JP4582823B2

JP4582823B2 - Aqueous composition comprising oil-soluble substance solubilized or dispersed

Info

Publication number: JP4582823B2
Application number: JP05484796A
Authority: JP
Inventors: 薫塩口; 明文結城
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 1995-03-29
Filing date: 1996-03-12
Publication date: 2010-11-17
Anticipated expiration: 2016-03-12
Also published as: JPH08323189A

Description

【０００１】
【産業上の利用分野】
本発明は、油溶性物質を水性媒体に可溶化ないし分散させてなる組成物に関するものである。さらに詳しくは、例えば、着色料、着香料、ビタミン類、酸化防止剤、保存料、殺菌料または油脂などの油溶性物質が、水性媒体に可溶化ないし分散されてなる組成物に関するものである。
【０００２】
【従来の技術】
従来、化粧品、消臭剤、入浴剤、芳香剤、脱臭剤、食品、医薬などにおいて、常温で液状を呈する各種の商品は、着色料、着香料、ビタミン類、酸化防止剤、保存料、殺菌料または油脂などの油溶性物質を、乳化剤によって、水性媒体に可溶化ないし分散させている。しかし、水性媒体に乳化剤によって可溶化ないし分散させた油溶性物質は、調製過程、または、調製した後の保存および輸送中に、水性媒体から分離してしまうという問題があった。
【０００３】
この様な油水分離を解決するために、従来提案されている方法は、多価アルコールや界面活性剤等を可溶化剤ないし分散剤として添加する方法が多く、その中には実用化されているものもある。提案されている可溶化剤ないし分散剤の代表的な例としては、レシチン、ポリオキシエチレンソルビタンモノオレエート（非イオン性界面活性剤）、硬化ヒマシ油エチレンオキシド付加物、ショ糖脂肪酸エステル等の界面活性剤が挙げられる。
【０００４】
従来の可溶化剤ないし分散剤のうち、レシチンは、天然の卵黄または大豆由来の物質であり、安全性も高いため広く用いられているが、親水性が弱く、水性媒体中に油溶性物質を可溶化ないし分散させる場合には、さらに多価アルコール等の他の水溶性溶媒が必須となるので、最終製品が食品である場合は、味覚の観点から問題があり、また天然由来成分であるため、腐敗・酸敗など安定性に欠けるという欠点もあった。
【０００５】
また、ポリオキシエチレン系非イオン性界面活性剤は、分子鎖中に親水性基としてエチレンオキシド鎖を有しているので、エチレンオキシド鎖が経時的に分解して可溶化力ないし分散力が低下してしまうほか、エチレンオキシドの分解生成物であるホルマリンが溶出するとか、ｐＨが低下するなどの危険があり、食品用途には安全性上の問題から、わが国では認可されておらず、用途に制約がある。
また、ショ糖肪酸エステルは酸性条件下で分解することがあり、低ｐＨの条件下では、充分な可溶化力ないし分散力を発揮できないという問題があった。
【０００６】
さらに、ポリグリセリン脂肪酸エステル（以下、ＰｏＧＥと言うことがある）は、食品添加物として認可されている乳化剤であり、これを用いた可溶化剤ないし分散剤も提案されてきている。しかしながら、提案されているＰｏＧＥを用いた可溶化剤ないし分散剤は、油溶性物質を水性媒体に可溶化ないし分散を行う際に、さらに多価アルコール等の他の添加物を添加する必要があり、経時安定性の低い不飽和脂肪酸を主構成脂肪酸とするなど、食品等へ用いる際の添加物による呈味問題や、商品の流通・保存に影響を及ぼすという問題があった。
【０００７】
さらにまた、従来の可溶化剤ないし分散剤では、油溶性物質を水性媒体に可溶化ないし分散を確実にするためには、可溶化ないし分散操作の際に、原料組成物に、強力な剪断力を与える乳化機や高圧ホモジナイザー等を用いることが必要となる等、製造工程にも問題があった。このため、簡単な操作で、油溶性物質を水性媒体に可溶化ないし分散させることができ、得られた可溶化系ないし分散系は、長期間に亘って安定性を維持し、しかも食品用途の場合には、味覚等に影響を与えない可溶化系ないし分散系の開発が望まれていた。
【０００８】
【発明が解決しようとする課題】
本発明は、従来から存在していた次の諸課題を解決することを目的とする。
１．添加物の種類を少なくしても、かつ、強力な剪断力を与える乳化機や高圧ホモジナイザー等を使用しなくとも調製することができる、油溶性物質が水性媒体に可溶化ないし分散されてなる組成物を提供すること。
２．得られた油溶性物質の可溶化ないし分散されてなる組成物は、長期間に亘って安定性を維持するものであること。
３．しかも、油溶性物質が可溶化ないし分散された組成物が食品用途の場合には、多価アルコールなどの味覚に影響を与えるものを含まなくとも、長期間に亘って安定性を維持する組成物を提供すること。
【０００９】
【課題を解決するための手段】
上記課題を解決するために、請求項１に記載の発明は、油溶性物質（以下Ｂ成分と言う）が、可溶化剤ないし分散剤（以下Ａ成分と言う）によって、水性媒体（以下Ｃ成分と言う）に可溶化ないし分散されてなる水性組成物において、Ａ成分は、その構成脂肪酸の７０重量％以上が炭素数１２〜１４の飽和脂肪酸であり、その構成ポリグリセリンの平均重合度が６〜１２であり、かつ、曇点が２０℃以上であるポリグリセリン飽和脂肪酸エステルよりなり、組成物中のＡ成分とＢ成分との割合が、Ｂ成分１重量部に対し、Ａ成分が１〜１０重量部の範囲で配合されてなることを特徴とする。
【００１０】
以下、本発明を詳細に説明する。
本発明における可溶化剤ないし分散剤（Ａ成分）は、油溶性物質（Ｂ成分）を水性媒体（Ｃ成分）に可溶化ないし分散させる目的で使用されるものであり、このＡ成分は、その構成脂肪酸の７０重量％以上が炭素数１２〜１４の飽和脂肪酸からなり、かつ、曇点が２０℃以上であるポリグリセリン飽和脂肪酸エステルよりなることを必須とする。
【００１１】
なお、本発明にいおて、可溶化ないし分散とは、油溶性物質（Ｂ成分）が水性媒体（Ｃ成分）中で熱力学的安定に可溶化された状態、マイクロエマルジョンの状態、油中水滴型、水中油滴型などの乳化分散状態のように、系が均一相を呈する状態を意味する。
【００１２】
以下、各成分につき詳細に説明する。
Ｂ成分：
Ｂ成分は、それ自体油溶性ではあるが実質的に水溶性でない物質を言い、後記するＡ成分によって、水性媒体に可溶化ないし分散させられて最終製品とされるものである。Ｂ成分は、上記性質を有するものであれば制限はないが、着色料、着香料、ビタミン類、酸化防止剤、保存料、殺菌料または油脂等が挙げられる。
着色料の具体例としては、β−カロチン、アナトー色素、ウコン色素等が挙げられ、着香料の具体例としては、オレンジオイル、メントール等が挙げられ、ビタミン類の具体例としては、ビタミンＡ、ビタミンＢ、ビタミンＥ等が挙げられ、酸化防止剤の具体例としては、ミックストコフェロール、アスコルビン酸ステアリン酸エステル、γ−オリザノール、保存料および殺菌料の具体例としては、デヒドロ酢酸等、油脂類の具体例としては、２−エチルヘキサン酸トリグリセライドのほか、任意の動物油・植物油脂等が挙げられる。
