JP6095998B2 - Method for producing powdered L-ascorbic acid fatty acid ester preparation - Google Patents
Method for producing powdered L-ascorbic acid fatty acid ester preparation Download PDFInfo
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- JP6095998B2 JP6095998B2 JP2013027576A JP2013027576A JP6095998B2 JP 6095998 B2 JP6095998 B2 JP 6095998B2 JP 2013027576 A JP2013027576 A JP 2013027576A JP 2013027576 A JP2013027576 A JP 2013027576A JP 6095998 B2 JP6095998 B2 JP 6095998B2
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- acid ester
- fatty acid
- oil
- ascorbic acid
- manufactured
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- -1 L-ascorbic acid fatty acid ester Chemical class 0.000 title claims description 172
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- 229960005070 ascorbic acid Drugs 0.000 title claims description 92
- 239000002211 L-ascorbic acid Substances 0.000 title claims description 90
- 235000000069 L-ascorbic acid Nutrition 0.000 title claims description 90
- 238000002360 preparation method Methods 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000000203 mixture Substances 0.000 claims description 67
- 239000000126 substance Substances 0.000 claims description 48
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940119463 sunflower seed extract Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- 229930003802 tocotrienol Natural products 0.000 description 1
- 239000011731 tocotrienol Substances 0.000 description 1
- 235000019148 tocotrienols Nutrition 0.000 description 1
- LADGBHLMCUINGV-UHFFFAOYSA-N tricaprin Chemical compound CCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC LADGBHLMCUINGV-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 239000001717 vitis vinifera seed extract Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 1
Landscapes
- General Preparation And Processing Of Foods (AREA)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Description
本発明は、粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤の製造方法に関する。 The present invention relates to a method for producing a powdered L-ascorbic acid fatty acid ester preparation.
Ｌ−アスコルビン酸脂肪酸エステルは、Ｌ−アスコルビン酸に脂肪酸をエステル結合させたものであり、ビタミンＣ作用、酸化防止作用を有し、且つ親油性なので食用油脂や脂肪を含む食品への栄養強化剤、酸化防止剤等として使用されている。しかし、Ｌ−アスコルビン酸脂肪酸エステルは、水に対する分散性（水分散性）に乏しいため清涼飲料水等の水性食品への使用が困難であった。 L-ascorbic acid fatty acid ester is obtained by esterifying a fatty acid with L-ascorbic acid, has vitamin C action, antioxidant action, and is lipophilic, so it is a nutrient enhancer for foods containing edible fats and fats. It is used as an antioxidant. However, since L-ascorbic acid fatty acid ester is poor in water dispersibility (water dispersibility), it has been difficult to use it in aqueous foods such as soft drinks.
Ｌ−アスコルビン酸脂肪酸エステルの水分散性を高める方法としては、例えば、アスコルビン酸脂肪酸エステル、親水性界面活性剤及び少糖類を配合してなる水分散性アスコルビン酸脂肪酸エステル組成物（特許文献１）、Ｌ−アスコルビン酸の高級脂肪酸エステルをシクロデキストリンに包接させて成る親水性包接複合体（特許文献２）等が知られている。 As a method for enhancing the water dispersibility of L-ascorbic acid fatty acid ester, for example, a water-dispersible ascorbic acid fatty acid ester composition comprising ascorbic acid fatty acid ester, hydrophilic surfactant and oligosaccharide (Patent Document 1). A hydrophilic inclusion complex (Patent Document 2) obtained by inclusion of a higher fatty acid ester of L-ascorbic acid in cyclodextrin is known.
しかし、これらの方法により得られる製剤を水に分散すると、その水分散液中のＬ−アスコルビン酸脂肪酸エステルの平均粒子径は１０〜１５μｍ程度であり十分に微細ではなく、またその粒度分布の形状もピーク値が２つ以上の歪なものであることから、分散状態が良好であるとは言えない。このような分散状態では、Ｌ−アスコルビン酸脂肪酸エステル製剤を分散させた水性食品の保存中等にＬ−アスコルビン酸脂肪酸エステルが析出、沈澱する場合があり、また期待する酸化防止効果等が十分に発揮されているとは言い難い。 However, when the preparation obtained by these methods is dispersed in water, the average particle size of L-ascorbic acid fatty acid ester in the aqueous dispersion is about 10 to 15 μm and is not sufficiently fine, and the shape of the particle size distribution However, since the peak value is two or more distortions, it cannot be said that the dispersion state is good. In such a dispersed state, the L-ascorbic acid fatty acid ester may precipitate and precipitate during storage of the aqueous food in which the L-ascorbic acid fatty acid ester preparation is dispersed. It is hard to say that it is.
本発明は、水に対する分散性が更に改善された粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤の製造方法を提供することを目的とする。 An object of this invention is to provide the manufacturing method of the powdery L-ascorbic-acid fatty-acid ester formulation in which the dispersibility with respect to water was further improved.
本発明者は、上記課題に対して鋭意検討を行った結果、水にＬ−アスコルビン酸脂肪酸エステル、粉末化基材及び油溶性物質を加えて水中油型乳化組成物を調製する際の乳化方法として新規なものを採用することにより上記課題が解決されることを見出し、この知見に基づいて本発明を成すに至った。 As a result of intensive studies on the above problems, the present inventor has added an L-ascorbic acid fatty acid ester, a powdered base material and an oil-soluble substance to water to prepare an oil-in-water emulsion composition. As a result, it has been found that the above-mentioned problems can be solved by adopting a novel one, and the present invention has been made based on this finding.
すなわち、本発明は、下記（１）及び（２）からなっている。
（１）Ｌ−アスコルビン酸脂肪酸エステル、粉末化基材及び油溶性物質を水に加えて乳化し、得られた水中油型乳化組成物を乾燥処理する粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤の製造方法であって、該乳化の方法が以下の方法１〜３のいずれかであることを特徴とする粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤の製造方法。
［方法１］
Ｌ−アスコルビン酸脂肪酸エステル及び粉末化基材を含有する水相に油溶性物質を加えて乳化する。
［方法２］
Ｌ−アスコルビン酸脂肪酸エステル及び粉末化基材のうちいずれか一方を含有する水相に、その他方と油溶性物質とを同時に直接加えて乳化する。
［方法３］
Ｌ−アスコルビン酸脂肪酸エステル、粉末化基材及び油溶性物質を同時に直接水に加えて乳化する。
（２）粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤１００質量％中、Ｌ−アスコルビン酸脂肪酸エステルの含有量が５〜６０質量％、粉末化基材の含有量が２０〜９２．５質量％、油溶性物質の含有量が２．５〜５０質量％となるように調整することを特徴とする前記（１）に記載の粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤の製造方法。
からなっている。
That is, this invention consists of following (1) and (2).
(1) Production of a powdered L-ascorbic acid fatty acid ester preparation in which L-ascorbic acid fatty acid ester, a powdered base material and an oil-soluble substance are added to water to emulsify, and the obtained oil-in-water emulsion composition is dried. It is a method, Comprising: The method of this emulsification is either of the following methods 1-3, The manufacturing method of the powdery L-ascorbic-acid fatty acid ester formulation characterized by the above-mentioned.
[Method 1]
An oil-soluble substance is added to an aqueous phase containing L-ascorbic acid fatty acid ester and a powdered base material and emulsified.
[Method 2]
The other side and the oil-soluble substance are added directly and emulsified simultaneously to an aqueous phase containing either one of L-ascorbic acid fatty acid ester and powdered base material.
[Method 3]
L-ascorbic acid fatty acid ester, powdered base material and oil-soluble substance are simultaneously added directly to water and emulsified.
(2) In 100% by mass of the powdered L-ascorbic acid fatty acid ester preparation, the content of L-ascorbic acid fatty acid ester is 5 to 60% by mass, the content of the powdered substrate is 20 to 92.5% by mass, oil It adjusts so that content of a soluble substance may be 2.5-50 mass%, The manufacturing method of the powdery L-ascorbic-acid fatty acid ester formulation as described in said (1) characterized by the above-mentioned.
It is made up of.
本発明の製造方法により得られる粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤は、その水分散液中のＬ−アスコルビン酸脂肪酸エステルの平均粒子径は１．０μｍ未満となり、水分散性に優れている。
本発明の製造方法により得られる粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤は、水分散性に優れるため、水性食品に添加して好ましく使用できるともに、Ｌ−アスコルビン酸脂肪酸エステルによる酸化防止効果等が水性食品に対して十分に発揮されることが期待できる。
The powdery L-ascorbic acid fatty acid ester preparation obtained by the production method of the present invention has an average particle size of L-ascorbic acid fatty acid ester in the aqueous dispersion of less than 1.0 μm and is excellent in water dispersibility.
Since the powdered L-ascorbic acid fatty acid ester preparation obtained by the production method of the present invention is excellent in water dispersibility, it can be preferably used by adding to an aqueous food, and the antioxidant effect by the L-ascorbic acid fatty acid ester is aqueous. It can be expected to be fully applied to food.
本発明で用いられるＬ−アスコルビン酸脂肪酸エステルとしては、例えばＬ−アスコルビン酸ステアリン酸エステル（食品添加物）及びＬ−アスコルビン酸パルミチン酸エステル（食品添加物）等が挙げられ、相対的に融点が低いこと、また分子量が小さいためビタミンＣ活性が高いことから、Ｌ−アスコルビン酸パルミチン酸エステルが好ましく用いられる。 Examples of the L-ascorbic acid fatty acid ester used in the present invention include L-ascorbic acid stearic acid ester (food additive) and L-ascorbic acid palmitic acid ester (food additive). L-ascorbic acid palmitic acid ester is preferably used because it is low and has a low molecular weight and high vitamin C activity.
