such as the type and amount used of the additive component, emulsification conditions (shearing force, temperature, pressure) in the production method, the amount of additive used, the ratio of oil phase to water phase, and the amount of surfactant used. Although it varies, there is no practical problem if the particle diameter of the present invention is used.
粒子径は、市販の粒度分布計等で計測することができる。エマルションの粒度分布測定法としては、光学顕微鏡法、共焦点レーザー顕微鏡法、電子顕微鏡法、原子間力顕微鏡法、静的光散乱法、レーザー回折法、動的光散乱法、遠心沈降法、電気パルス計測法、クロマトグラフィー法、超音波減衰法等が知られており、それぞれの原理に対応した装置が市販されている。
本発明における粒径範囲および測定の容易さから、本発明のエマルション粒径測定では動的光散乱法が好ましい。動的光散乱を用いた市販の測定装置としては、ナノトラックUPA(日機装(株))、動的光散乱式粒径分布測定装置LB−550((株)堀場製作所)、濃厚系粒径アナライザーFPAR−1000(大塚電子(株))等が挙げられる。また測定温度としては、粒子径の測定に通常用いられる温度であればよいが、20℃であることが好ましい。
本発明における粒子径は、測定温度を20℃とし、前記動的光散乱式粒径分布測定装置を用いて測定した値とする。
The particle diameter can be measured with a commercially available particle size distribution meter or the like. Emulsion particle size distribution measurement methods include optical microscopy, confocal laser microscopy, electron microscopy, atomic force microscopy, static light scattering, laser diffraction, dynamic light scattering, centrifugal sedimentation, electricity A pulse measurement method, a chromatography method, an ultrasonic attenuation method, and the like are known, and apparatuses corresponding to the respective principles are commercially available.
In view of the particle size range and the ease of measurement in the present invention, the dynamic light scattering method is preferred for the emulsion particle size measurement of the present invention. As a commercially available measuring device using dynamic light scattering, Nanotrac UPA (Nikkiso Co., Ltd.), dynamic light scattering type particle size distribution measuring device LB-550 (Horiba, Ltd.), a concentrated particle size analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.) etc. are mentioned. The measurement temperature may be any temperature usually used for measuring the particle diameter, but is preferably 20 ° C.
The particle diameter in the present invention is a value measured using the dynamic light scattering particle size distribution measuring apparatus at a measurement temperature of 20 ° C.
本発明にかかる水分散物を構成する水性媒体としては、主として水を挙げることができ、蒸留水、イオン交換水、純水等のいずれも用いることができる。 Examples of the aqueous medium constituting the aqueous dispersion according to the present invention include water, and any of distilled water, ion-exchanged water, pure water, and the like can be used.
本発明におけるカロテノイド含有油溶性成分を含む水分散物は、特に限定されないが、例えば、a)水性媒体に、水溶性乳化剤を溶解させて、水相を得、b)前述したカロテノイドや、トコフェロール、リン脂質、及び必要に応じてその他の油脂を混合・溶解して、油相を得、c)攪拌下で水相と油相を混合して、乳化分散を行うことによって得ることができる。 The aqueous dispersion containing the carotenoid-containing oil-soluble component in the present invention is not particularly limited. For example, a) a water-soluble emulsifier is dissolved in an aqueous medium to obtain an aqueous phase, and b) the aforementioned carotenoid, tocopherol, It can be obtained by mixing and dissolving phospholipids and other fats and oils as necessary to obtain an oil phase, and c) mixing an aqueous phase and an oil phase with stirring, and emulsifying and dispersing.
乳化分散の際、例えば、スターラーやインペラー攪拌、ホモミキサー、連続流通式剪断装置等の剪断作用を利用する通常の乳化装置を用いて乳化をした後、高圧ホモジナイザーを通す等の方法で2種以上の乳化装置を併用するのが特に好ましい。高圧ホモジナイザーを使用することで、乳化物を更に均一な微粒子の液滴に揃えることができる。また、更に均一な粒子径の液滴とする目的で複数回行ってもよい。 When emulsifying and dispersing, for example, after emulsification using a normal emulsifier using a shearing action such as a stirrer, impeller agitation, homomixer, continuous flow type shearing device, etc., two or more types are passed by a method such as passing through a high-pressure homogenizer. It is particularly preferable to use the above emulsifying apparatus together. By using a high-pressure homogenizer, the emulsion can be arranged into even more uniform droplets of fine particles. Further, it may be performed a plurality of times for the purpose of forming a droplet having a more uniform particle diameter.
高圧ホモジナイザーには、処理液の流路が固定されたチャンバーを有するチャンバー型高圧ホモジナイザー及び均質バルブを有する均質バルブ型高圧ホモジナイザーが挙げられる。これらの中では、均質バルブ型高圧ホモジナイザーは、処理液の流路の幅を容易に調節することができるので、操作時の圧力及び流量を任意に設定することができ、その操作範囲が広いため、本発明において好ましく用いることができる。また、操作の自由度は低いが、圧力を高める機構が作りやすいため、超高圧を必要とする用途にはチャンバー型高圧ホモジナイザーも好適に用いることができる。 Examples of the high-pressure homogenizer include a chamber-type high-pressure homogenizer having a chamber in which a flow path for processing liquid is fixed, and a homogeneous valve-type high-pressure homogenizer having a homogeneous valve. Among these, the homogeneous valve type high-pressure homogenizer can easily adjust the width of the flow path of the processing liquid, so the pressure and flow rate during operation can be set arbitrarily, and the operation range is wide. Can be preferably used in the present invention. In addition, although the degree of freedom of operation is low, a mechanism for increasing the pressure is easy to make, and therefore a chamber type high-pressure homogenizer can be suitably used for applications that require ultra-high pressure.