【００１３】
Ａ成分：
Ａ成分は、上記Ｂ成分を、水性媒体に可溶化ないし分散させる機能を果たすものであり、上記要件を満たすポリグリセリン飽和脂肪酸エステル（以下ＰｏＧＥと言う）よりなる。このＰｏＧＥを構成するポリグリセリン（以下ＰｏＧと言う）の平均重合度は、添加物としての安全性の面から平均重合度は６〜１２、特に好ましいのは１０〜１２である。
ＰｏＧＥを製造する際の、脂肪酸とＰｏＧ由来の水酸基とのモル比は、１：６〜１：１００の範囲で選ぶことができる。
【００１４】
本発明者らの実験によれば、ＰｏＧＥの構成脂肪酸の７０重量％以上が炭素数１２〜１４の飽和脂肪酸であることが必要と分かった。これは、構成脂肪酸の炭素数が１２未満であると、可溶化力ないし分散力が低下したり、飲料等の食品に添加した場合には風味が悪くなることがあり、逆に構成脂肪酸の炭素数が１４より大きいと、ｐＨ３以下の酸性条件下で可溶化ないし分散させた際に、安定な可溶化系ないし分散系を形成するのが困難であり、沈澱物等が生ずることがあり、いずれも好ましくない。構成脂肪酸の飽和脂肪酸が７０重量％未満であると、長期間の保存中に風味が悪くなることがあり好ましくない。炭素数が１２〜１４の飽和脂肪酸の具体例としては、ラウリン酸、ミリスチン酸などが挙げられ、これらは単独でも混合物であってもよい。
【００１５】
ＰｏＧＥの構成脂肪酸の炭素数１２〜１４の飽和脂肪酸の割合は、上記範囲の中でも８０重量％以上が好ましく、とりわけ９０重量％以上が好適である。
構成脂肪酸の種類は、ＰｏＧＥを製造する原料を選択する際に、脂肪酸の炭素数、飽和脂肪酸の割合などを、上記範囲にあるものを選択すればよい。
【００１６】
本発明者らの実験によれば、さらに、濃度１０重量％硫酸ナトリウム水溶液におけるＰｏＧＥの曇点が２０℃未満であると、安定な可溶化ないし分散した組成物の形成が困難となり、油溶性物質が分離してしまったり、沈澱物等が生ずることもあることが分かった。
なお、本発明におけるＰｏＧＥの曇点は、次の曇点測定法で求めた。予め調整した濃度１０重量％硫酸ナトリウム水溶液に、ＰｏＧＥ濃度１重量％となるようにＰｏＧＥを混合させてこの混合液をガラス管に封入した。このガラス管を加熱して混合液を均一にした後、所定温度に設定した恒温槽に浸漬し、数分ないし１時間位放置した後にガラス管内の液体の分離の有無を目視観察する方法で行った。
恒温槽の温度を一定の温度きざみで昇温して上の操作を繰り返し、初めて油溶性成分が分離する温度を曇点とした。
【００１７】
上記特性を備えたＰｏＧＥは、炭素数１２〜１４の飽和脂肪酸と、ＰｏＧとを、反応器に仕込み、常圧〜数気圧下、１５０〜３００℃の温度範囲で、触媒の存在下で反応させることによって製造することができる。使用できる触媒としては、水酸化カリウム、水酸化ナトリウムなどのアルカリ類が挙げられ、その使用量は、反応原料の総量に対して０．００１〜０．０２５重量％に範囲で適宜選択することができる。
【００１８】
ＰｏＧＥの曇点は、その合成反応操作条件を選択することにより、容易に調節することができる。例えば、曇点が２０℃よりも低温側にある場合は、ＰｏＧＥに対する脂肪酸のモル数を少なくするか、ＰｏＧＥ製造時のアルカリ触媒が原料脂肪酸と反応して副生する脂肪酸アルカリ塩（石鹸）が曇点を高める傾向にあるのでアルカリ触媒量を多くしたり、または、原料ＰｏＧの平均重合度を高くする等の方法のいずれかを採用することで、曇点を高めることができる。
【００１９】
Ｃ成分：
Ｃ成分は水であり、油溶性物質（Ｂ成分）を可溶化ないし分散させる媒体としての機能を果たす。水は、工業用水を原料とし、脱イオン交換処理によって、陽イオン、陰イオンを除去したものが好ましい。
【００２０】
本発明に係る、油溶性物質（Ｂ成分）が水性媒体（Ｃ成分）に可溶化ないし分散されてなる組成物は、上記の可溶化剤ないし分散剤（Ａ成分）と、Ｂ成分とを、各所定量秤量し、加熱下、攪拌・混合し、これを水性媒体（Ｃ成分）に添加し、油溶性物質を可溶化ないし分散させ、室温に冷却して、容易に調製することが出来る。この際の攪拌は、従来のように強力な機械攪拌を適用することは必須ではなく、振とう攪拌程度で十分である。ただし、強力な剪断力を適用する攪拌を全く排除するものではない。
【００２１】
本発明者らの実験によれば、油溶性物質（Ｂ成分）の種類にもよるが、Ｂ成分１重量部に対し可溶化剤ないし分散剤（Ａ成分）を１〜１０重量部の範囲で選ぶことができる。１重量部未満では、Ｂ成分を可溶化ないし分散化させることが困難であり、１０重量部を越えるときは、添加量を増加してもそれに比例して効果が向上しないので、好ましくない。特に、組成物のｐＨが３未満の場合に、１重量部以上含有させると、本発明の目的が効果的に達成でき、好ましい。組成物のｐＨが３未満の場合に、Ｂ成分１重量部に対するＡ成分の割合を１重量部未満とすると、油溶性物質を可溶化ないし分散する操作を行っても、可溶化系ないし分散系が不安定であるために、油溶性物質（Ｂ成分）が分離したり、特に酸性条件下では沈澱物が生ずる等、油溶性物質が水性媒体に安定に可溶化ないし分散されてなる組成物が得られない。
【００２２】
本発明に係る組成物は、油溶性物質（Ｂ成分）を任意の割合で含有し、中性ではもちろん、Ａ成分の量を調節することにより、ｐＨ２〜５の酸性条件下においても安定であり、Ｂ成分の分離や、沈殿等が生じない可溶化ないし分散された組成物が得られる。一般に、酸性食品のｐＨ値はｐＨ３．３以上であるが、本発明に係る組成物は、このｐＨ以下でも安定である。
全組成物中における、Ｂ成分の配合割合は１０〜１００００ｐｐｍ、特に好ましくは１００〜５０００ｐｐｍであると、ｐＨが５以下の低ｐＨにおいても安定であるので好ましい。
【００２３】
本発明に係る組成物は、Ｃ成分である水性媒体にＡ成分とＢ成分とを混合することを必須とするほか、さらに必要に応じて他の成分を添加・配合することができる。添加・配合することができる他の成分としては、組成物の用途にもよるが、糖類や多価アルコール類等の水溶性添加物、ｐＨ調節剤などであり、具体的にはプロピレングリコール、グリセリン、ソルビトール、キシリトール、アラビトール、マルチトール、ラクチトール、ソルビタン、キシロース、アラビノース、マンノース、乳糖、砂糖、カップリングシュガー、ブドウ糖、酵素糖化水飴、酸糖化水飴、麦芽糖水飴、麦芽糖、異性化糖、果糖、還元麦芽糖水飴、還元澱粉糖水飴、蜂蜜などが挙げられる。また、ｐＨ調節剤としてはクエン酸が挙げられる。これらは、単独でも複数の混合物であってもよい。
全組成物中におけるこれら他の成分の添加・配合量は、製品の用途に応じて適宜選択することができる。
【００２４】
本発明に係る組成物は、化粧品、消臭剤、入浴剤、芳香剤、脱臭剤、食品、医薬などにおいて、常温で液状を呈する各種の用途がある。そして、これら製品は、油溶性物質が分離したり、特に酸性条件下でも沈澱物が生ずることがなく、油溶性物質が水性媒体に安定に可溶化ないし分散されている。
【００２５】
【発明の効果】
本発明は、次のような特別に有利な効果を奏し、その産業上の利用価値は極めて大である。