本発明で用いられる粉末化基材としては、糖類、増粘多糖類・ガム質、澱粉類等が挙げられる。糖類としては、例えばブドウ糖、果糖、麦芽糖、乳糖、ショ糖、デキストリン、サイクロデキストリン、コーンシロップ等が挙げられる。増粘多糖類・ガム質としては、例えばキサンタンガム、ローカストビーンガム、トラガントガム、アラビアガム、ペクチン等が挙げられる。 Examples of the powdered substrate used in the present invention include saccharides, thickening polysaccharides / gum and starches. Examples of the saccharide include glucose, fructose, maltose, lactose, sucrose, dextrin, cyclodextrin, corn syrup and the like. Examples of thickening polysaccharides and gums include xanthan gum, locust bean gum, tragacanth gum, gum arabic, and pectin.
澱粉類としては、例えば、馬鈴薯澱粉、コーンスターチ、ワキシーコーンスターチ、甘藷澱粉、小麦澱粉、米澱粉、タピオカ澱粉等の天然澱粉又はこれらの加工澱粉（酸分解澱粉、酸化澱粉、酵素分解澱粉、エーテル化、エステル化、架橋化等の澱粉誘導体、湿熱処理澱粉、アルファー化澱粉等）が挙げられる。これらの中でも、天然澱粉及び／又は加工澱粉をアルカリ触媒の存在下に無水アルケニルコハク酸と反応させて得られるアルケニルコハク酸エステル化澱粉が好ましく用いられる。無水アルケニルコハク酸のアルケニルの炭素数は約２〜２２、好ましくは約６〜１４が良く、具体的には、例えばヘキセニル無水コハク酸、オクテニル無水コハク酸、デセニル無水コハク酸、ドデセニル無水コハク酸、テトラデセニル無水コハク酸、ヘキサデセニル無水コハク酸、オクタデセニル無水コハク酸等が挙げられる。 As starches, for example, potato starch, corn starch, waxy corn starch, sweet potato starch, wheat starch, rice starch, tapioca starch and other natural starches or processed starches thereof (acid-decomposed starch, oxidized starch, enzymatically-decomposed starch, etherified, And starch derivatives such as esterification and crosslinking, wet heat-treated starch, pregelatinized starch, etc.). Among these, alkenyl succinic esterified starch obtained by reacting natural starch and / or processed starch with alkenyl succinic anhydride in the presence of an alkali catalyst is preferably used. The number of carbon atoms in the alkenyl succinic anhydride is about 2 to 22, preferably about 6 to 14. Specifically, for example, hexenyl succinic anhydride, octenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, Examples include tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, and octadecenyl succinic anhydride.
また、アルケニルコハク酸エステル化澱粉としては、澱粉とコハク酸のアルケニル誘導体とのエステルであれば特に制限はなく、例えばオクテニルコハク酸エステル化澱粉、デセニルコハク酸エステル化澱粉、ドデセニルコハク酸エステル化澱粉、テトラデセニルコハク酸エステル化澱粉、ヘキサデセニルコハク酸エステル化澱粉及びオクタデセニルコハク酸エステル化澱粉並びにこれら澱粉をα化又は加水分解等の処理をしたものが挙げられる。これらの中でも、とりわけα化オクテニルコハク酸エステル化澱粉又はその塩が好ましい。 The alkenyl succinate esterified starch is not particularly limited as long as it is an ester of starch and an alkenyl derivative of succinic acid. For example, octenyl succinate esterified starch, decenyl succinate esterified starch, dodecenyl succinate esterified starch, tetrade Examples include senyl succinic esterified starch, hexadecenyl succinic esterified starch and octadecenyl succinic esterified starch, and those obtained by subjecting these starches to α-formation or hydrolysis. Among these, pregelatinized octenyl succinate esterified starch or a salt thereof is particularly preferable.
ここで、アルケニルコハク酸エステル化澱粉は、加水分解の度合いにより、また加水分解をする時期、即ちエステル化反応の前か後かにより、水溶液としたときの粘度が異なるため、その粘度により２種類に分類される。即ち、アルケニルコハク酸エステル化澱粉は、１５質量％に調整した水溶液の粘度（以下、単に「粘度」ともいう。）が約１００〜２５０ミリパスカル秒の範囲内であるアルケニルコハク酸エステル化澱粉（以下、「アルケニルコハク酸エステル化澱粉Ａ」という。）と粘度が約５ミリパスカル秒以上約１００ミリパスカル秒未満の範囲内であるアルケニルコハク酸エステル化澱粉（以下、「アルケニルコハク酸エステル化澱粉Ｂ」という。）とに分類される。 Here, alkenyl succinate esterified starch has two types of viscosity depending on the viscosity of the aqueous solution depending on the degree of hydrolysis and the time of hydrolysis, that is, before or after the esterification reaction. are categorized. That is, the alkenyl succinic esterified starch is an alkenyl succinic esterified starch whose viscosity (hereinafter also simply referred to as “viscosity”) adjusted to 15% by mass is within a range of about 100 to 250 millipascal seconds ( Hereinafter, “alkenyl succinate esterified starch A”) and alkenyl succinate esterified starch (hereinafter referred to as “alkenyl succinate esterified starch”) having a viscosity in the range of about 5 millipascal seconds or more and less than about 100 millipascal seconds. B ”)).
アルケニルコハク酸エステル化澱粉Ａとしては、粘度が約１００〜２５０ミリパスカル秒のオクテニルコハク酸エステル化澱粉が好ましい。具体的には、例えば市販品のエヌクリーマー４６（製品名；粘度約２４５ミリパスカル秒；日本エヌエスシー社製）、エマルスターＥＭＳ−１０（製品名；粘度約２０８ミリパスカル秒；松谷化学工業社製）等が挙げられる。また、アルケニルコハク酸エステル化澱粉Ｂとしては、粘度が約５ミリパスカル秒以上約１００ミリパスカル秒未満のオクテニルコハク酸エステル化澱粉が好ましい。具体的には、例えば市販品のカプシュールＳＴ（製品名；粘度約７ミリパスカル秒；日本エヌエスシー社製）、ハイキャップ１００（製品名；粘度約７ミリパスカル秒；日本エヌエスシー社製）、ピュリティガムＢＥ（製品名；粘度約２４ミリパスカル秒；日本エヌエスシー社製）、エマルスター３０Ａ（製品名；粘度約２１ミリパスカル秒；松谷化学工業社製）等が挙げられる。 As the alkenyl succinate esterified starch A, octenyl succinate esterified starch having a viscosity of about 100 to 250 millipascal seconds is preferable. Specifically, for example, commercially available N Creamer 46 (product name; viscosity of about 245 millipascal seconds; manufactured by NSC Japan), Emarstar EMS-10 (product name; viscosity of about 208 millipascal seconds; manufactured by Matsutani Chemical Industry Co., Ltd.) ) And the like. The alkenyl succinic esterified starch B is preferably octenyl succinic esterified starch having a viscosity of about 5 millipascal seconds or more and less than about 100 millipascal seconds. Specifically, for example, commercially available Capsule ST (product name; viscosity of about 7 millipascal seconds; manufactured by NSC Japan), high cap 100 (product name; viscosity of about 7 millipascal seconds; manufactured by NSC Japan) , Purity Gum BE (product name; viscosity of about 24 millipascal seconds; manufactured by NSC Japan), Emulstar 30A (product name; viscosity of about 21 millipascal seconds; manufactured by Matsutani Chemical Industry Co., Ltd.), and the like.
ここで、本発明で言うところの粘度は、第８版食品添加物公定書記載「２８.粘度測定法」の「第２法 回転粘度計法」に基づいて測定される。具体的な測定条件及び操作条件を以下に示す。なお、回転数は想定される粘度に応じて適宜選択される。
［測定方法］
試料を入れた容器中にローターとガードを静かに入れ、試料の液面をローターの液浸マークに一致させる。スイッチを入れてから６０秒経過後の指針の示す目盛を読み取り、この指示値に、使用したローターの種類及び回転数によって定まる換算乗数を乗じて、試料の粘度を算出する。
［操作条件］
測定装置：ブルックフィールド型粘度計
ローター：１号
回転数：６０、３０、１２又は６回転／分のいずれか
測定：回転開始６０秒後
測定温度：２５℃
Here, the viscosity referred to in the present invention is measured based on the “second method rotational viscometer method” of “28. Specific measurement conditions and operation conditions are shown below. The rotation speed is appropriately selected according to the assumed viscosity.
[Measuring method]
Gently place the rotor and guard into the container containing the sample, and align the liquid level of the sample with the immersion mark on the rotor. The scale indicated by the pointer 60 seconds after the switch is turned on is read, and the viscosity of the sample is calculated by multiplying the indicated value by a conversion multiplier determined by the type of rotor used and the number of rotations.