チャンバー型高圧ホモジナイザーとしては、マイクロフルイダイザー(マイクロフルイディクス社製)、ナノマイザー(吉田機械興業(株)製)、アルティマイザー((株)スギノマシン製)等が挙げられる。
均質バルブ型高圧ホモジナイザーとしては、ゴーリンタイプホモジナイザー(APV社製)、ラニエタイプホモジナイザー(ラニエ社製)、高圧ホモジナイザー(ニロ・ソアビ社製)、ホモゲナイザー(三和機械(株)製)、高圧ホモゲナイザー(イズミフードマシナリ(株)製)、超高圧ホモジナイザー(イカ社製)等が挙げられる。
Examples of the chamber type high-pressure homogenizer include a microfluidizer (manufactured by Microfluidics), a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), an optimizer (manufactured by Sugino Machine Co., Ltd.), and the like.
As the homogeneous valve type high-pressure homogenizer, Gorin type homogenizer (manufactured by APV), Lanier type homogenizer (manufactured by Lanier), high-pressure homogenizer (manufactured by Niro Soabi), homogenizer (manufactured by Sanwa Machinery Co., Ltd.), high-pressure homogenizer ( Izumi Food Machinery Co., Ltd.), ultra-high pressure homogenizer (manufactured by Ika), and the like.
本発明において、前記高圧ホモジナイザーの圧力は、好ましくは50MPa以上、より好ましくは50〜250MPa、更に好ましくは100〜250MPaで処理することが好ましい。また、乳化分散された組成物である乳化液はチャンバー通過直後30秒以内、好ましくは3秒以内に何らかの冷却器を通して冷却することが、分散粒子の粒子径保持の観点から好ましい。 In the present invention, the pressure of the high-pressure homogenizer is preferably 50 MPa or more, more preferably 50 to 250 MPa, and still more preferably 100 to 250 MPa. Moreover, it is preferable from the viewpoint of maintaining the particle size of the dispersed particles that the emulsified liquid, which is an emulsified and dispersed composition, is cooled through some cooler within 30 seconds, preferably within 3 seconds immediately after passing through the chamber.
次に、本発明における水性組成物について説明する。
本発明における水性組成物は、アスコルビン酸又はその誘導体を含むものである。
本発明では、水性組成物にアスコルビン酸又はその誘導体が含まれるので、水性組成物とカロテノイド含有油溶性成分を含む水分散物とを混合することによって、カロテノイドの褪色を抑制し、エマルション粒子の分散性と色味とを共に安定させることができる。また、香料を更に含む分散組成物では、香料による賦香性を良好に維持することができる。
アスコルビン酸又はその誘導体としては、水溶性アスコルビン酸又はその誘導体であることが好ましい。
このようなアスコルビン酸又はアスコルビン酸誘導体としては、アスコルビン酸、アスコルビン酸ナトリウム、アスコルビン酸カリウム、アスコルビン酸カルシウム、L−アスコルビン酸リン酸エステル、リン酸アスコルビルマグネシウム、硫酸アスコルビル、硫酸アスコルビル2ナトリウム塩、アスコルビル−2−グルコシド等が挙げられる。また、エリソルビン酸又はその誘導体、例えばエリソルビン酸、エリソルビン酸ナトリウム、エリソルビン酸カリウム、エリソルビン酸カルシウム、リン酸エリソルビン酸、硫酸エリソルビン酸なども、本発明におけるアスコルビン酸又はその誘導体に含むことができる。
これらのうち、カロテノイドの褪色防止やエマルジョン粒子の分散安定性の観点から、リン酸アスコルビルマグネシウム、リン酸アスコルビルナトリウム、アスコルビル−2−グルコシド、アスコルビン酸ナトリウムが好ましく、リン酸アルコルビルマグネシウム及びリン酸アスコルビルナトリウムが特に好ましい。
Next, the aqueous composition in the present invention will be described.
The aqueous composition in the present invention contains ascorbic acid or a derivative thereof.
In the present invention, ascorbic acid or a derivative thereof is contained in the aqueous composition. By mixing the aqueous composition and the aqueous dispersion containing the carotenoid-containing oil-soluble component, the discoloration of the carotenoid is suppressed, and the emulsion particles are dispersed. Both sex and color can be stabilized. Moreover, in the dispersion composition which further contains a fragrance | flavor, the fragrance | flavor property by a fragrance | flavor can be maintained favorable.
Ascorbic acid or a derivative thereof is preferably water-soluble ascorbic acid or a derivative thereof.
Examples of such ascorbic acid or ascorbic acid derivatives include ascorbic acid, sodium ascorbate, potassium ascorbate, calcium ascorbate, L-ascorbic acid phosphate, ascorbyl magnesium phosphate, ascorbyl sulfate, ascorbyl sulfate disodium salt, ascorbyl -2-glucoside and the like. In addition, erythorbic acid or a derivative thereof such as erythorbic acid, sodium erythorbate, potassium erythorbate, calcium erythorbate, erythorbic acid phosphate, erythorbic acid sulfate, etc. can also be included in the ascorbic acid or derivative thereof in the present invention.