１．本発明に係る組成物は、油溶性物質を水性媒体に可溶化ないし分散させる際に、添加物の種類を少なくしても、強力な剪断力を与える乳化機や高圧ホモジナイザー等を使用せずに、容易に調製することができる。
２．本発明に係る組成物は、長期間に亘って安定性を維持し、貯蔵中または流通過程にある間に、変質することがない。
３．本発明に係る組成物は、飲料等の食品、医薬品、化粧品等の呈味、香りなどを損なうことがない。
【００２６】
【実施例】
次に、本発明を、製造例、実施例に基づいてさらに詳細に説明するが、本発明はその要旨を越えない限り以下の記載例に限定されるものではない。
なお、以下の製造例において、生成物の曇点は、以下に記載の方法で測定したものであり、以下の製造例、実施例、比較例で使用した原料は、以下の通りである。
【００２７】
＜生成物の曇点測定法＞
予め調整した濃度１０重量％硫酸ナトリウム水溶液に、製造例において得られた反応生成物の濃度が１重量％となるように反応生成物を混合させてこの混合液をガラス管に封入した。このガラス管を加熱して混合液を均一にした後、所定温度に設定した恒温槽に浸漬し、３０分間放置した後にガラス管内の液体の分離の有無を目視観察する方法で行った。恒温槽の温度を５℃きざみで昇温させて上の操作を繰り返し、初めて油溶性成分が分離する温度を曇点とした。
＜使用した試料＞
【００２８】
【表１】

【００２９】
［製造例１］（ＰｏＧＥ−Ａ〜−Ｃの製造例）
攪拌機、温度計、加熱ジャケット、ガス仕込み口、原材料仕込み口を備えた容量２リッターの反応容器に、まず、ポリグリセリン（ＰｏＧ）を１２００ｇ仕込んだ。ついで、同じ反応容器に、ラウリン酸と１０％水酸化ナトリウム水溶液とを仕込んだ。なお、ラウリン酸の仕込み量は、ラウリン酸とＰｏＧのモル比は表−１に示したよう変更した。水酸化ナトリウム量は、ＰｏＧとラウリン酸との総量に対して０．００２５重量％とした。
【００３０】
窒素気流下、常圧で、内温を２４０℃に昇温し、この温度で２．５時間反応させた後、内温をさらに２６０℃に昇温し、この温度で４時間反応させた。反応終了後、内温を常温まで冷却し、液状のポリグリセリンラウリン酸エステル（ＰｏＧＥ）−Ａ〜−Ｃを得た。
得られた反応生成物について、上記方法で曇点を測定した。結果を表−１に示す。
【００３１】
【表２】

【００３２】
［製造例２］（ＰｏＧＥ−Ｄの製造例）
製造例１において使用した反応容器に、まず、ＰｏＧを１２００ｇ仕込んだ。
ついで、同じ反応容器に、ミリスチン酸（ミリスチン酸とＰｏＧのモル比を１に調製した）と、１０％水酸化ナトリウム水溶液（水酸化ナトリウム量を反応原料の総量に対して０．００２５重量％）とを仕込んだ。
【００３３】
製造例１におけると同じ条件で反応させ、ポリグリセリンミリスチン酸エステルを得た。このものを、約５倍量のアセトンに分散・加熱し、デカンテーションして不溶部と可溶部に分離し、減圧乾燥して得たアセトン不溶物をＰｏＧＥ−Ｄと言う。
この不溶物について曇点を測定したところ、９０℃以上であった。
【００３４】
［製造例３］（ＰｏＧＥ−Ｅ、ＰｏＧＥ−Ｆの製造例）
製造例１において使用した反応容器に、まず、ＰｏＧを１２００ｇ仕込んだ。
ついで、同じ反応容器に、パルミチン酸またはステアリン酸（パルミチン酸、ステアリン酸とＰｏＧのモル比は表−２の通りとした。）と１０％水酸化ナトリウム水溶液（同上）とを仕込んだ。
【００３５】
製造例１におけると同じ条件で反応させ、ポリグリセリンパルミチン酸（以下ＰｏＧＥ−Ｅと言う）またはステアリン酸エステル（以下ＰｏＧＥ−Ｆと言う）を得た。
得られた反応生成物について、上記方法で曇点を測定した。結果を表−２に示す。
【００３６】
【表３】

【００３７】
［実施例１］
油溶性物質としてのＤ，Ｌ−α−トコフェロール（ビタミンＥ）｛東京化成（株）製、特級｝２５重量部と、製造例１で製造したＰｏＧＥ−Ａ７５重量部とを秤量し(B成分/A成分=1/3) 、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．２ｇを、クエン酸によってｐＨを３とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、油溶性物質が均一に可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置し、さらに５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００３８】
［実施例２］
ビタミンＥ（実施例１と同種）１５重量部と、ＰｏＧＥ−Ａ８５重量部とを秤量し(B成分/A成分=1/5.7）、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物を、０．０７ｇ、０．１３ｇ、０．３３ｇ、０．６７ｇ、１．３３ｇそれぞれ秤量し、いずれもクエン酸によってｐＨを３とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、いずれの場合も、均一に可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置し、さらに５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００３９】
［実施例３］
ビタミンＥ（実施例１と同種）２０重量部と、ＰｏＧＥ−Ｂ８０重量部とを秤量し(B成分/A成分=1/4）、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．２５ｇを、クエン酸によってｐＨを３とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、均一な可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置し、さらに５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００４０】
［実施例４］
ビタミンＥ（実施例１と同種）２０重量部と、ＰｏＧＥ−Ｄ８０重量部とを秤量し(B成分/A成分=1/4）、６０〜７０℃で攪拌混合して混合物を得た。
この混合物０．２５ｇを、クエン酸によってｐＨを３とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、均一な可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置し、さらに５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００４１】
［実施例５］
油溶性物質としてのオレンジオイル｛協和香料（株）製｝１５重量部と、ＰｏＧＥ−Ａ８５重量部とを秤量し(B成分/A成分=1/5.7）、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．３３ｇを、クエン酸によってｐＨを３とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、均一な可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００４２】