[Operation conditions]
Measuring device: Brookfield viscometer Rotor: No. 1 Rotation speed: 60, 30, 12, or 6 rotations / minute Measurement: 60 seconds after starting rotation Measurement temperature: 25 ° C
上述した粉末化基材は、例えば粉末化基材を含有する水相等の粘度低下、乳化時間の短縮化等の製造時の作業性の向上の観点から、２種又はそれ以上を組合せて用いることが好ましく、中でも、（１）アルケニルコハク酸エステル化澱粉Ａとアルケニルコハク酸エステル化澱粉Ｂとの組合せ、（２）アルケニルコハク酸エステル化澱粉Ａとデキストリンとの組合せ、（３）アルケニルコハク酸エステル化澱粉Ａとアラビアガムとの組合せ、（４）デキストリンとアラビアガムとの組合せ等が特に好ましい。 The above-mentioned powdered base material should be used in combination of two or more types from the viewpoint of improving workability at the time of production, such as viscosity reduction of an aqueous phase containing the powdered base material, shortening of emulsification time, etc. Among them, (1) a combination of alkenyl succinate esterified starch A and alkenyl succinate esterified starch B, (2) a combination of alkenyl succinate esterified starch A and dextrin, (3) alkenyl succinate A combination of modified starch A and gum arabic, (4) a combination of dextrin and gum arabic, etc. are particularly preferred.
ここで、上記（１）〜（４）の２種類の粉末化基材の組合せにおいて、その配合比率（重量比）には特に制限はなく、約１：９９〜約９９：１の任意の比率で使用して良い。 Here, in the combination of the above two types of powdered base materials (1) to (4), the blending ratio (weight ratio) is not particularly limited, and an arbitrary ratio of about 1:99 to about 99: 1. May be used with.
本発明で用いられる油溶性物質としては、水に不溶性又は難溶性でかつ油に溶解し易い物質であれば特に制限はないが、例えば（約０〜３０℃）で液体の物質であることが好ましく、例えばサフラワー油、大豆油、綿実油、コメ油、ナタネ油、オリーブ油等の食用油脂、中鎖脂肪酸ジグリセリド（例えば、カプリル酸ジグリセリド、カプリン酸ジグリセリド等）、中鎖脂肪酸トリグリセリド（例えば、カプリル酸トリグリセリド、カプリン酸トリグリセリド等）、グリセリン酢酸脂肪酸エステル、グリセリン脂肪酸ジエステル、プロピレングリコール脂肪酸ジエステル、ビタミンＡ、ビタミンＤ及びビタミンＥ等が挙げられる。ビタミンＥとしては、例えばｄｌ−α−トコフェロール、ｄ−α−トコフェロール、ｄ−γ−トコフェロール、ｄ−δ−トコフェロール、ミックストコフェロール、トコフェロール酢酸エステル、ｄ−α−トコフェロール酢酸エステル及びトコトリエノール等が挙げられる。また、ビタミンＥとしては、植物油が精製される過程で副生する脱臭留出物（例えば脱臭スカム、脱臭スラッジまたはホットウエル油等）から回収される抽出トコフェロール（ミックストコフェロールともいう）を用いることができる。本発明においては、これら油溶性物質を１種類で用いても良く２種類以上を任意に組合せて用いても良い。 The oil-soluble substance used in the present invention is not particularly limited as long as it is a substance that is insoluble or hardly soluble in water and easily soluble in oil. For example, it may be a liquid substance at (about 0 to 30 ° C.). Preferably, edible oils such as safflower oil, soybean oil, cottonseed oil, rice oil, rapeseed oil, olive oil, medium chain fatty acid diglycerides (for example, caprylic acid diglyceride, capric acid diglyceride), medium chain fatty acid triglycerides (for example, caprylic acid) Triglyceride, capric acid triglyceride, etc.), glycerin acetic acid fatty acid ester, glycerin fatty acid diester, propylene glycol fatty acid diester, vitamin A, vitamin D, vitamin E and the like. Examples of vitamin E include dl-α-tocopherol, d-α-tocopherol, d-γ-tocopherol, d-δ-tocopherol, mixed tocopherol, tocopherol acetate, d-α-tocopherol acetate, and tocotrienol. . Further, as vitamin E, an extracted tocopherol (also referred to as mixed tocopherol) recovered from a deodorized distillate by-produced in the process of refining vegetable oil (for example, deodorized scum, deodorized sludge or hot well oil) is used. it can. In the present invention, these oil-soluble substances may be used alone or in any combination of two or more.
本発明の粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤の製造方法は、Ｌ−アスコルビン酸脂肪酸エステル、粉末化基材及び油溶性物質を水に加えて乳化し、得られた水中油型乳化組成物を乾燥処理する粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤の製造方法であって、該乳化の方法が以下の方法１〜３のいずれかであることを特徴とする。 The method for producing a powdered L-ascorbic acid fatty acid ester preparation of the present invention is obtained by emulsifying an L-ascorbic acid fatty acid ester, a powdered base material and an oil-soluble substance in water, and obtaining the oil-in-water emulsion composition thus obtained. A method for producing a powdery L-ascorbic acid fatty acid ester preparation to be dried, wherein the emulsification method is any one of the following methods 1 to 3.
［方法１］
方法１では、Ｌ−アスコルビン酸脂肪酸エステル及び粉末化基材を含有する水相に油溶性物質を加えて乳化する。具体的には、先ず、約４０〜８０℃、好ましくは約６０〜８０℃に加熱した水にＬ−アスコルビン酸脂肪酸エステル及び粉末化基材を加えて分散・溶解して水相とする。粉末化基材及びＬ−アスコルビン酸脂肪酸エステルを水に加えて分散・溶解する順序については特に制限はなく、これらのうちいずれか一方を水に加えて分散・溶解した後に、これにその他方を加えて分散・溶解しても良く、また、これらを同時に水に加えて分散・溶解しても良い。これらを同時に加える場合において「同時」とは、完全に同一のタイミングでこれらを水に加えることに制限されるものではなく、Ｌ−アスコルビン酸脂肪酸エステル及び粉末化基材を含有する水相を調製するものである限りにおいて、ある程度の時間差は許容される。
続いて、Ｌ−アスコルビン酸脂肪酸エステル及び粉末化基材を含有する水相を攪拌しながら、この中に約１００℃以下、好ましくは約４０〜８０℃に保温された油溶性物質をゆっくり加え、高速回転式分散・乳化機を用いて、回転数約４０００〜２００００ｒｐｍにて、攪拌時間約１０〜６０分間で乳化することにより水中油型乳化組成物を調製することができる。
[Method 1]
In Method 1, an oil-soluble substance is added to an aqueous phase containing an L-ascorbic acid fatty acid ester and a powdered base material and emulsified. Specifically, first, L-ascorbic acid fatty acid ester and a powdered base material are added to water heated to about 40 to 80 ° C., preferably about 60 to 80 ° C., and dispersed and dissolved to form an aqueous phase. The order of adding and dispersing / dissolving the powdered base material and L-ascorbic acid fatty acid ester in water is not particularly limited, and after adding or dispersing one of these in water, the other is added to this. In addition, they may be dispersed and dissolved, or these may be added to water at the same time to be dispersed and dissolved. In the case of adding these simultaneously, “simultaneously” is not limited to adding them to water at exactly the same timing, but preparing an aqueous phase containing L-ascorbic acid fatty acid ester and a powdered base material. As long as it does, some time difference is allowed.
Subsequently, while stirring the aqueous phase containing L-ascorbic acid fatty acid ester and the powdered base material, an oil-soluble substance kept at a temperature of about 100 ° C. or lower, preferably about 40 to 80 ° C., is slowly added thereto, An oil-in-water emulsion composition can be prepared by emulsifying using a high-speed rotating dispersion / emulsifier at a rotational speed of about 4000 to 20000 rpm and a stirring time of about 10 to 60 minutes.
［方法２］
方法２では、Ｌ−アスコルビン酸脂肪酸エステル及び粉末化基材のうちいずれか一方を含有する水相に、その他方と油溶性物質とを同時に直接加えて乳化する。具体的には、先ず、Ｌ−アスコルビン酸脂肪酸エステル及び粉末化基材のうちいずれか一方を、約４０〜８０℃、好ましくは約６０〜８０℃に加熱した水に加えて分散・溶解し、水相とする。その後、得られた水相に、その他方及び約１００℃以下、好ましくは約４０〜８０℃に保温された油溶性物質を同時に加え、高速回転式分散・乳化機を用いて、回転数約４０００〜２００００ｒｐｍにて、攪拌時間約１０〜６０分間で乳化することにより水中油型乳化組成物を調製することができる。
ここで、上記他方及び油溶性物質を同時に水相に加えて乳化する場合において「同時」とは、完全に同一のタイミングでこれらを水相に加えることに制限されるものではなく、これらを別個に水相に加えて溶解又は分散するものではない限りにおいて、ある程度の時間差は許容される。
また、方法２において「直接」とは、Ｌ−アスコルビン酸脂肪酸エステルを油溶性物質に溶解したものを水相に加えることは、方法２から除外する意味である。
[Method 2]
In Method 2, the other side and the oil-soluble substance are added directly and emulsified simultaneously to an aqueous phase containing one of L-ascorbic acid fatty acid ester and powdered base material. Specifically, first, either L-ascorbic acid fatty acid ester or powdered base material is dispersed and dissolved in water heated to about 40 to 80 ° C., preferably about 60 to 80 ° C., Let it be an aqueous phase. Thereafter, the other phase and an oil-soluble substance kept at about 100 ° C. or lower, preferably about 40 to 80 ° C., are simultaneously added to the obtained aqueous phase, and the rotational speed is about 4000 using a high-speed rotary dispersion / emulsifier. An oil-in-water emulsion composition can be prepared by emulsifying at about 20,000 rpm with a stirring time of about 10 to 60 minutes.
Here, in the case where the other and the oil-soluble substance are added to the aqueous phase and emulsified at the same time, “simultaneous” is not limited to adding them to the aqueous phase at exactly the same timing. As long as it does not dissolve or disperse in addition to the aqueous phase, a certain time difference is allowed.