Of these, from the viewpoints of preventing carotenoid discoloration and dispersion stability of emulsion particles, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, ascorbyl-2-glucoside, and sodium ascorbate are preferred, and magnesium ascorbyl phosphate and ascorbyl phosphate are preferred. Sodium is particularly preferred.
これらのアスコルビン酸又はその誘導体は、一般に市販されているものを適宜用いることができる。例えば、L−アスコルビン酸(武田薬品工業、扶桑化学、BASFジャパン、第一製薬ほか)、L−アスコルビン酸Na(武田薬品工業、扶桑化学、BASFジャパン、第一製薬ほか)、アスコルビン酸2−グルコシド(商品名 AA−2G:林原生物化学研究所)、L−アスコルビン酸燐酸Mg(商品名 アスコルビン酸PM「SDK」(昭和電工)、商品名 NIKKOL VC−PMG(日光ケミカルズ)、商品名 シーメート(武田薬品工業))等が挙げられる。 These ascorbic acid or its derivative can use what is generally marketed suitably. For example, L-ascorbic acid (Takeda Pharmaceutical, Fuso Chemical, BASF Japan, Daiichi Pharmaceutical, etc.), L-ascorbic acid Na (Takeda Pharmaceutical, Fuso Chemical, BASF Japan, Daiichi Pharmaceutical, etc.), Ascorbic acid 2-glucoside (Product name: AA-2G: Hayashibara Biochemical Research Institute), Mg as L-ascorbate phosphate (Product name: Ascorbic acid PM “SDK” (Showa Denko), Product name: NIKKOL VC-PMG (Nikko Chemicals), Product name: Seamate (Takeda) Pharmaceutical industry)) and the like.
アスコルビン酸又はその誘導体は、水性組成物としたときにカロテノイドの褪色を抑制すると共にエマルジョン粒子の分散性を維持できる量で水性組成物に存在していればよい。このため、アスコルビン酸又はその誘導体の量は、カロテノイド類の分解防止の観点から水性組成物全体の質量に対して、0.1質量%〜10質量%未満、好ましくは0.5質量%〜5質量%以下とすることができる。 Ascorbic acid or a derivative thereof may be present in the aqueous composition in an amount capable of suppressing the discoloration of the carotenoid and maintaining the dispersibility of the emulsion particles in the aqueous composition. For this reason, the amount of ascorbic acid or a derivative thereof is 0.1% by mass to less than 10% by mass, preferably 0.5% by mass to 5% with respect to the total mass of the aqueous composition from the viewpoint of preventing the decomposition of carotenoids. It can be made into the mass% or less.
本発明にかかる水性組成物には、カロテノイド含有油溶性成分以外の上述した油溶性成分を含んでいてもよい。カロテノイド含有油溶性成分以外の油溶性成分を含有する場合、これらの油溶性成分は、分散組成物全体の質量に対して20質量%以下であることが好ましく、5質量%以下であることが特に好ましい。分散組成物中に20質量%以下の量であれば、油相と水相の分離を抑えることが容易なため、好ましい。 The aqueous composition according to the present invention may contain the oil-soluble component described above other than the carotenoid-containing oil-soluble component. When the oil-soluble component other than the carotenoid-containing oil-soluble component is contained, the oil-soluble component is preferably 20% by mass or less, particularly preferably 5% by mass or less, based on the total mass of the dispersion composition. preferable. An amount of 20% by mass or less in the dispersion composition is preferable because it is easy to suppress separation of the oil phase and the aqueous phase.
本発明にかかる水性組成物には、水性基材として、グリセリン、PG(プロピレングリコール)、BG(1,3−ブチレングリコール)、ペンチレングリコールなどのポリオール類を含むことができる。
また、粒子の安定化剤などとして、種々の水溶性高分子化合物や水分散性微粒子を含むことができる。
水溶性高分子化合物としては、広く合成高分子、天然高分子、半合成高分子のいずれも用いることができ、中でも、カロテノイド含有油溶性成分などを良好に安定化させることができる観点から、特に糖類、タンパク質類およびそれらの複合体が好ましい。
The aqueous composition according to the present invention may contain polyols such as glycerin, PG (propylene glycol), BG (1,3-butylene glycol), and pentylene glycol as an aqueous base material.
In addition, various water-soluble polymer compounds and water-dispersible fine particles can be included as particle stabilizers.
As the water-soluble polymer compound, any of a wide range of synthetic polymers, natural polymers, and semi-synthetic polymers can be used, and in particular, from the viewpoint of satisfactorily stabilizing carotenoid-containing oil-soluble components and the like. Saccharides, proteins and their complexes are preferred.