［実施例６］
油溶性物質としての２−エチルヘキサン酸トリグリセライド｛日清製油（株）製｝１０重量部と、ＰｏＧＥ−Ａ９０重量部とを秤量し(B成分/A成分=1/9）、６０〜７０℃で攪拌混合して混合物を得た。
この混合物０．５０ｇを、クエン酸によってｐＨを３とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、均一な可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置し、さらに５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００４３】
［実施例７］
２−エチルヘキサン酸トリグリセライド（実施例６と同種）１０重量部と、ＰｏＧＥ−Ｂ９０重量部とを秤量し(B成分/A成分=1/9）、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．５０ｇを、クエン酸によってｐＨを３とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、均一な可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００４４】
［実施例８］
ビタミンＥ（実施例１と同種）１０重量部と、ＰｏＧＥ−Ａ６０重量部とを秤量し(B成分/A成分=1/6）、さらに特級グリセリン｛キシダ化学（株）製｝を３０重量部加え、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．５０ｇを、クエン酸によってｐＨを３とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、均一な可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置し、さらに５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００４５】
［実施例９］
油溶性物質としてのビタミンＡパルミテート｛理研ビタミン（株）｝７重量部と、ＰｏＧＥ−Ｂ６３重量部とを秤量し(B成分/A成分=1/9）、さらに特級グリセリン（実施例８と同種）を３０重量部加え、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．１４ｇを、クエン酸によってｐＨを３とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、均一な可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００４６】
［実施例１０］
ビタミンＥ（実施例１と同種）４０重量部と、ＰｏＧＥ−Ｂ８０重量部とを秤量し(B成分/A成分=1/2）、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．１５ｇを、クエン酸によってｐＨを４とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、均一な可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置し、さらに５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００４７】
［実施例１１］
２−エチルヘキサン酸トリグリセライド（実施例６と同種）３０重量部と、ＰｏＧＥ−Ｂ４５重量部とを秤量し(B成分/A成分=1/1.5）、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．１３ｇを、クエン酸によってｐＨを５とした、温度２５℃の水１００ｍｌに混合・攪拌したところ、均一な可溶化ないし分散した組成物が得られた。この組成物を２５℃で１ヶ月間静置し、さらに５℃で１ヶ月間静置しても、油水分離や沈澱は生じなかった。
【００４８】
［比較例１］
ビタミンＥ（実施例１と同種）１０重量部と、ＰｏＧＥ−Ｃ（このものの曇点は１０℃である）９０重量部とを秤量し(B成分/A成分=1/9）、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．５ｇを、クエン酸によってｐＨを３とした温度２５℃の水１００ｍｌに混合・攪拌したところ、沈澱を生じ均一な可溶化ないし分散した組成物は得られなかった。
【００４９】
［比較例２］
ビタミンＥ（実施例１と同種）１５重量部と、ＰｏＧＥ−Ｅ（このものの脂肪酸はパルミチン酸である）８５重量部とを秤量し(B成分/A成分=1/5.7）、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．３３ｇを、クエン酸によってｐＨを３とした温度２５℃の水１００ｍｌに混合・攪拌したところ、沈澱を生じ、均一な可溶化ないし分散した組成物は得られなかった。
【００５０】
［比較例３］
ビタミンＥ（実施例１と同種）２０重量部と、ＰｏＧＥ−Ｆ（このものの脂肪酸はステアリン酸である）８０重量部とを秤量し(B成分/A成分=1/4）、６０〜７０℃で混合・攪拌して混合物を得た。
この混合物０．２５ｇを、クエン酸によってｐＨを３とした温度２５℃の水１００ｍｌに混合・攪拌したところ、沈澱を生じ、均一な可溶化ないし分散した組成物は得られなかった。
【００５１】
【表４】

【００５２】
実施例１〜実施例１１、比較例１〜比較例３より、次のことが明らかである。
(1) 本発明に係る油溶性物質が可溶化ないし分散された組成物は、均一な可溶系ないし分散系を形成し、この系は長期間静置しても油水分離や沈澱が生じず安定である（実施例１〜実施例１１参照）。
(2) これに対して、また、ＰｏＧＥの曇点が請求項１の要件を満たさない場合は、組成物には沈殿が生じ、均一な可溶系ないし分散系が形成されない（比較例１参照）。
(3) さらに、ＰｏＧＥを構成する脂肪酸が請求項１の要件を満たさない場合は、組成物には沈殿が生じ、均一な可溶系ないし分散系が形成されない（比較例２〜比較例３参照）。[0001]
[Industrial application fields]
The present invention relates to a composition obtained by solubilizing or dispersing an oil-soluble substance in an aqueous medium. More specifically, for example, the present invention relates to a composition obtained by solubilizing or dispersing an oil-soluble substance such as a coloring agent, a flavoring agent, vitamins, an antioxidant, a preservative, a disinfectant, or an oil and fat in an aqueous medium.