Further, in the method 2, “directly” means that the addition of the L-ascorbic acid fatty acid ester dissolved in the oil-soluble substance to the aqueous phase is excluded from the method 2.
［方法３］
方法３では、Ｌ−アスコルビン酸脂肪酸エステル、粉末化基材及び油溶性物質を同時に直接水に加えて乳化する。具体的には、約４０〜８０℃、好ましくは約６０〜８０℃に加熱した水に、Ｌ−アスコルビン酸脂肪酸エステル及び粉末化基材並びに約１００℃以下、好ましくは約４０〜８０℃に保温された油溶性物質を同時に加え、高速回転式分散・乳化機を用いて、回転数約４０００〜２００００ｒｐｍにて、攪拌時間約１０〜６０分間で乳化することにより水中油型乳化組成物を調製することができる。
ここで、方法３において「同時」とは、Ｌ−アスコルビン酸脂肪酸エステル、粉末化基材及び油溶性物質を完全に同一のタイミングで水に加えることに制限されるものではなく、これらを別個に水に加えて溶解又は分散するものではない限りにおいて、ある程度の時間差は許容される。
また、方法３において「直接」とは、Ｌ−アスコルビン酸脂肪酸エステルを油溶性物質に溶解したものを水に加えることは、方法３から除外する意味である。
[Method 3]
In Method 3, L-ascorbic acid fatty acid ester, powdered base material and oil-soluble substance are simultaneously added to water and emulsified. Specifically, in water heated to about 40 to 80 ° C., preferably about 60 to 80 ° C., L-ascorbic acid fatty acid ester and powdered base material and about 100 ° C. or less, preferably about 40 to 80 ° C. An oil-in-water emulsion composition is prepared by simultaneously adding the oil-soluble substance and emulsifying with a high-speed rotary dispersion / emulsifier at a rotational speed of about 4000 to 20000 rpm and a stirring time of about 10 to 60 minutes. be able to.
Here, in the method 3, “simultaneous” is not limited to adding L-ascorbic acid fatty acid ester, powdered base material and oil-soluble substance to water at the same timing, but separately Some time difference is acceptable as long as it does not dissolve or disperse in addition to water.
Further, in the method 3, “directly” means that adding L-ascorbic acid fatty acid ester dissolved in water to water is excluded from the method 3.
上記１〜３の方法を実施することにより、水中油型乳化組成物中のＬ−アスコルビン酸脂肪酸エステルの平均粒子径は約１．０μｍ未満に微細化されるため、該水中油型乳化組成物中に分散するＬ−アスコルビン酸脂肪酸エステルの含有量を安定に高めることが可能になる。これにより、該水中油型乳化組成物を乾燥して得られる粉末状の製剤中のＬ−アスコルビン酸脂肪酸エステルの含有量を高めることが可能となる。さらに、該製剤は、水に対する分散性が高く、これを水に分散させて得られる水分散液中のＬ−アスコルビン酸脂肪酸エステルの平均粒子径も同様に微細なものとなる。 Since the average particle size of the L-ascorbic acid fatty acid ester in the oil-in-water emulsion composition is refined to less than about 1.0 μm by carrying out the above methods 1 to 3, the oil-in-water emulsion composition The content of the L-ascorbic acid fatty acid ester dispersed therein can be stably increased. Thereby, it becomes possible to raise content of L-ascorbic-acid fatty acid ester in the powder-form preparation obtained by drying this oil-in-water-type emulsion composition. Further, the preparation is highly dispersible in water, and the average particle size of the L-ascorbic acid fatty acid ester in the aqueous dispersion obtained by dispersing the preparation in water is also fine.
上記水としては、飲用可能なものであれば特に制限はなく、例えば蒸留水、イオン交換樹脂処理水、逆浸透膜処理水及び限外ろ過膜処理水等の精製水、水道水、地下水又は涌水等の天然水並びにアルカリイオン水等が挙げられる。 The water is not particularly limited as long as it is drinkable, for example, purified water such as distilled water, ion exchange resin treated water, reverse osmosis membrane treated water and ultrafiltration membrane treated water, tap water, ground water or brine. And natural water such as alkaline ionized water.
上記水中油型乳化組成物を調製するための装置としては特に限定されず、例えば、攪拌機、加熱用のジャケット及び邪魔板等を備えた通常の攪拌・混合槽を用いることができる。装備する攪拌機としては、ＴＫホモミクサー（プライミクス社製）又はクレアミックス（エムテクニック社製）等の高速回転式分散・乳化機が好ましく用いられる。 The apparatus for preparing the oil-in-water emulsion composition is not particularly limited. For example, a normal stirring / mixing tank equipped with a stirrer, a heating jacket, a baffle plate, and the like can be used. As a stirrer to be equipped, a high-speed rotating dispersion / emulsifier such as TK homomixer (manufactured by PRIMIX Co., Ltd.) or CLEARMIX (manufactured by M Technique Co., Ltd.) is preferably used.
また、これらの装置で乳化した液を、高圧式均質化処理機を使用して、さらに均質化しても良い。ここで高圧式均質化処理機としては、例えばＡＰＶゴーリンホモジナイザー（ＡＰＶ社製）、マイクロフルイダイザー（マイクロフルイデックス社製）、アルティマイザー（スギノマシン社製）又はナノマイザー（大和製罐社製）等を好ましく使用することができる。上記均質化処理機に代えて、例えば超音波乳化機等の均質化処理機を用いても良い。 Moreover, you may further homogenize the liquid emulsified with these apparatuses using a high-pressure type homogenizer. Here, examples of the high-pressure homogenizer include an APV gorin homogenizer (manufactured by APV), a microfluidizer (manufactured by Microfluidics), an optimizer (manufactured by Sugino Machine), or a nanomizer (manufactured by Daiwa Steel). Can be preferably used. Instead of the homogenizer, a homogenizer such as an ultrasonic emulsifier may be used.
上記水中油型乳化組成物１００質量％中には、Ｌ−アスコルビン酸脂肪酸エステルが約１．５〜１８質量％、好ましくは約１．５〜１２質量％、粉末化基材が約６〜２７．８質量％、好ましくは約９〜２７．８質量％、油溶性物質が約０．７５〜１５質量％、好ましくは約１．５〜１２質量％、残余が水となるように調整するのが好ましい。その水の量に特に制限はないが、水中油型乳化組成物の固形分濃度が２０〜６０質量％となるよう調整するのが好ましい。 In 100% by mass of the oil-in-water emulsion composition, L-ascorbic acid fatty acid ester is about 1.5 to 18% by mass, preferably about 1.5 to 12% by mass, and the powdered substrate is about 6 to 27%. 0.8% by mass, preferably about 9-27.8% by mass, oil-soluble substance is adjusted to about 0.75-15% by mass, preferably about 1.5-12% by mass, and the remainder is water. Is preferred. Although there is no restriction | limiting in particular in the quantity of the water, It is preferable to adjust so that the solid content concentration of an oil-in-water type emulsion composition may be 20-60 mass%.
次に、水中油型乳化組成物は乾燥され粉末化される。乾燥方法としては、例えば、噴霧乾燥、ドラム乾燥、ベルト乾燥、真空乾燥あるいは真空凍結乾燥等が挙げられるが、好ましくは噴霧乾燥である。本発明で使用される噴霧乾燥装置に特に制限はなく、噴射式噴霧乾燥装置又は回転円盤式噴霧乾燥装置等公知の装置を使用することができる。また、噴霧乾燥の操作条件に特に制限は無く、例えば、乳化組成物を加圧ノズル式噴霧乾燥装置に供給し、熱風入口温度約１５０〜２７０℃、排気温度約７０〜１３０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより、流動性の良い粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤を得ることができる。得られる粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤の平均粒子径は約２０〜２００μｍ、好ましくは約５０〜１００μｍである。また得られる粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤の乾燥減量は約１０質量％以下、好ましくは約７質量％以下、更に好ましくは約５質量％以下である。 Next, the oil-in-water emulsion composition is dried and powdered. Examples of the drying method include spray drying, drum drying, belt drying, vacuum drying, vacuum freeze drying, and the like, and spray drying is preferable. There is no restriction | limiting in particular in the spray-drying apparatus used by this invention, Well-known apparatuses, such as a spray-type spray-drying apparatus or a rotary disk type spray-drying apparatus, can be used. There are no particular restrictions on the operating conditions for spray drying. For example, the emulsified composition is supplied to a pressure nozzle type spray drying apparatus, and the hot air inlet temperature is about 150 to 270 ° C. and the exhaust temperature is about 70 to 130 ° C. By spray-drying and collecting the dried product with a cyclone, a powdery L-ascorbic acid fatty acid ester preparation with good fluidity can be obtained. The resulting powdery L-ascorbic acid fatty acid ester preparation has an average particle size of about 20 to 200 μm, preferably about 50 to 100 μm. Further, the loss on drying of the obtained powdered L-ascorbic acid fatty acid ester preparation is about 10% by mass or less, preferably about 7% by mass or less, more preferably about 5% by mass or less.
本発明により得られる粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤の好ましい実施態様の一例は、該製剤１００質量％中、Ｌ−アスコルビン酸脂肪酸エステルを約５〜６０質量％、好ましくは約５〜４０質量％、粉末化基材を約２０〜９２．５質量％、好ましくは約３０〜９２．５質量％、油溶性物質を２．５〜５０質量％、好ましくは約５〜４０質量％含む粉末である。 An example of a preferred embodiment of the powdered L-ascorbic acid fatty acid ester preparation obtained by the present invention is about 5 to 60% by mass, preferably about 5 to 40% by mass of L-ascorbic acid fatty acid ester in 100% by mass of the preparation. A powder containing about 20 to 92.5% by mass of a powdered substrate, preferably about 30 to 92.5% by mass, and 2.5 to 50% by mass, preferably about 5 to 40% by mass of an oil-soluble substance. is there.