糖類としては、単糖類、二糖類、オリゴ糖類、多糖類、デキストリン、デンプン誘導体、ガム類、ムコ多糖類、セルロース類等を含むがこれらに限定されるものではない。
これらの中で、代表的なものは、アガロース、アラビノース、アミロース、アミロペクチン、アカシアガム、アラビアガム、アラビノガラクタン、アルキルグリコシド、アルギン酸、アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル、アルドース、イヌリン、オリゴ糖、ガッティガム、カードラン、カラギーナン、ガラクトマンナン、ガラクトース、キサンタンガム、キシロース、キシログルカン、キチン、キトサン、グアーガム、クラスターデキストリン、β−グルカン、グルクロン酸、グリコーゲン、グリコサミノグリカン、グリセルアルデヒド、グルコサミン、グルコース、グルコマンナン、ケトース、コンドロイチン硫酸、サイリウムシードガム、ジェランガム、シクロデキストリン、スクロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース、メチルセルロース、セロビオース、ソルビトール、デオキシリボース、デキストリン、転化糖、デンプン、大豆多糖類、糖アルコール、糖タンパク質、トラガントガム、トレハロース、ヒアルロン酸、フコース、フルクトース、プルラン、ペクチン、ヘパリン、ヘミセルロース、マルトース、マンニトール、マンナン、ラクトース、リボース等が挙げられるが、これに限定されるものではない。
これらの糖類の中では、粘度増加による分散安定性の観点から多糖類が好ましく、カロテノイド類の安定性の観点から、アラビアガム、プルランなどが更に好ましい。
Examples of saccharides include, but are not limited to, monosaccharides, disaccharides, oligosaccharides, polysaccharides, dextrins, starch derivatives, gums, mucopolysaccharides, and celluloses.
Among these, representative ones are agarose, arabinose, amylose, amylopectin, acacia gum, gum arabic, arabinogalactan, alkylglycoside, alginic acid, sodium alginate, propylene glycol alginate, aldose, inulin, oligosaccharide, gati gum , Curdlan, carrageenan, galactomannan, galactose, xanthan gum, xylose, xyloglucan, chitin, chitosan, guar gum, cluster dextrin, β-glucan, glucuronic acid, glycogen, glycosaminoglycan, glyceraldehyde, glucosamine, glucose, gluco Mannan, ketose, chondroitin sulfate, psyllium seed gum, gellan gum, cyclodextrin, sucrose, hydroxyethyl Cellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose, cellobiose, sorbitol, deoxyribose, dextrin, invert sugar, starch, soy polysaccharide, sugar alcohol, glycoprotein, tragacanth gum, trehalose, hyaluronic acid, fucose, fructose, pullulan, pectin, Examples include heparin, hemicellulose, maltose, mannitol, mannan, lactose, and ribose, but are not limited thereto.
Among these saccharides, polysaccharides are preferable from the viewpoint of dispersion stability due to an increase in viscosity, and gum arabic and pullulan are more preferable from the viewpoint of stability of carotenoids.
また、タンパク質類としては、アミノ酸がペプチド結合で重合したポリマー又はオリゴマーであればいかなる種類のものも用いることができるが、より好ましくは天然由来で且つ水溶性のものである。
タンパク質にはアミノ酸からなる単純タンパク質と、アミノ酸以外の構成成分を含む複合タンパク質とがあり、いずれも用いることが出来る。単純タンパク質の例としては、ゼラチン、コラーゲン、カゼイン、フィブロイン、セリシン、ケラチン、プロタミン等が挙げられる。また複合タンパク質としては、炭水化物に結合したタンパク質である糖タンパク質、脂質に結合したタンパク質であるリポタンパク質、金属イオンに結合したタンパク質である金属タンパク質、リボ核酸に結合したタンパク質である核タンパク質、リン酸基に結合したタンパク質であるリンタンパク質等がある。
一方、一般的には、タンパク質原料から呼称される場合も多く、動物性筋肉タンパク質、乳タンパク質、卵タンパク質、米タンパク質、小麦タンパク質(小麦グルテン)、大豆タンパク質、酵母タンパク質、細菌タンパク質等が挙げられる。
なお、このようなタンパク質は、混合物としても使用してもよい。
これらのタンパク質類の中では、分散安定性の観点から、特にゼラチンと水溶性コラーゲンが好ましい。
Any kind of protein can be used as long as it is a polymer or oligomer in which amino acids are polymerized by peptide bonds, but it is preferably naturally derived and water-soluble.
Proteins include simple proteins composed of amino acids and complex proteins containing components other than amino acids, and both can be used. Examples of simple proteins include gelatin, collagen, casein, fibroin, sericin, keratin, protamine and the like. In addition, complex proteins include glycoproteins that bind to carbohydrates, lipoproteins that bind to lipids, metal proteins that bind to metal ions, nucleoproteins that bind to ribonucleic acid, and phosphates. There are phosphoproteins that are proteins bound to groups.
On the other hand, in general, it is often referred to as a protein raw material, and examples include animal muscle protein, milk protein, egg protein, rice protein, wheat protein (wheat gluten), soy protein, yeast protein, and bacterial protein. .
Such proteins may be used as a mixture.
Among these proteins, gelatin and water-soluble collagen are particularly preferable from the viewpoint of dispersion stability.
これらの安定化剤は、油性成分全体に対して任意の割合で添加することができるが、エマルションの安定化のためには、油性成分に対して0.1倍以上100倍以下が好ましく、0.5倍以上50倍以下がより好ましい。 These stabilizers can be added in an arbitrary ratio with respect to the entire oil component, but for stabilization of the emulsion, it is preferably 0.1 to 100 times the oil component, and 0 It is more preferably 5 times or more and 50 times or less.
本発明にかかる水性組成物には、水性組成物について特に上述した成分の以外にも、水分散物に関して記述した事項のうち、水性媒体に対して添加可能な成分として挙げた化合物を同様に含有することができる。この場合には、各成分の量比は、水分散物及び水性組成物それぞれの合計量として、本発明の分散組成物全体に対して、通常用いられる量で使用できればよい。 The aqueous composition according to the present invention contains, in addition to the components specifically described above for the aqueous composition, the compounds mentioned as components that can be added to the aqueous medium among the matters described regarding the aqueous dispersion. can do. In this case, the amount ratio of each component should just be able to be used by the quantity normally used with respect to the whole dispersion composition of this invention as a total amount of each of an aqueous dispersion and an aqueous composition.