[0002]
[Prior art]
Conventionally, in cosmetics, deodorants, bathing agents, fragrances, deodorants, foods, medicines, etc., various products that are liquid at room temperature include coloring agents, flavoring agents, vitamins, antioxidants, preservatives, and sterilizing agents. An oil-soluble substance such as an oil or fat is solubilized or dispersed in an aqueous medium by an emulsifier. However, the oil-soluble substance solubilized or dispersed in an aqueous medium by an emulsifier has a problem that it is separated from the aqueous medium during the preparation process or during storage and transportation after preparation.
[0003]
In order to solve such oil-water separation, there are many methods that have been proposed in the past, such as adding a polyhydric alcohol, a surfactant or the like as a solubilizing agent or a dispersing agent. There are also things. Typical examples of proposed solubilizers or dispersants include lecithin, polyoxyethylene sorbitan monooleate (nonionic surfactant), hardened castor oil ethylene oxide adduct, sucrose fatty acid ester, and other interfaces. An activator is mentioned.
[0004]
Among conventional solubilizers or dispersants, lecithin is a substance derived from natural egg yolk or soybean, and is widely used because of its high safety. However, it has low hydrophilicity, and oil-soluble substances are contained in aqueous media. In the case of solubilization or dispersion, other water-soluble solvents such as polyhydric alcohol are essential, so if the final product is a food, there is a problem from the viewpoint of taste, and it is a naturally derived component. In addition, there was a drawback of lack of stability such as spoilage and acidity.
[0005]
In addition, since polyoxyethylene-based nonionic surfactants have ethylene oxide chains as hydrophilic groups in the molecular chains, the ethylene oxide chains decompose over time and solubilization power or dispersion power decreases. In addition, there is a risk that formalin, which is a decomposition product of ethylene oxide, elutes or pH is lowered, and food applications are not approved in Japan due to safety issues, and there are restrictions on applications .
In addition, sucrose fatty acid esters may decompose under acidic conditions, and there is a problem that sufficient solubilizing power or dispersing power cannot be exhibited under low pH conditions.
[0006]
Furthermore, polyglycerin fatty acid ester (hereinafter sometimes referred to as PoGE) is an emulsifier approved as a food additive, and a solubilizer or dispersant using the emulsifier has also been proposed. However, the proposed solubilizer or dispersant using PoGE needs to add another additive such as a polyhydric alcohol when solubilizing or dispersing the oil-soluble substance in an aqueous medium. In addition, there are problems such as taste problems due to additives when used in foods and the like, and influence on distribution and storage of products, such as using unsaturated fatty acids with low temporal stability as the main constituent fatty acids.
[0007]
Furthermore, in the conventional solubilizer or dispersant, in order to ensure the solubilization or dispersion of the oil-soluble substance in the aqueous medium, a strong shear force is applied to the raw material composition during the solubilization or dispersion operation. There was also a problem in the production process, such as the necessity of using an emulsifier or high-pressure homogenizer that gave the water. For this reason, the oil-soluble substance can be solubilized or dispersed in an aqueous medium by a simple operation, and the resulting solubilized system or dispersed system maintains stability over a long period of time, and is also suitable for food applications. In some cases, it has been desired to develop a solubilization system or a dispersion system that does not affect the taste.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to solve the following problems that have existed in the past.
1. A composition in which an oil-soluble substance is solubilized or dispersed in an aqueous medium, which can be prepared without using an emulsifier or high-pressure homogenizer that gives a strong shearing force even if the number of additives is reduced. To provide things.
2. The composition obtained by solubilizing or dispersing the obtained oil-soluble substance should maintain stability over a long period of time.
3. In addition, when the composition in which the oil-soluble substance is solubilized or dispersed is used for foods, the composition maintains stability over a long period of time, even if it does not include those that affect the taste such as polyhydric alcohols. To provide.
[0009]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the invention according to claim 1 is characterized in that an oil-soluble substance (hereinafter referred to as component B) is converted into an aqueous medium (hereinafter referred to as component C) by a solubilizing agent or a dispersant (hereinafter referred to as component A). In the aqueous composition solubilized or dispersed in the component A, 70% by weight or more of the constituent fatty acid is a saturated fatty acid having 12 to 14 carbon atoms, and the average degree of polymerization of the constituent polyglycerol is 6 It consists of a polyglycerin saturated fatty acid ester having a cloud point of 20 ° C. or higher, and the ratio of the A component and the B component in the composition is 1 to 1 part by weight of the B component. It is characterized by being blended in the range of 10 parts by weight.
[0010]
Hereinafter, the present invention will be described in detail.
The solubilizer or dispersant (component A) in the present invention is used for the purpose of solubilizing or dispersing an oil-soluble substance (component B) in an aqueous medium (component C). It is essential that 70% by weight or more of the constituent fatty acids consist of a saturated fatty acid ester having 12 to 14 carbon atoms and a cloud point of 20 ° C. or higher.
[0011]
In the present invention, solubilization or dispersion refers to a state in which an oil-soluble substance (component B) is solubilized thermodynamically in an aqueous medium (component C), a state of microemulsion, It means a state in which the system exhibits a uniform phase, such as an emulsified dispersion state such as a water droplet type or an oil-in-water type.
[0012]
Hereinafter, each component will be described in detail.
B component:
The component B is a substance that is itself oil-soluble but not substantially water-soluble, and is solubilized or dispersed in an aqueous medium by the component A described later to be a final product. The component B is not limited as long as it has the above properties, and examples thereof include coloring agents, flavoring agents, vitamins, antioxidants, preservatives, bactericides, and fats and oils.
Specific examples of the colorant include β-carotene, anato dye, turmeric dye, and the like. Specific examples of the flavor include orange oil and menthol. Specific examples of vitamins include vitamin A, Specific examples of antioxidants include mixed tocopherol, ascorbic acid stearate, γ-oryzanol, preservatives and bactericides such as dehydroacetic acid, fats and oils, and the like. Specific examples include 2-ethylhexanoic acid triglyceride and any animal oil / vegetable oil.