なお、本発明で得られる粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤中には、本発明の目的・効果を阻害しない範囲で、例えば食品用乳化剤及び酸化防止剤等を加えることができる。 In addition, in the powdery L-ascorbic acid fatty acid ester preparation obtained in the present invention, for example, an emulsifier for food, an antioxidant and the like can be added within a range not inhibiting the purpose and effect of the present invention.
食品用乳化剤としては、グリセリン脂肪酸エステル、ショ糖脂肪酸エステル、ソルビタン脂肪酸エステル、プロピレングリコール脂肪酸エステル、レシチン又はポリオキシエチレンソルビタン脂肪酸エステル等が挙げられる。ここで、グリセリン脂肪酸エステルには、グリセリンと脂肪酸のエステルの外、グリセリン酢酸エステル、グリセリン酢酸脂肪酸エステル、グリセリン乳酸脂肪酸エステル、グリセリンクエン酸脂肪酸エステル、グリセリンコハク酸脂肪酸エステル、グリセリンジアセチル酒石酸脂肪酸エステル、ポリグリセリン脂肪酸エステル及びポリグリセリン縮合リシノール酸エステル等が含まれる。またレシチンには、分別レシチン、酵素分解レシチン及び酵素処理レシチン等が含まれる。 Examples of the emulsifier for food include glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, lecithin or polyoxyethylene sorbitan fatty acid ester. Here, glycerin fatty acid ester includes glycerin and fatty acid ester, glycerin acetate ester, glycerin acetic acid fatty acid ester, glycerin lactic acid fatty acid ester, glycerin citrate fatty acid ester, glycerin succinic acid fatty acid ester, glycerin diacetyl tartaric acid fatty acid ester, poly Examples include glycerin fatty acid ester and polyglycerin condensed ricinoleic acid ester. Lecithin includes fractionated lecithin, enzyme-decomposed lecithin, enzyme-treated lecithin, and the like.
酸化防止剤としては、例えばＬ−アスコルビン酸及びその塩類、カテキン類、酵素処理ルチン、ヒマワリ種子抽出物、ブドウ種子抽出物及び酵素分解リンゴ抽出物等が挙げられる。 Examples of the antioxidant include L-ascorbic acid and salts thereof, catechins, enzyme-treated rutin, sunflower seed extract, grape seed extract, and enzyme-decomposed apple extract.
以下、実施例をもって本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
［実施例１］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解した。
３）上記２）の水相を低速でさらに攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散し、Ｌ−アスコルビン酸パルミチン酸エステル及び粉末化基材を含有する水相とした。
４）上記３）の水相を低速でさらに攪拌しながら、これに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを徐々に加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品１）４６０ｇを得た。得られた粉末の乾燥減量は約２．３質量％であった。
[Example 1]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 96 g) and alkenyl succinic esterified starch B (product name: Purity Gum BE; Nippon NS Co., Ltd.) 234 g were added, and this was stirred and dissolved at low speed for 10 minutes with the same mixer.
3) While further stirring the aqueous phase of 2) at a low speed, 180 g of L-ascorbic acid palmitic acid ester (product name; manufactured by DSM Nutrition Japan) was added thereto. The mixture was stirred and dispersed for a minute to obtain an aqueous phase containing L-ascorbyl palmitate and a powdered substrate.
4) While further stirring the aqueous phase of 3) at a low speed, 90 g of mixed tocopherol (product name: Riken E Oil 600; manufactured by Riken Vitamin Co., Ltd.) previously heated to 60 ° C. as an oil-soluble substance was gradually added thereto. After that, the mixture was stirred and emulsified at 10,000 rpm for 15 minutes with the same mixer to obtain a homogenized liquid that was an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Example Product 1) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.3% by mass.
［実施例２］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散した。
３）上記２）低速でさらに攪拌しながら、粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解し、Ｌ−アスコルビン酸パルミチン酸エステル及び粉末化基材を含有する水相とした。
４）上記３）の水相を低速でさらに攪拌しながら、これに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを徐々に加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品２）４６０ｇを得た。得られた粉末の乾燥減量は約２．２質量％であった。
[Example 2]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring 1) above at a low speed with a TK homomixer (model: MARK 2.5; manufactured by Primix), 180 g of L-ascorbyl palmitate (product name: manufactured by DSM Nutrition Japan) was added thereto. This was stirred and dispersed with the same mixer at low speed for 10 minutes.
3) Above 2) While further stirring at low speed, 96 g of alkenyl succinate esterified starch A (product name: N Creamer 46; manufactured by NSC Japan) and alkenyl succinate esterified starch B (product name) as a powdered base material : Purity Gum BE; manufactured by Nippon SC Co., Ltd.) was added, and this was stirred and dissolved at low speed for 10 minutes with the same mixer to obtain an aqueous phase containing L-ascorbyl palmitate and a powdered substrate.
4) While further stirring the aqueous phase of 3) at a low speed, 90 g of mixed tocopherol (product name: Riken E Oil 600; manufactured by Riken Vitamin Co., Ltd.) previously heated to 60 ° C. as an oil-soluble substance was gradually added thereto. After that, the mixture was stirred and emulsified at 10,000 rpm for 15 minutes with the same mixer to obtain a homogenized liquid that was an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.) 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Example Product 2) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.2% by mass.
［実施例３］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇ並びにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを同時に加え、これを同ミクサーにて低速で１０分間撹拌して分散・溶解し、Ｌ−アスコルビン酸パルミチン酸エステル及び粉末化基材を含有する水相とした。
３）上記２）の水相を低速で攪拌しながら、これに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを徐々に加えた後、これを同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
４）上記３）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品３）４６０ｇ得た。得られた粉末の乾燥減量は約２．３質量％であった。
[Example 3]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 96 g of alkenyl succinate esterified starch B (product name: Purity Gum BE; manufactured by NSC Japan) and 180 g of L-ascorbic acid palmitate ester (product name: manufactured by DSM Nutrition Japan) At the same time, this was stirred at low speed for 10 minutes with the same mixer to disperse and dissolve to obtain an aqueous phase containing L-ascorbyl palmitate and a powdered substrate.
3) While stirring the aqueous phase of 2) at a low speed, 90 g of mixed tocopherol (product name: Riken E Oil 600; manufactured by Riken Vitamin Co., Ltd.), which was preheated to 60 ° C. as an oil-soluble substance, was gradually added thereto. Thereafter, this was stirred and emulsified with the same mixer at 10,000 rpm for 15 minutes to obtain a homogenized liquid which was an oil-in-water emulsion composition.
4) The homogenized liquid of the above 3) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdery L-ascorbic acid fatty acid ester preparation (Example Product 3) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.3% by mass.
［実施例４］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解し、粉末化基材を含有する水相とした。
３）上記２）の水相をさらに低速で攪拌しながら、これに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇ及びＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを同時に加え、これを同ミクサーにて低速で１０分間撹拌し、分散した。
４）上記３）を同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品４）４６０ｇ得た。得られた粉末の乾燥減量は約２．５質量％であった。
[Example 4]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 96 g) and 234 g of alkenyl succinate esterified starch B (product name: Purity Gum BE; manufactured by NSC Japan) were added, and the mixture was stirred and dissolved at low speed for 10 minutes with the same mixer. An aqueous phase containing
3) 90 g of mixed tocopherol (product name: RIKEN E Oil 600; manufactured by Riken Vitamin Co., Ltd.) and L-ascorbine, which were previously heated to 60 ° C. as an oil-soluble substance while stirring the aqueous phase of 2) at a lower speed. 180 g of acid palmitic acid ester (product name; manufactured by DSM Nutrition Japan Co., Ltd.) was added at the same time, and the mixture was stirred at low speed for 10 minutes with the same mixer to disperse.
4) The above 3) was stirred and emulsified with the same mixer at 10,000 rpm for 15 minutes to obtain a homogenized liquid which was an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). Then, 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Example Product 4) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.5% by mass.
［実施例５］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散し、Ｌ−アスコルビン酸パルミチン酸エステルを含有する水相とした。
３）上記２）の水相を低速でさらに攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇ並びに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを同時に加え、これを同ミクサーにて低速で１０分間撹拌し、溶解・分散した。
４）上記３）を同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品５）４６０ｇ得た。得られた粉末の乾燥減量は約２．６質量％であった。
[Example 5]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring 1) above at a low speed with a TK homomixer (model: MARK 2.5; manufactured by Primix), 180 g of L-ascorbyl palmitate (product name: manufactured by DSM Nutrition Japan) was added thereto. This was stirred and dispersed at low speed for 10 minutes with the same mixer to obtain an aqueous phase containing L-ascorbyl palmitate.
3) While further stirring the aqueous phase of 2) at a low speed, 96 g of alkenyl succinate esterified starch A (product name: N Creamer 46; manufactured by NSC Japan) and alkenyl succinate as a powdered substrate 234 g of modified starch B (product name: Purity Gum BE; manufactured by NSC Japan) and 90 g of mixed tocopherol (product name: Riken E Oil 600; manufactured by Riken Vitamin Co., Ltd.) preheated to 60 ° C. as an oil-soluble substance are simultaneously added. This was stirred at low speed for 10 minutes with the same mixer to dissolve and disperse.