本発明の分散組成物は、上記水分散物と水性組成物とを混合することによって得られたものである。
本分散組成物に含まれるエマルジョン粒子の平均粒子径は、透明性保持の観点から200nm以下のものであり、水分散物におけるエマルジョン粒子の粒子径よりも大きくてもよいが、透明性保持及び分散安定性保持の観点から、好ましくは150nm以下、更に好ましくは100nm以下とすることができる。分散組成物におけるエマルジョン粒子の測定方法は、水分散物におけるエマルジョン粒子の測定方法と同様に行うことができる。
The dispersion composition of the present invention is obtained by mixing the aqueous dispersion and the aqueous composition.
The average particle size of the emulsion particles contained in the dispersion composition is 200 nm or less from the viewpoint of maintaining transparency, and may be larger than the particle size of the emulsion particles in the aqueous dispersion. From the viewpoint of maintaining stability, the thickness is preferably 150 nm or less, more preferably 100 nm or less. The method for measuring the emulsion particles in the dispersion composition can be performed in the same manner as the method for measuring the emulsion particles in the aqueous dispersion.
水分散物と水性組成物との混合は、特に限定されず、水分散物が分酸組成物の一部となるように多量の水性組成物に対して少量の水分散物を添加すればよい。
水性組成物に対する水分散物の添加量としては、分散組成物の用途に依存して適宜変更することができるが、分散組成物全体の質量に対して、一般に0.01質量%〜10質量%、水分散物の着色濃度の観点から0.05質量%〜5質量%の配合量となるように水分散物を添加することが好ましく、0.1質量%〜1質量%であることが更に好ましい。
The mixing of the aqueous dispersion and the aqueous composition is not particularly limited, and a small amount of the aqueous dispersion may be added to the large amount of the aqueous composition so that the aqueous dispersion becomes a part of the split acid composition. .
The amount of the aqueous dispersion added to the aqueous composition can be appropriately changed depending on the use of the dispersion composition, but is generally 0.01% by mass to 10% by mass with respect to the total mass of the dispersion composition. From the viewpoint of the coloring concentration of the aqueous dispersion, it is preferable to add the aqueous dispersion so that the blending amount is 0.05% by mass to 5% by mass, and further 0.1% by mass to 1% by mass. preferable.
本発明の分散組成物は、香料を更に含むことができる。本発明の分散組成物には、アスコルビン酸又はその誘導体を水性組成物中に含むので、香料の賦香性を安定させ、カロテノイドからの香りを良好にマスキングすることができる。
本発明で使用可能な香料としては、動物系、植物系、鉱物系の天然香料および合成香料のいずれも使用可能であり、例えば、ローズ抽出エキス、カモミール抽出エキス、グリーンティー香料、ラベンダー油、ゼラニウム油、ジャスミン油、ベルガモット油、ムスク油、イランイラン油、リモネン、リナロール、β−フェニルエチルアルコール、2,6−ノナジエナール、シトラール、シクロペンタデカノン、オイゲノール、ローズオキサイド、インドール、フェニルアセトアルデヒドジメチルアセタール、オーランチオールなどを挙げることができる。これらの香料のうち、カロテノイドの香りに対するマスキング特性と賦香性の観点から、ローズ抽出エキス、カモミール抽出エキス、グリーンティー香料が特に好ましい。
これらの香料は、本発明の分散組成物中に配合してもよいが、分散安定性の観点から好ましくは水性組成物に配合することが好ましい。この場合には、水性組成物において、水分散物の添加質量に対して1質量%〜50質量%、香りの強さの観点から好ましくは5質量%〜20質量%の配合量とすることができる。
The dispersion composition of the present invention may further contain a fragrance. Since the dispersion composition of the present invention contains ascorbic acid or a derivative thereof in the aqueous composition, it is possible to stabilize the fragrance of the fragrance and mask the scent from the carotenoid.
As the fragrance usable in the present invention, any of animal-based, plant-based, mineral-based natural fragrance and synthetic fragrance can be used. For example, rose extract, chamomile extract, green tea fragrance, lavender oil, geranium Oil, jasmine oil, bergamot oil, musk oil, ylang ylang oil, limonene, linalool, β-phenylethyl alcohol, 2,6-nonadienal, citral, cyclopentadecanone, eugenol, rose oxide, indole, phenylacetaldehyde dimethyl acetal, Examples include auranthiol. Among these fragrances, a rose extract, a chamomile extract, and a green tea fragrance are particularly preferable from the viewpoints of masking properties and aromas for carotenoid fragrance.
Although these fragrance | flavors may be mix | blended in the dispersion composition of this invention, it is preferable to mix | blend with an aqueous composition from a viewpoint of dispersion stability. In this case, in the aqueous composition, the blending amount is preferably 1% by mass to 50% by mass and preferably 5% by mass to 20% by mass with respect to the added mass of the aqueous dispersion. it can.