[0013]
A component:
The A component serves to solubilize or disperse the B component in an aqueous medium, and is composed of a polyglycerin saturated fatty acid ester (hereinafter referred to as PoGE) that satisfies the above requirements. The average degree of polymerization of polyglycerin (hereinafter referred to as PoG) constituting this PoGE is 6 to 12, particularly preferably 10 to 12, from the viewpoint of safety as an additive.
The molar ratio between the fatty acid and the PoG-derived hydroxyl group when producing PoGE can be selected in the range of 1: 6 to 1: 100.
[0014]
According to the experiments by the present inventors, it was found that 70% by weight or more of the constituent fatty acids of PoGE needs to be saturated fatty acids having 12 to 14 carbon atoms. This is because if the number of carbon atoms of the constituent fatty acid is less than 12, the solubilizing power or dispersibility may be reduced, or the flavor may deteriorate when added to foods such as beverages. When the number is larger than 14, it is difficult to form a stable solubilization system or dispersion when solubilized or dispersed under acidic conditions of pH 3 or less, and precipitates may be formed. Is also not preferable. If the saturated fatty acid of the constituent fatty acid is less than 70% by weight, the flavor may deteriorate during long-term storage, which is not preferred. Specific examples of the saturated fatty acid having 12 to 14 carbon atoms include lauric acid and myristic acid, and these may be used alone or as a mixture.
[0015]
The proportion of the saturated fatty acid having 12 to 14 carbon atoms in the constituent fatty acids of PoGE is preferably 80% by weight or more, and particularly preferably 90% by weight or more, within the above range.
When selecting the raw material which manufactures PoGE, what is necessary is just to select the thing of the carbon number of a fatty acid, the ratio of a saturated fatty acid, etc. in the said range.
[0016]
According to the experiments by the present inventors, when the cloud point of PoGE in a 10% by weight aqueous sodium sulfate solution is less than 20 ° C., it becomes difficult to form a stable solubilized or dispersed composition, resulting in an oil-soluble substance. It has been found that may be separated or precipitates may be formed.
In addition, the cloud point of PoGE in this invention was calculated | required with the following cloud point measuring method. PoGE was mixed with a 10% by weight aqueous sodium sulfate solution prepared in advance so that the PoGE concentration was 1% by weight, and this mixture was sealed in a glass tube. After heating this glass tube to make the mixed solution uniform, it is immersed in a thermostat set to a predetermined temperature and left for several minutes to about 1 hour, followed by a method of visually observing the presence or absence of liquid separation in the glass tube. It was.
The temperature of the thermostatic chamber was raised in steps of a constant temperature, and the above operation was repeated.
[0017]
PoGE having the above-mentioned characteristics is prepared by charging a saturated fatty acid having 12 to 14 carbon atoms and PoG into a reactor and reacting them in the presence of a catalyst in a temperature range of 150 to 300 ° C. under normal pressure to several atmospheres. Can be manufactured. Examples of the catalyst that can be used include alkalis such as potassium hydroxide and sodium hydroxide, and the amount used can be appropriately selected within a range of 0.001 to 0.025% by weight based on the total amount of the reaction raw materials. it can.
[0018]
The cloud point of PoGE can be easily adjusted by selecting the synthetic reaction operating conditions. For example, when the cloud point is lower than 20 ° C., the number of moles of fatty acid with respect to PoGE is reduced, or the alkali catalyst at the time of PoGE production reacts with the raw material fatty acid to produce a fatty acid alkali salt (soap). Since it tends to increase the cloud point, the cloud point can be increased by increasing the amount of alkali catalyst or by adopting any method such as increasing the average degree of polymerization of the raw material PoG.
[0019]
C component:
The component C is water and functions as a medium for solubilizing or dispersing the oil-soluble substance (component B). The water is preferably water from which industrial water is used and from which cations and anions are removed by deionization exchange treatment.
[0020]
According to the present invention, a composition comprising an oil-soluble substance (component B) solubilized or dispersed in an aqueous medium (component C) comprises the above-described solubilizer or dispersant (component A) and component B. Each predetermined amount is weighed, stirred and mixed under heating, added to an aqueous medium (component C), solubilized or dispersed as an oil-soluble substance, and cooled to room temperature to prepare easily. For stirring at this time, it is not essential to apply strong mechanical stirring as in the prior art, and shaking stirring is sufficient. However, this does not completely exclude stirring that applies a strong shearing force.
[0021]
According to the experiments by the present inventors, although depending on the type of oil-soluble substance (component B), the solubilizer or dispersant (component A) is in the range of 1 to 10 parts by weight with respect to 1 part by weight of component B. You can choose. If the amount is less than 1 part by weight, it is difficult to solubilize or disperse the component B. If the amount exceeds 10 parts by weight, the effect is not improved proportionally even if the amount added is increased. In particular, when the pH of the composition is less than 3, it is preferable to contain 1 part by weight or more because the object of the present invention can be effectively achieved. When the pH of the composition is less than 3 and the ratio of the A component to 1 part by weight of the B component is less than 1 part by weight, the solubilization system or dispersion system can be obtained even if the oil-soluble substance is solubilized or dispersed. Is a composition in which an oil-soluble substance is stably solubilized or dispersed in an aqueous medium, such as separation of an oil-soluble substance (component B) or formation of a precipitate under acidic conditions. I can't get it.
[0022]
The composition according to the present invention contains an oil-soluble substance (component B) in an arbitrary ratio, and is not only neutral, but also stable under acidic conditions of pH 2 to 5 by adjusting the amount of component A. Thus, a solubilized or dispersed composition that does not cause separation or precipitation of the B component is obtained. In general, acidic foods have a pH value of 3.3 or higher, but the composition according to the present invention is stable even below this pH.
The blending ratio of the component B in the whole composition is preferably 10 to 10,000 ppm, particularly preferably 100 to 5000 ppm, because it is stable even at a low pH of 5 or less.
[0023]
In the composition according to the present invention, it is essential to mix the A component and the B component in the aqueous medium which is the C component, and other components can be added and blended as necessary. Other components that can be added and blended are water-soluble additives such as sugars and polyhydric alcohols, pH adjusters, etc., depending on the use of the composition, specifically propylene glycol, glycerin , Sorbitol, xylitol, arabitol, maltitol, lactitol, sorbitan, xylose, arabinose, mannose, lactose, sugar, coupling sugar, glucose, enzymatic saccharified starch syrup, acidified starch syrup, maltose starch syrup, maltose, isomerized sugar, fructose, reduced Examples include maltose starch syrup, reduced starch sugar syrup, and honey. Moreover, citric acid is mentioned as a pH adjuster. These may be used singly or as a plurality of mixtures.