4) The above 3) was stirred and emulsified with the same mixer at 10,000 rpm for 15 minutes to obtain a homogenized liquid which was an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Example Product 5) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.6% by mass.
［実施例６］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇ、油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇ並びにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを同時に加え、これを同ミクサーにて低速で１０分間撹拌し、溶解・分散した。
３）上記２）を同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
４）上記３）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品６）４６０ｇ得た。得られた粉末の乾燥減量は約２．５質量％であった。
[Example 6]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 96 g and alkenyl succinic esterified starch B (product name: Purity Gum BE; manufactured by NSC Japan) 234 g, mixed tocopherol (product name: RIKEN E Oil 600) preheated to 60 ° C. as an oil-soluble substance 90 g of Riken Vitamin Co., Ltd.) and 180 g of L-ascorbic acid palmitate ester (product name; DSM Nutrition Japan Co., Ltd.) were added at the same time, and the mixture was stirred at low speed for 10 minutes with the same mixer to dissolve and disperse.
3) The above 2) was stirred and emulsified with the same mixer at 10,000 rpm for 15 minutes to obtain a homogenized liquid which was an oil-in-water emulsion composition.
4) The homogenized liquid of the above 3) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). Then, 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Example Product 6) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.5% by mass.
［実施例７］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解した。
３）上記２）の水相を低速でさらに攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散し、Ｌ−アスコルビン酸パルミチン酸エステル及び粉末化基材を含有する水相とした。
４）上記３）の水相を低速でさらに攪拌しながら、これに油溶性物質として予め６０℃に加温したナタネ油（ボーソー油脂社製）９０ｇを徐々に加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品７）４６０ｇを得た。得られた粉末の乾燥減量は約２．５質量％であった。
[Example 7]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 96 g) and alkenyl succinic esterified starch B (product name: Purity Gum BE; Nippon NS Co., Ltd.) 234 g were added, and this was stirred and dissolved at low speed for 10 minutes with the same mixer.
3) While further stirring the aqueous phase of 2) at a low speed, 180 g of L-ascorbic acid palmitic acid ester (product name; manufactured by DSM Nutrition Japan) was added thereto. The mixture was stirred and dispersed for a minute to obtain an aqueous phase containing L-ascorbyl palmitate and a powdered substrate.
4) While further stirring the aqueous phase of the above 3) at a low speed, 90 g of rapeseed oil (manufactured by Borso Oil & Fats Co., Ltd.) previously heated to 60 ° C. was gradually added as an oil-soluble substance, and then 10000 rpm with the mixer. The mixture was stirred and emulsified for 15 minutes to obtain a homogenized liquid that was an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Example Product 7) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.5% by mass.
［実施例８］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）１５０ｇ及びデキストリン（商品名：パインデックス＃２；松谷化学社製）１２０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解した。
３）上記２）の水相を低速でさらに攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）２４０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散し、Ｌ−アスコルビン酸パルミチン酸エステル及び粉末化基材を含有する水相とした。
４）上記３）の水相を低速でさらに攪拌しながら、これに油溶性物質として予め６０℃に加温した中鎖脂肪酸トリグリセリド（製品名；アクターＭ１；理研ビタミン社製）９０ｇを徐々に加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品８）４６０ｇを得た。得られた粉末の乾燥減量は約２．４質量％であった。
[Example 8]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 150 g of a product manufactured by Cee Co., Ltd. and 120 g of dextrin (trade name: Paindex # 2; manufactured by Matsutani Chemical Co., Ltd.) were added, and this was stirred and dissolved at low speed for 10 minutes with the same mixer.
3) While further stirring the aqueous phase of 2) at a low speed, 240 g of L-ascorbic acid palmitic acid ester (product name; manufactured by DSM Nutrition Japan) was added thereto. The mixture was stirred and dispersed for a minute to obtain an aqueous phase containing L-ascorbyl palmitate and a powdered substrate.
4) While further stirring the aqueous phase of the above 3) at low speed, 90 g of medium chain fatty acid triglyceride (product name; Actor M1; manufactured by Riken Vitamin Co., Ltd.) previously heated to 60 ° C. as an oil-soluble substance was gradually added thereto. After that, the mixture was stirred and emulsified at 10,000 rpm for 15 minutes with the same mixer to obtain a homogenized liquid that was an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). Then, 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Example Product 8) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.4% by mass.
［実施例９］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）１５６ｇ及びアラビアガム（商品名：サンアラビック；三栄薬品貿易社製）２３４ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解した。
３）上記２）を低速でさらに攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散し、Ｌ−アスコルビン酸パルミチン酸エステル及び粉末化基材を含有する水相とした。
４）上記３）の水相を低速でさらに攪拌しながら、これに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）３０ｇを徐々に加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品９）４６０ｇを得た。得られた粉末の乾燥減量は約２．６質量％であった。
[Example 9]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 156 g manufactured by Cee) and 234 g gum arabic (trade name: San Arabic, manufactured by Sanei Pharmaceutical Trading Co., Ltd.) were added, and the mixture was stirred and dissolved at low speed for 10 minutes using the same mixer.
3) While further stirring the above 2) at low speed, 180 g of L-ascorbic acid palmitate ester (product name; manufactured by DSM Nutrition Japan) was added thereto, and this was stirred at low speed for 10 minutes with the same mixer. Dispersed to form an aqueous phase containing L-ascorbic acid palmitate and a powdered substrate.
4) While further stirring the aqueous phase of 3) at a low speed, 30 g of mixed tocopherol (product name: Riken E Oil 600; manufactured by Riken Vitamin Co., Ltd.) previously heated to 60 ° C. as an oil-soluble substance was gradually added. After that, the mixture was stirred and emulsified at 10,000 rpm for 15 minutes with the same mixer to obtain a homogenized liquid that was an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). Then, 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Example Product 9) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.6% by mass.
［実施例１０］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてデキストリン（商品名：パインデックス＃２；松谷化学社製）３０ｇ及びアラビアガム（商品名：サンアラビック；三栄薬品貿易社製）３００ｇ、油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）２４０ｇ並びにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）３０ｇを同時に加え、これを同ミクサーにて低速で１０分間撹拌して溶解・分散した。
３）上記２）を同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
４）上記３）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品１０）４６０ｇ得た。得られた粉末の乾燥減量は約２．７質量％であった。
[Example 10]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring 1) above at a low speed with a TK homomixer (model: MARK 2.5; manufactured by Primix), 30 g of dextrin (trade name: Paindex # 2; manufactured by Matsutani Chemical Co., Ltd.) 300 g of gum arabic (trade name: San Arabic; manufactured by Sanei Pharmaceutical Trading Co., Ltd.), 240 g of mixed tocopherol (product name: Riken E Oil 600; manufactured by Riken Vitamin Co., Ltd.) preheated to 60 ° C. as an oil-soluble substance and L-ascorbic acid 30 g of palmitic acid ester (product name; manufactured by DSM Nutrition Japan Co., Ltd.) was added at the same time, and this was agitated and dispersed at low speed for 10 minutes with the same mixer.
3) The above 2) was stirred and emulsified with the same mixer at 10,000 rpm for 15 minutes to obtain a homogenized liquid which was an oil-in-water emulsion composition.
4) The homogenized liquid of the above 3) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). Then, 460 g of a powdery L-ascorbic acid fatty acid ester preparation (Example Product 10) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.7% by mass.
［比較例１］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解した。
３）上記２）を低速でさらに攪拌しながら、油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散した。
４）上記３）を低速でさらに攪拌しながら、Ｌ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを上記３）に徐々に加えた後、これを同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（比較例品１）を４６０ｇ得た。得られた粉末の乾燥減量は約２．８質量％であった。
[Comparative Example 1]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 96 g) and alkenyl succinic esterified starch B (product name: Purity Gum BE; Nippon NS Co., Ltd.) 234 g were added, and this was stirred and dissolved at low speed for 10 minutes with the same mixer.
3) While further stirring the above 2) at a low speed, 90 g of mixed tocopherol (product name: Riken E Oil 600; manufactured by Riken Vitamin Co., Ltd.) previously heated to 60 ° C. as an oil-soluble substance was added, and this was mixed with the same mixer. Stir and disperse for 10 minutes at low speed.
4) While further stirring the above 3) at a low speed, 180 g of L-ascorbic acid palmitic acid ester (product name; manufactured by DSM Nutrition Japan) was gradually added to the above 3), and this was mixed with the mixer. The mixture was stirred and emulsified at 10,000 rpm for 15 minutes to obtain a homogenized liquid that was an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Comparative Example Product 1) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.8% by mass.
［比較例２］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散した。
３）上記２）を低速でさらに攪拌しながら、これに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散した。
４）上記３）を低速でさらに攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇを加えた後、これを同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（比較例品２）を４６０ｇ得た。得られた粉末の乾燥減量は約３．１質量％であった。
[Comparative Example 2]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring 1) above at a low speed with a TK homomixer (model: MARK 2.5; manufactured by Primix), 180 g of L-ascorbyl palmitate (product name: manufactured by DSM Nutrition Japan) was added thereto. This was stirred and dispersed with the same mixer at low speed for 10 minutes.
3) While further stirring the above 2) at a low speed, 90 g of mixed tocopherol (product name: Riken E Oil 600; manufactured by Riken Vitamin Co., Ltd.) previously heated to 60 ° C. as an oil-soluble substance was added thereto, and this was mixed with the same mixer. And stirred at low speed for 10 minutes.