本発明の分散組成物は、上述したように、カロテノイド含有油溶性成分及びリン脂質又はその誘導体と、水相とを混合して、エマルジョン粒子を有する水分散物を得ること、前記水分散物と、アスコルビン酸又はその誘導体及び、分散組成物全体の質量に対して20質量%以下の油状成分を含む水性組成物とを混合すること、を含む製造方法によって得ることができる。
このように水分散物を得るための混合と、得られた水分散物と上記水性組成物との混合という二段階の混合工程を経ることによって、カロテノイド油溶性成分と、アスコルビン酸又はその誘導体とを特に含み、平均粒子径200nm以下のエマルジョン粒子が分散した保存安定性に優れた分散組成物を容易に得ることができる。
As described above, the dispersion composition of the present invention mixes a carotenoid-containing oil-soluble component and a phospholipid or derivative thereof with an aqueous phase to obtain an aqueous dispersion having emulsion particles, and the aqueous dispersion , Ascorbic acid or a derivative thereof and an aqueous composition containing 20% by mass or less of an oily component based on the total mass of the dispersion composition.
The carotenoid oil-soluble component, ascorbic acid or a derivative thereof are obtained through a two-step mixing process of mixing to obtain an aqueous dispersion and mixing the obtained aqueous dispersion and the aqueous composition. In particular, a dispersion composition excellent in storage stability in which emulsion particles having an average particle diameter of 200 nm or less are dispersed can be easily obtained.
本発明のスキンケア用化粧料は、本発明の分散組成物を含むものである。
上述したように本発明の分散組成物は、アスコルビン酸又はその誘導体とを特に含み、平均粒子径200nm以下のエマルジョン粒子が分散した保存安定性に優れる分散組成物であるので、この分散組成物を含むスキンケア用化粧料も同様に、良好な保存安定性を示すことができる。
本分散組成物と共に使用可能な他の成分には、特に制限はなく、通常、化粧料として配合可能な成分を種類及び配合量に制限なく、そのまま使用することができる。
The skin care cosmetic of the present invention comprises the dispersion composition of the present invention.
As described above, the dispersion composition of the present invention is a dispersion composition that particularly includes ascorbic acid or a derivative thereof and has excellent storage stability in which emulsion particles having an average particle diameter of 200 nm or less are dispersed. The skin care cosmetics to be included can similarly exhibit good storage stability.
There is no restriction | limiting in particular in the other component which can be used with this dispersion composition, Usually, the component which can be mix | blended as cosmetics can be used as it is, without a restriction | limiting in kind and compounding quantity.
以下、本発明を実施例によって説明するが、本発明はこれに限定されるものではない。なお、以下の記載で「部」と「%}表示してあるものは、特に断らない限り質量基準である。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this. In the following description, “parts” and “%}” are based on mass unless otherwise specified.
(1)水分散物(i)−a、(i)−bの作製
下記表1記載の各成分を、70℃で加熱しながら1時間溶解して、水性組成物を得た。
また、下記表2記載の各成分を、70℃で加熱しながら1時間溶解して、油相組成物を得た。
(1) Preparation of aqueous dispersions (i) -a and (i) -b Each component shown in Table 1 below was dissolved for 1 hour while heating at 70 ° C. to obtain an aqueous composition.
Moreover, each component of following Table 2 was melt | dissolved for 1 hour, heating at 70 degreeC, and the oil phase composition was obtained.
水相を70℃に保ったままホモジナイザー(みづほ工業(株)製真空乳化装置PVQ−1D型)で攪拌し(10000rpm)、そこへ上記油相組成物を添加して乳化物を得た。得られた乳化物を、40℃で、アルティマイザーHJP−25005(株式会社スギノマシン社製)を用いて、200MPaの圧力で高圧乳化を行った。
その後、平均孔径1μmのミクロフィルターでろ過して、アスタキサンチン類含有水分散物(i)−aを調製した。
While maintaining the aqueous phase at 70 ° C., the mixture was stirred with a homogenizer (vacuum emulsifier PVQ-1D type manufactured by Mizuho Kogyo Co., Ltd.) (10000 rpm), and the oil phase composition was added thereto to obtain an emulsion. The obtained emulsion was subjected to high-pressure emulsification at 40 ° C. using an optimizer HJP-25005 (manufactured by Sugino Machine Co., Ltd.) at a pressure of 200 MPa.
Then, it filtered with the micro filter with an average hole diameter of 1 micrometer, and prepared astaxanthin containing water dispersion (i) -a.
油相組成物におけるレシチン90gの代わりに、純水90gを加えた以外は同様にして、アスタキサンチン類含有水分散物(i)−bを作製した。 Astaxanthin-containing aqueous dispersion (i) -b was prepared in the same manner except that 90 g of pure water was added instead of 90 g of lecithin in the oil phase composition.
(2)水性組成物(ii)−a〜(ii)−gの作製
下記表3の成分を室温で混合溶解して、水性組成物(ii)−a〜(ii)−gを得た。
(2) Preparation of aqueous compositions (ii) -a to (ii) -g The components in Table 3 below were mixed and dissolved at room temperature to obtain aqueous compositions (ii) -a to (ii) -g.