The addition and blending amount of these other components in the entire composition can be appropriately selected according to the use of the product.
[0024]
The composition according to the present invention has various uses that are liquid at room temperature in cosmetics, deodorants, bathing agents, fragrances, deodorants, foods, medicines, and the like. In these products, oil-soluble substances are not separated and precipitates are not generated even under acidic conditions, and the oil-soluble substances are stably solubilized or dispersed in an aqueous medium.
[0025]
【The invention's effect】
The present invention has the following particularly advantageous effects, and its industrial utility value is extremely great.
1. When the oil-soluble substance is solubilized or dispersed in an aqueous medium, the composition according to the present invention can be used without using an emulsifier or a high-pressure homogenizer that gives a strong shearing force even if the type of additive is reduced. Can be easily prepared.
2. The composition according to the present invention maintains stability over a long period of time and does not change in quality during storage or during the distribution process.
3. The composition according to the present invention does not impair the taste, aroma and the like of foods such as beverages, pharmaceuticals and cosmetics.
[0026]
【Example】
Next, although this invention is demonstrated further in detail based on a manufacture example and an Example, this invention is not limited to the following description examples, unless the summary is exceeded.
In the following production examples, the cloud point of the product was measured by the method described below, and the raw materials used in the following production examples, examples, and comparative examples are as follows.
[0027]
<Method for measuring cloud point of product>
The reaction product was mixed with a 10% by weight aqueous sodium sulfate solution prepared in advance so that the concentration of the reaction product obtained in the production example was 1% by weight, and this mixture was sealed in a glass tube. This glass tube was heated to make the mixed solution uniform, then immersed in a thermostatic bath set to a predetermined temperature, left for 30 minutes, and then visually observed for the presence or absence of liquid separation in the glass tube. The temperature was raised in steps of 5 ° C. and the above operation was repeated, and the temperature at which the oil-soluble component separated for the first time was taken as the cloud point.
<Sample used>
[0028]
[Table 1]

[0029]
[Production Example 1] (Production Example of PoGE-A to -C)
First, 1200 g of polyglycerin (PoG) was charged into a reaction vessel having a capacity of 2 liters equipped with a stirrer, a thermometer, a heating jacket, a gas charging port, and a raw material charging port. Next, lauric acid and a 10% aqueous sodium hydroxide solution were charged in the same reaction vessel. The amount of lauric acid charged was changed as shown in Table 1 for the molar ratio of lauric acid to PoG. The amount of sodium hydroxide was 0.0025% by weight with respect to the total amount of PoG and lauric acid.
[0030]
The internal temperature was raised to 240 ° C. and normal pressure under a nitrogen stream, and after reacting at this temperature for 2.5 hours, the internal temperature was further raised to 260 ° C. and reacted at this temperature for 4 hours. After completion of the reaction, the internal temperature was cooled to room temperature to obtain liquid polyglycerol laurate (PoGE) -A to -C.
About the obtained reaction product, the cloud point was measured by the said method. The results are shown in Table-1.
[0031]
[Table 2]

[0032]
[Production Example 2] (Production example of PoGE-D)
First, 1200 g of PoG was charged into the reaction vessel used in Production Example 1.
Then, in the same reaction vessel, myristic acid (the molar ratio of myristic acid and PoG was adjusted to 1) and 10% aqueous sodium hydroxide solution (the amount of sodium hydroxide was 0.0025% by weight with respect to the total amount of reaction raw materials) And charged.
[0033]
Reaction was carried out under the same conditions as in Production Example 1 to obtain a polyglycerin myristic acid ester. This product is dispersed and heated in about 5 times the amount of acetone, decanted to separate into an insoluble part and a soluble part, and dried under reduced pressure, which is called PoGE-D.
It was 90 degreeC or more when the cloud point was measured about this insoluble matter.
[0034]
[Production Example 3] (Production Examples of PoGE-E and PoGE-F)
First, 1200 g of PoG was charged into the reaction vessel used in Production Example 1.
Next, palmitic acid or stearic acid (the molar ratio of palmitic acid, stearic acid and PoG was as shown in Table 2) and a 10% aqueous sodium hydroxide solution (same as above) were charged in the same reaction vessel.
[0035]
Reaction was carried out under the same conditions as in Production Example 1 to obtain polyglycerin palmitic acid (hereinafter referred to as PoGE-E) or stearic acid ester (hereinafter referred to as PoGE-F).
About the obtained reaction product, the cloud point was measured by the said method. The results are shown in Table-2.
[0036]
[Table 3]

[0037]
[Example 1]
25 parts by weight of D, L-α-tocopherol (vitamin E) as an oil-soluble substance {Tokyo Chemical Industry Co., Ltd., special grade} and 75 parts by weight of PoGE-A produced in Production Example 1 (B component / A component = 1/3) was mixed and stirred at 60 to 70 ° C to obtain a mixture.
When 0.2 g of this mixture was mixed and stirred in 100 ml of water having a pH of 3 with citric acid and a temperature of 25 ° C., a composition in which the oil-soluble substance was uniformly solubilized or dispersed was obtained. Even when this composition was allowed to stand at 25 ° C. for 1 month and further allowed to stand at 5 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0038]
[Example 2]
15 parts by weight of vitamin E (the same kind as in Example 1) and 85 parts by weight of PoGE-A were weighed (B component / A component = 1 / 5.7), and mixed and stirred at 60 to 70 ° C. to obtain a mixture.
0.07 g, 0.13 g, 0.33 g, 0.67 g, and 1.33 g of this mixture were weighed and mixed with 100 ml of water at a temperature of 25 ° C., each adjusted to pH 3 with citric acid. In either case, a uniformly solubilized or dispersed composition was obtained. Even when this composition was allowed to stand at 25 ° C. for 1 month and further allowed to stand at 5 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0039]
[Example 3]
20 parts by weight of vitamin E (the same kind as in Example 1) and 80 parts by weight of PoGE-B were weighed (B component / A component = 1/4), and mixed and stirred at 60 to 70 ° C. to obtain a mixture.
When 0.25 g of this mixture was mixed and stirred in 100 ml of water having a pH of 3 with citric acid and a temperature of 25 ° C., a uniform solubilized or dispersed composition was obtained. Even when this composition was allowed to stand at 25 ° C. for 1 month and further allowed to stand at 5 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0040]
[Example 4]
20 parts by weight of vitamin E (same type as in Example 1) and 80 parts by weight of PoGE-D were weighed (B component / A component = 1/4) and stirred and mixed at 60 to 70 ° C. to obtain a mixture.