4) While further stirring the above 3) at a low speed, 96 g of alkenyl succinate esterified starch A (product name: N Creamer 46; manufactured by NSC Japan) and alkenyl succinate esterified starch B as a powdered substrate were added thereto. (Product name: Purity Gum BE; manufactured by NSC Japan) After adding 234 g, the mixture was stirred and emulsified with the same mixer at 10000 rpm for 15 minutes to obtain a homogenized liquid which was an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Comparative Example Product 2) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 3.1% by mass.
［比較例３］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散した。
３）上記２）を低速でさらに攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解した。
４）上記２）を低速でさらに攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（比較例品３）を４６０ｇ得た。得られた粉末の乾燥減量は約３．５質量％であった。
[Comparative Example 3]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) Mix tocopherol (product name: RIKEN E Oil 600; preheated to 60 ° C. as an oil-soluble substance while stirring the above 1) with a TK homomixer (model: MARK2.5; manufactured by Primix) at a low speed. 90 g) (manufactured by Riken Vitamin Co., Ltd.) was added, and this was stirred and dispersed with the same mixer at low speed for 10 minutes.
3) While further stirring the above 2) at a low speed, 96 g of alkenyl succinate esterified starch A (product name: N Creamer 46; manufactured by NSC Japan) and alkenyl succinate esterified starch B as a powdered substrate were added thereto. (Product name: Purity Gum BE; manufactured by NSC Japan) 234 g was added, and this was stirred and dissolved with the same mixer at low speed for 10 minutes.
4) While further stirring the above 2) at low speed, 180 g of L-ascorbic acid palmitic acid ester (product name; manufactured by DSM Nutrition Japan) was added thereto, and then the mixture was stirred at 10,000 rpm for 15 minutes. The mixture was emulsified to obtain a homogenized liquid that is an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdery L-ascorbic acid fatty acid ester preparation (Comparative Example Product 3) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 3.5% by mass.
［比較例４］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散した。
３）上記２）を低速でさらに攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散した。
４）上記３）を低速でさらに攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇを加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（比較例品４）４６０ｇを得た。得られた粉末の乾燥減量は約３．２質量％であった。
[Comparative Example 4]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) Mix tocopherol (product name: RIKEN E Oil 600; preheated to 60 ° C. as an oil-soluble substance while stirring the above 1) with a TK homomixer (model: MARK2.5; manufactured by Primix) at a low speed. 90 g) (manufactured by Riken Vitamin Co., Ltd.) was added, and this was stirred and dispersed with the same mixer at low speed for 10 minutes.
3) While further stirring the above 2) at low speed, 180 g of L-ascorbic acid palmitate ester (product name; manufactured by DSM Nutrition Japan) was added thereto, and this was stirred at low speed for 10 minutes with the same mixer. Distributed.
4) While further stirring the above 3) at a low speed, 96 g of alkenyl succinate esterified starch A (product name: N Creamer 46; manufactured by NSC Japan) and alkenyl succinate esterified starch B as a powdered substrate were added thereto. (Product name: Purity Gum BE; manufactured by NSC Japan) After adding 234 g, the mixture was stirred and emulsified at 10,000 rpm for 15 minutes to obtain a homogenized liquid as an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Comparative Example Product 4) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 3.2% by mass.
［比較例５］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・分散した。
３）上記２）を低速でさらに攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇ並びにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを同時に加え、これを同ミクサーにて低速で１０分間撹拌・溶解した。
４）上記３）を同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（比較例品５）４６０ｇを得た。得られた粉末の乾燥減量は約３．５質量％であった。
[Comparative Example 5]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) Mix tocopherol (product name: RIKEN E Oil 600; preheated to 60 ° C. as an oil-soluble substance while stirring the above 1) with a TK homomixer (model: MARK2.5; manufactured by Primix) at a low speed. 90 g) (manufactured by Riken Vitamin Co., Ltd.) was added, and this was stirred and dispersed with the same mixer at low speed for 10 minutes.
3) While further stirring the above 2) at a low speed, 96 g of alkenyl succinate esterified starch A (product name: N Creamer 46; manufactured by NSC Japan) and alkenyl succinate esterified starch B as a powdered substrate were added thereto. (Product name: Purity Gum BE; manufactured by NSC Japan) 234g and L-ascorbic acid palmitate ester (Product name: manufactured by DSM Nutrition Japan) 180g were added at the same time, and this was mixed at low speed for 10 minutes. Stir and dissolve.
4) The above 3) was stirred and emulsified with the same mixer at 10,000 rpm for 15 minutes to obtain a homogenized liquid which was an oil-in-water emulsion composition.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Comparative Example Product 5) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 3.5% by mass.
［比較例６］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇ並びに油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを同時に加え、これを同ミクサーにて低速で１０分間撹拌して溶解・分散した。
３）上記２）を低速でさらに攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
４）上記３）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（比較例品６）４６０ｇを得た。得られた粉末の乾燥減量は約２．８質量％であった。
[Comparative Example 6]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 96 g and alkenyl succinic esterified starch B (product name: Purity Gum BE; manufactured by NSC Japan) and mixed tocopherol (product name: RIKEN E Oil 600) preheated to 60 ° C. as an oil-soluble substance ; Manufactured by Riken Vitamin Co., Ltd.) was added at the same time and dissolved and dispersed by stirring at low speed for 10 minutes with the same mixer.
3) While further stirring the above 2) at a low speed, 180 g of L-ascorbic acid palmitic acid ester (product name; manufactured by DSM Nutrition Japan) was added thereto, and then the mixture was stirred at 10,000 rpm for 15 minutes. The mixture was emulsified to obtain a homogenized liquid that is an oil-in-water emulsion composition.
4) The homogenized liquid of the above 3) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of powdered L-ascorbic acid fatty acid ester preparation (Comparative Example Product 6) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 2.8% by mass.
［比較例７］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇ及び油溶性物質として予め６０℃に加温したミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇを同時に加え、これを同ミクサーにて低速で１０分間撹拌・分散した。
３）上記２）を低速でさらに撹拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇを加えて混合した後、同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
４）上記３）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（比較例品７）４６０ｇを得た。得られた粉末の乾燥減量は約３．５質量％であった。
[Comparative Example 7]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring 1) above at a low speed with a TK homomixer (model: MARK 2.5; manufactured by Primix), 180 g of L-ascorbic acid palmitate (product name: manufactured by DSM Nutrition Japan) and oil 90 g of mixed tocopherol (product name: Riken E Oil 600; manufactured by Riken Vitamin Co., Ltd.) preheated to 60 ° C. as a soluble substance was added simultaneously, and this was stirred and dispersed at low speed for 10 minutes with the same mixer.
3) While further stirring the above 2) at a low speed, 96 g of alkenyl succinate esterified starch A (product name: N Creamer 46; manufactured by NSC Japan) and alkenyl succinate esterified starch B as a powdered substrate were added thereto. (Product name: Purity Gum BE; manufactured by NSC Japan) 234 g was added and mixed, and then stirred and emulsified with the same mixer at 10000 rpm for 15 minutes to obtain a homogenized liquid which was an oil-in-water emulsion composition.
4) The homogenized liquid of the above 3) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Comparative Example Product 7) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 3.5% by mass.
［比較例８］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）９６ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２３４ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解し、水相とした。
３）油溶性物質であるミックストコフェロール（製品名：理研Ｅオイル６００；理研ビタミン社製）９０ｇにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加え、これを１１０℃にて加熱・混合して溶解し、油相とした。該油相は、１００℃以下になると固化して析出物を多量に生じるため、その前に以下の操作を行った。
４）上記２）の水相を低速でさらに撹拌しながら、これに上記３）の油相を徐々に加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌・乳化し、水中油型乳化組成物である均質化液を得た。
５）上記４）の均質化液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（比較例品８）４６０ｇを得た。得られた粉末の乾燥減量は約３．６質量％であった。
[Comparative Example 8]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 96 g) and alkenyl succinic acid esterified starch B (product name: Purity Gum BE; Nippon NS Co., Ltd.) 234 g was added, and this was stirred and dissolved at low speed for 10 minutes with the same mixer to obtain an aqueous phase. .
3) 90 g of mixed tocopherol (product name: Riken E Oil 600; manufactured by Riken Vitamin Co., Ltd.), which is an oil-soluble substance, is added with 180 g of L-ascorbyl palmitate (product name: manufactured by DSM Nutrition Japan). It melt | dissolved by heating and mixing at 110 degreeC, and was set as the oil phase. Since the oil phase solidifies and produces a large amount of precipitates when the temperature becomes 100 ° C. or lower, the following operation was performed before that.
4) While further stirring the aqueous phase of 2) at a low speed, the oil phase of 3) above was gradually added thereto, and then stirred and emulsified with the same mixer at 10,000 rpm for 15 minutes to obtain an oil-in-water emulsion composition A homogenized liquid was obtained.
5) The homogenized liquid of the above 4) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying device (model: L-8i; Okawara Chemical Co., Ltd.). 460 g of a powdered L-ascorbic acid fatty acid ester preparation (Comparative Example Product 8) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 3.6% by mass.
［比較例９］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）２１０ｇ及びアルケニルコハク酸エステル化澱粉Ｂ（製品名：ピュリティガムＢＥ；日本エヌエスシー社製）２１０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解した。
３）上記２）の水相を低速でさらに攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌し、分散液とした。
５）上記３）の分散液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（比較例品９）４６０ｇを得た。得られた粉末の乾燥減量は約３．４質量％であった。
[Comparative Example 9]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 210 g of CEC) and 210 g of alkenyl succinic esterified starch B (product name: Purity Gum BE; manufactured by NSC Japan) were added, and this was stirred and dissolved at low speed for 10 minutes with the same mixer.