(3)分散組成物の調製
[実施例1]
上記水性組成物(ii)−a 999.5gに、ヘマトコッカス藻抽出物の水分散物(i)−a 0.5gを添加し、均一に混合し、赤色透明の分散液(A)を得た。
[実施例2]
水性組成物(ii)−a 999gに、ヘマトコッカス藻抽出物の水分散物(i)−a 1gを添加し、均一に混合し、赤色透明の分散液(B)を得た。
[実施例3]
水性組成物(ii)−a 990gに、ヘマトコッカス藻抽出物の水分散物(i)−a 10gを添加し、均一に混合し、赤色透明の分散液(C)を得た。
[実施例4]
水性組成物(ii)−a 980gに、ヘマトコッカス藻抽出物の水分散物(i)−a 20gを添加し、均一に混合し、赤色透明の分散液(D)を得た。
[実施例5]
水性組成物(ii)−b 999gに、ヘマトコッカス藻抽出物の水分散物(i)−a 1gを添加し、均一に混合し、赤色透明の分散液(E)を得た。
(3) Preparation of dispersion composition [Example 1]
0.5 g of an aqueous dispersion (i) -a of Haematococcus alga extract is added to 999.5 g of the aqueous composition (ii) -a and mixed uniformly to obtain a red transparent dispersion (A). It was.
[Example 2]
1 g of an aqueous dispersion (i) -a of Haematococcus alga extract was added to 999 g of the aqueous composition (ii) -a and mixed uniformly to obtain a red transparent dispersion liquid (B).
[Example 3]
10 g of an aqueous dispersion (i) -a of Haematococcus alga extract was added to 990 g of the aqueous composition (ii) -a and mixed uniformly to obtain a red transparent dispersion liquid (C).
[Example 4]
20 g of an aqueous dispersion (i) -a of Haematococcus alga extract was added to 980 g of the aqueous composition (ii) -a, and mixed uniformly to obtain a red transparent dispersion (D).
[Example 5]
1 g of an aqueous dispersion (i) -a of Haematococcus alga extract was added to 999 g of the aqueous composition (ii) -b and mixed uniformly to obtain a red transparent dispersion liquid (E).
[実施例6]
水性組成物(ii)−b 980gに、ヘマトコッカス藻抽出物の水分散物(i)−a20gを添加し、均一に混合し、赤色透明の分散液(F)を得た。
[実施例7]
水性組成物(ii)−c 999gに、ヘマトコッカス藻抽出物の水分散物(i)−a 1gを添加し、均一に混合し、赤色透明の分散液(G)を得た。
[実施例8]
水性組成物(ii)−d 999gに、ヘマトコッカス藻抽出物の水分散物(i)−a 1gを添加し、均一に混合し、赤色透明の分散液(H)を得た。
[実施例9]
水性組成物(ii)−e 999gに、ヘマトコッカス藻抽出物の水分散物(i)−a 1gを添加し、均一に混合し、赤色透明の分散液(I)を得た。
[実施例10]
[Example 6]
Aqueous composition (ii) -b (980 g) was added with Haematococcus alga extract aqueous dispersion (i) -a (20 g) and mixed uniformly to obtain a red transparent dispersion (F).
[Example 7]
1 g of an aqueous dispersion (i) -a of Haematococcus alga extract was added to 999 g of the aqueous composition (ii) -c and mixed uniformly to obtain a red transparent dispersion liquid (G).
[Example 8]
1 g of an aqueous dispersion (i) -a of Haematococcus alga extract was added to 999 g of the aqueous composition (ii) -d and mixed uniformly to obtain a red transparent dispersion liquid (H).
[Example 9]
1 g of an aqueous dispersion (i) -a of Haematococcus alga extract was added to 999 g of the aqueous composition (ii) -e, and mixed uniformly to obtain a red transparent dispersion liquid (I).
[Example 10]
水性組成物(ii)−f 999gに、ヘマトコッカス藻抽出物の水分散物(i)−a 1gを添加し、均一に混合し、赤色透明の分散液(J)を得た。
[比較例1]
水性組成物(ii)−g 999gに、ヘマトコッカス藻抽出物の水分散物(i)−a 1gを添加し、均一に混合し、赤色透明の分散液(K)を得た。
[比較例2]
水性組成物(ii)−a 999gに、ヘマトコッカス藻抽出物の水分散物(i)−b 1gを添加し、均一に混合し、赤色透明の分散液(L)を得た。
1 g of an aqueous dispersion (i) -a of Haematococcus alga extract was added to 999 g of the aqueous composition (ii) -f and mixed uniformly to obtain a red transparent dispersion (J).
[Comparative Example 1]
1 g of an aqueous dispersion (i) -a of Haematococcus alga extract was added to 999 g of the aqueous composition (ii) -g and mixed uniformly to obtain a red transparent dispersion liquid (K).
[Comparative Example 2]
1 g of an aqueous dispersion (i) -b of Hematococcus alga extract was added to 999 g of the aqueous composition (ii) -a, and mixed uniformly to obtain a red transparent dispersion (L).
(4)物性値の測定
上記で得られた水性組成物にヘマトコッカス藻抽出物の水分散物を添加して、均一に混合し、本発明の分散組成物に対応する赤色透明の分散液(A)〜(L)を得た。
得られた分散液(A)〜(L)をそれぞれ遮光容器に充填し、蓋を閉めた後、50℃の恒温槽に入れて経時30日間での分散液の褪色レベル(λmax:478nmでの吸光度変化)、粒子径、目視での性状変化(濁り、析出)を下記のようにして確認した。結果を表4に示す。
(4) Measurement of physical property value An aqueous dispersion of Haematococcus alga extract is added to the aqueous composition obtained above and mixed uniformly, and a red transparent dispersion liquid corresponding to the dispersion composition of the present invention ( A) to (L) were obtained.