3) While further stirring the aqueous phase of the above 2) at low speed, 180 g of L-ascorbic acid palmitic acid ester (product name; manufactured by DSM Nutrition Japan) was added thereto, and then 15 minutes at 10,000 rpm with the same mixer. Stir for minutes to give a dispersion.
5) The dispersion of the above 3) is spray-dried under the conditions of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying apparatus (model: L-8i; Okawara Chemical Co., Ltd.) 460 g of powdery L-ascorbic acid fatty acid ester preparation (Comparative Example product 9) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 3.4% by mass.
［比較例１０］
１）３Ｌ容ステンレス製ジョッキに水道水１４００ｍＬを入れ８０℃に加温した。
２）上記１）をＴＫホモミクサー（型式：ＭＡＲＫ２．５；プライミクス社製）で低速で攪拌しながら、これに粉末化基材としてアルケニルコハク酸エステル化澱粉Ａ（製品名：エヌクリーマー４６；日本エヌエスシー社製）２１０ｇ及びアラビアガム（商品名：サンアラビック；三栄薬品貿易社製）２１０ｇを加え、これを同ミクサーにて低速で１０分間撹拌・溶解し、水相とした。
３）上記２）の水相を低速でさらに攪拌しながら、これにＬ−アスコルビン酸パルミチン酸エステル（製品名；ＤＳＭニュートリッションジャパン社製）１８０ｇを加えた後、同ミクサーにて１００００ｒｐｍで１５分間攪拌し、分散液とした。
４）上記３）の分散液を、加圧ノズル式噴霧乾燥装置（型式：Ｌ−８ｉ；大川原化工機社）にて、熱風入口温度１７０℃、排気温度８０℃の条件下で噴霧乾燥し、乾燥物をサイクロンで捕集することにより粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（比較例品１０）４６０ｇを得た。得られた粉末の乾燥減量は約３．６質量％であった。
[Comparative Example 10]
1) 1400 mL of tap water was placed in a 3 L stainless steel mug and heated to 80 ° C.
2) While stirring the above 1) with a TK homomixer (model: MARK 2.5; manufactured by Primix) at a low speed, alkenyl succinate esterified starch A (product name: N Creamer 46; Nippon NS) 210 g made by Sea Co., Ltd. and 210 g gum arabic (trade name: San Arabic; made by Sanei Pharmaceutical Co., Ltd.) were added, and this was stirred and dissolved at low speed for 10 minutes with the same mixer to obtain an aqueous phase.
3) While further stirring the aqueous phase of the above 2) at low speed, 180 g of L-ascorbic acid palmitic acid ester (product name; manufactured by DSM Nutrition Japan) was added thereto, and then 15 minutes at 10,000 rpm with the same mixer. Stir for minutes to give a dispersion.
4) The dispersion of the above 3) is spray-dried under a condition of a hot air inlet temperature of 170 ° C. and an exhaust temperature of 80 ° C. in a pressure nozzle type spray drying apparatus (model: L-8i; Okawara Chemical Co., Ltd.) 460 g of powdery L-ascorbic acid fatty acid ester preparation (Comparative Example product 10) was obtained by collecting the dried product with a cyclone. The loss on drying of the obtained powder was about 3.6% by mass.
ここで、上述した実施例１〜１０及び比較例１〜１０の製造方法における乳化方法（即ち、方法１〜３のいずれに該当するか否か）並びにこれら実施例及び比較例で製造した粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品１〜１０及び比較例品１〜１０）の配合組成を表１及び表２に示す。 Here, the emulsification method in the production methods of Examples 1 to 10 and Comparative Examples 1 to 10 described above (that is, whether the method corresponds to any of Methods 1 to 3) and the powder form produced in these Examples and Comparative Examples. Tables 1 and 2 show the composition of L-ascorbic acid fatty acid ester preparations (Example products 1 to 10 and Comparative products 1 to 10).
［評価及び結果］
実施例１〜１０及び比較例１〜１０の製造過程で調整した水中油型乳化組成物の乳化状態並びにこれらにより製造した粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品１〜１０及び比較例品１〜１０）を水に分散して得た水分散液の分散状態（水分散性）を評価した。これら評価では、レーザー回折／分散粒度分布測定機（型式：ＬＡ−９２０；堀場製作所社製）を使用し、粒子径の大きさを体積頻度からメジアン径として算出することにより、上記水中油型乳化組成物及び水分散液について、平均粒子径及び粒度分布を測定した。また、粒度分布は、以下の基準に従い記号化した。結果を表３に示す。
◎：粒度分布は１山でシャープな形状であり、乳化・分散状態は非常に良好
○：粒度分布は１山でやや広がった状態であるが、乳化・分散状態は良好
△：粒度分布は２山であり、乳化・分散状態はやや悪い
×：粒度分布は２山以上の形状であり、乳化・分散状態は非常に悪い
[Evaluation and results]
The emulsified state of the oil-in-water emulsion composition prepared in the production process of Examples 1 to 10 and Comparative Examples 1 to 10, and the powdered L-ascorbic acid fatty acid ester preparations produced by these (Example products 1 to 10 and Comparative Examples) The dispersion state (water dispersibility) of the aqueous dispersion obtained by dispersing the products 1 to 10) in water was evaluated. In these evaluations, a laser diffraction / dispersion particle size distribution analyzer (model: LA-920; manufactured by HORIBA, Ltd.) is used, and the above-mentioned oil-in-water emulsification is performed by calculating the size of the particle diameter from the volume frequency as the median diameter. The average particle size and particle size distribution were measured for the composition and the aqueous dispersion. The particle size distribution was symbolized according to the following criteria. The results are shown in Table 3.
A: The particle size distribution is a sharp shape with one peak, and the emulsified / dispersed state is very good. ○: The particle size distribution is slightly expanded with one peak, but the emulsified / dispersed state is good. Δ: The particle size distribution is 2. It is a mountain and the emulsified / dispersed state is a little bad.
表３の結果から明らかなように、本発明の製造方法（実施例１〜１０）によれば、その製造過程で調整される水中油型乳化組成物中のＬ−アスコルビン酸脂肪酸エステルは非常に微細であり、乳化状態が良好であった。また、本発明の製造方法により得られた粉末状Ｌ−アスコルビン酸脂肪酸エステル製剤（実施例品１〜１０）を水に分散して得た水分散液中のＬ−アスコルビン酸脂肪酸エステルも同様に微細であり、該製剤は水分散性が良好であった。これに対し、比較例１〜１０（比較例品１〜１０）では、いずれの評価項目も本発明のものに比べて劣っていた。以上より、本発明の優れた効果は、水中油型乳化組成物の調製において、特定の乳化方法（即ち、上記方法１〜３）を実施することにより発揮されることが実証された。 As is clear from the results in Table 3, according to the production method of the present invention (Examples 1 to 10), the L-ascorbic acid fatty acid ester in the oil-in-water emulsion composition prepared in the production process is very high. It was fine and the emulsified state was good. Similarly, the L-ascorbic acid fatty acid ester in the aqueous dispersion obtained by dispersing the powdered L-ascorbic acid fatty acid ester preparation (Example products 1 to 10) obtained by the production method of the present invention in water is also the same. It was fine and the formulation had good water dispersibility. On the other hand, in Comparative Examples 1 to 10 (Comparative Examples 1 to 10), all evaluation items were inferior to those of the present invention. From the above, it was demonstrated that the excellent effect of the present invention is exhibited by carrying out a specific emulsification method (that is, the above methods 1 to 3) in the preparation of an oil-in-water emulsion composition.
Claims (2)
［方法１］
Ｌ−アスコルビン酸脂肪酸エステル及び粉末化基材を含有する水相に油溶性物質を加えて乳化する。
［方法２］
Ｌ−アスコルビン酸脂肪酸エステル及び粉末化基材のうちいずれか一方を含有する水相に、その他方と油溶性物質とを同時に直接加えて乳化する（但し、Ｌ−アスコルビン酸脂肪酸エステルを油溶性物質に溶解したものを水相に加えて乳化することを除く）。
［方法３］
Ｌ−アスコルビン酸脂肪酸エステル、粉末化基材及び油溶性物質を同時に直接水に加えて乳化する（但し、Ｌ−アスコルビン酸脂肪酸エステルを油溶性物質に溶解したものを水に加えて乳化することを除く）。 A method for producing a powdered L-ascorbic acid fatty acid ester preparation comprising emulsifying an L-ascorbic acid fatty acid ester, a powdered base material and an oil-soluble substance in water and emulsifying the resulting oil-in-water emulsion composition. And the method of this emulsification is either of the following methods 1-3, The manufacturing method of the powdery L-ascorbic acid fatty acid ester formulation characterized by the above-mentioned.
[Method 1]
An oil-soluble substance is added to an aqueous phase containing L-ascorbic acid fatty acid ester and a powdered base material and emulsified.
[Method 2]
The aqueous phase containing either one of L-ascorbic acid fatty acid ester and powdered base material is added and emulsified by directly adding the other side and the oil-soluble substance simultaneously (however, L-ascorbic acid fatty acid ester is oil-soluble substance) Except for emulsification of the water dissolved in the aqueous phase) .
[Method 3]
L-ascorbic acid fatty acid ester, powdered base material and oil-soluble substance are simultaneously added to water and emulsified simultaneously (however, L-ascorbic acid fatty acid ester dissolved in oil-soluble substance is added to water and emulsified. Except) .
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