Each of the obtained dispersions (A) to (L) was filled into a light-shielding container, the lid was closed, and then placed in a thermostatic bath at 50 ° C., and the discoloration level of the dispersion over a period of 30 days (λmax: at 478 nm) Absorbance change), particle diameter, and visual property change (turbidity, precipitation) were confirmed as follows. The results are shown in Table 4.
吸光度は、UV−VIBLEスペクトルフォトメーターUV−2550(島津製作所製)を使用し、478nmでの吸収スペクトルの測定を行い、吸光度を求めた。評価は、水性組成物と水分散物との混合直後の吸光度に対する50℃経時30日の吸光度から吸光度残存率を分散液の褪色レベルとし、下記の評価基準に基づいて行った。
○:吸光度残存率85%以上
△:吸光度残存率70%以上
×:吸光度残存率70%未満
Absorbance was determined by measuring an absorption spectrum at 478 nm using a UV-VIVE spectrum photometer UV-2550 (manufactured by Shimadzu Corporation). The evaluation was performed based on the following evaluation criteria, using the absorbance remaining rate as the discoloration level of the dispersion from the absorbance at 50 ° C. for 30 days with respect to the absorbance immediately after mixing the aqueous composition and the aqueous dispersion.
○: Absorbance remaining ratio of 85% or more Δ: Absorbance remaining ratio of 70% or more
粒子径は、動的光散乱粒径分散測定装置LB−550(株式会社堀場製作所社製)を使用して、分散液中の乳化物の粒子径を測定した。評価は、水性組成物と水分散物との混合直後と50℃30日経時との粒子径の変化を求め、以下の評価基準に基づいて行った。
○:20nm以下
△:70nm以下
×:70nm超
The particle size of the emulsion in the dispersion was measured using a dynamic light scattering particle size dispersion measuring device LB-550 (manufactured by Horiba, Ltd.). The evaluation was performed based on the following evaluation criteria by determining the change in particle diameter immediately after mixing the aqueous composition and the aqueous dispersion and after 30 days at 50 ° C.
○: 20 nm or less Δ: 70 nm or less ×: Over 70 nm
目視での性状変化は、50℃30日経過後の水性組成物における性状を目視観察して、下記の評価基準によって評価した。
○:混合直後品と見た目の性状変化が認識できない。
△:液に若干濁りが感じられる。
×:激しく濁りが生じている。液が分離している。析出が起こっている。
(加筆をお願い致します。)
The visual property change was evaluated according to the following evaluation criteria by visually observing the properties of the aqueous composition after 30 days at 50 ° C.
○: Appearance change cannot be recognized immediately after mixing.
Δ: Some turbidity is felt in the liquid.
×: Vigorous turbidity occurs. The liquid is separated. Precipitation is occurring.
(Please add it.)
上記の結果より、本発明の実施例にかかる分散液は、乳化直後の平均粒径が小さく、保存経時後でもその粒径にほとんど変化が見られなかった。強制保存経時後のエマルションの目視観察においても、褪色変化や性状変化が小さく、濁りや析出なども認めらなかった。
このように本発明によれば、経時での粒子径、色、性状変化が小さく安定性に優れた水性組成物を供給することができる。
From the above results, the dispersions according to the examples of the present invention had a small average particle size immediately after emulsification, and the particle size hardly changed even after storage. In visual observation of the emulsion after forced storage, the color change and property change were small, and no turbidity or precipitation was observed.
Thus, according to the present invention, it is possible to supply an aqueous composition that is small in particle diameter, color, and property change with time and excellent in stability.
Claims (9)
(b)リン酸アスコルビルマグネシウム、及びリン酸アスコルビルナトリウムから選ばれる少なくとも1種のアスコルビン酸誘導体;並びに、
(c)分散組成物全体の質量に対して20質量%以下の油状成分
を含有する、分散組成物。 (A) Emulsion particles having an average particle size of 200 nm or less containing astaxanthin, polyglycerin fatty acid ester, and phospholipid or a derivative thereof;
(B) at least one ascorbic acid derivative selected from magnesium ascorbyl phosphate and sodium ascorbyl phosphate; and
(C) Oil component of 20% by mass or less based on the mass of the entire dispersion composition
A dispersion composition comprising:
アスタキサンチンを含有するカロテノイド含有油溶性成分、ポリグリセリン脂肪酸エステル及びリン脂質又はその誘導体と、水相とを混合して、エマルジョン粒子を有する水分散物を得ること、
前記水分散物と、リン酸アスコルビルナトリウム及びリン酸アスコルビルマグネシウムから選ばれる少なくとも1種のアスコルビン酸誘導体及び、分散組成物全体の質量に対して20質量%以下の油状成分を含む水性組成物とを混合して、平均粒子径200nm以下のエマルジョン粒子を有する分散組成物を得ること、
を含む分散組成物の製造方法。 It is a manufacturing method of the dispersion composition of any one of Claims 1-5, Comprising :
Mixing an aqueous phase with a carotenoid-containing oil-soluble component containing astaxanthin , polyglycerin fatty acid ester and phospholipid or a derivative thereof, to obtain an aqueous dispersion having emulsion particles,
The aqueous dispersion, an aqueous composition comprising at least one ascorbic acid derivative selected from sodium ascorbyl phosphate and magnesium ascorbyl phosphate, and an oily component of 20% by mass or less based on the total mass of the dispersion composition. Mixing to obtain a dispersion composition having emulsion particles with an average particle size of 200 nm or less,
The manufacturing method of the dispersion composition containing this.
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