When 0.25 g of this mixture was mixed and stirred in 100 ml of water having a pH of 3 with citric acid and a temperature of 25 ° C., a uniform solubilized or dispersed composition was obtained. Even when this composition was allowed to stand at 25 ° C. for 1 month and further allowed to stand at 5 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0041]
[Example 5]
Weigh 15 parts by weight of orange oil (manufactured by Kyowa Fragrance Co., Ltd.) as an oil-soluble substance and 85 parts by weight of PoGE-A (B component / A component = 1 / 5.7), and mix and stir at 60 to 70 ° C. To obtain a mixture.
When 0.33 g of this mixture was mixed and stirred in 100 ml of water at a temperature of 25 ° C. having a pH of 3 with citric acid, a uniform solubilized or dispersed composition was obtained. Even when the composition was allowed to stand at 25 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0042]
[Example 6]
10 parts by weight of 2-ethylhexanoic acid triglyceride {manufactured by Nissin Oil Co., Ltd.) as an oil-soluble substance and 90 parts by weight of PoGE-A (B component / A component = 1/9), 60 to 70 ° C. And mixed with stirring to obtain a mixture.
When 0.50 g of this mixture was mixed and stirred in 100 ml of water having a pH of 3 with citric acid and a temperature of 25 ° C., a uniform solubilized or dispersed composition was obtained. Even when this composition was allowed to stand at 25 ° C. for 1 month and further allowed to stand at 5 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0043]
[Example 7]
10 parts by weight of 2-ethylhexanoic acid triglyceride (same as Example 6) and 90 parts by weight of PoGE-B (B component / A component = 1/9), and mixed and stirred at 60 to 70 ° C. Got.
When 0.50 g of this mixture was mixed and stirred in 100 ml of water having a pH of 3 with citric acid and a temperature of 25 ° C., a uniform solubilized or dispersed composition was obtained. Even when the composition was allowed to stand at 25 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0044]
[Example 8]
10 parts by weight of vitamin E (same as Example 1) and 60 parts by weight of PoGE-A (B component / A component = 1/6) were weighed, and 30 parts by weight of special grade glycerin {manufactured by Kishida Chemical Co., Ltd.} In addition, the mixture was mixed and stirred at 60 to 70 ° C. to obtain a mixture.
When 0.50 g of this mixture was mixed and stirred in 100 ml of water having a pH of 3 with citric acid and a temperature of 25 ° C., a uniform solubilized or dispersed composition was obtained. Even when this composition was allowed to stand at 25 ° C. for 1 month and further allowed to stand at 5 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0045]
[Example 9]
7 parts by weight of vitamin A palmitate {RIKEN VITAMIN Co., Ltd.) as an oil-soluble substance and 63 parts by weight of PoGE-B (B component / A component = 1/9) are further weighed, and a special grade glycerin (same as Example 8) ) Was added and mixed and stirred at 60 to 70 ° C. to obtain a mixture.
When 0.14 g of this mixture was mixed and stirred in 100 ml of water having a pH of 3 with citric acid and a temperature of 25 ° C., a uniform solubilized or dispersed composition was obtained. Even when the composition was allowed to stand at 25 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0046]
[Example 10]
40 parts by weight of vitamin E (the same kind as in Example 1) and 80 parts by weight of PoGE-B were weighed (B component / A component = 1/2), and mixed and stirred at 60 to 70 ° C. to obtain a mixture.
When 0.15 g of this mixture was mixed and stirred in 100 ml of water having a pH of 4 with citric acid and a temperature of 25 ° C., a uniform solubilized or dispersed composition was obtained. Even when this composition was allowed to stand at 25 ° C. for 1 month and further allowed to stand at 5 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0047]
[Example 11]
30 parts by weight of 2-ethylhexanoic acid triglyceride (same type as Example 6) and 45 parts by weight of PoGE-B (B component / A component = 1 / 1.5) were mixed and stirred at 60 to 70 ° C. Got.
When 0.13 g of this mixture was mixed and stirred in 100 ml of water having a pH of 5 with citric acid and a temperature of 25 ° C., a uniform solubilized or dispersed composition was obtained. Even when this composition was allowed to stand at 25 ° C. for 1 month and further allowed to stand at 5 ° C. for 1 month, no oil-water separation or precipitation occurred.
[0048]
[Comparative Example 1]
Weighing 10 parts by weight of vitamin E (same type as Example 1) and 90 parts by weight of PoGE-C (the cloud point of this is 10 ° C.) (B component / A component = 1/9), 60-70 The mixture was obtained by mixing and stirring at 0 ° C.
When 0.5 g of this mixture was mixed and stirred in 100 ml of water at a temperature of 25 ° C. adjusted to pH 3 with citric acid, a uniform solubilized or dispersed composition was not obtained.
[0049]
[Comparative Example 2]
Weighing 15 parts by weight of vitamin E (same type as Example 1) and 85 parts by weight of PoGE-E (the fatty acid of this is palmitic acid) (B component / A component = 1 / 5.7), 60-70 ° C. Were mixed and stirred to obtain a mixture.
When 0.33 g of this mixture was mixed and stirred in 100 ml of water having a temperature of 25 ° C. adjusted to pH 3 with citric acid, precipitation occurred and a uniform solubilized or dispersed composition could not be obtained.
[0050]
[Comparative Example 3]
Weigh 20 parts by weight of vitamin E (same type as Example 1) and 80 parts by weight of PoGE-F (the fatty acid of this is stearic acid) (B component / A component = 1/4), 60-70 ° C. Were mixed and stirred to obtain a mixture.
When 0.25 g of this mixture was mixed and stirred in 100 ml of water at a temperature of 25 ° C. adjusted to pH 3 with citric acid, precipitation occurred and a uniform solubilized or dispersed composition could not be obtained.
[0051]
[Table 4]

[0052]
From Examples 1 to 11 and Comparative Examples 1 to 3, the following is clear.
(1) The composition in which the oil-soluble substance according to the present invention is solubilized or dispersed forms a uniform soluble system or dispersion, and this system is stable without oil-water separation or precipitation even after standing for a long period of time. (See Example 1 to Example 11).
(2) On the other hand, when the cloud point of PoGE does not satisfy the requirements of claim 1, precipitation occurs in the composition, and a uniform soluble system or dispersion system is not formed (see Comparative Example 1). .
(3) Further, when the fatty acid constituting PoGE does not satisfy the requirements of claim 1, precipitation occurs in the composition, and a uniform soluble system or dispersion system is not formed (see Comparative Examples 2 to 3). .

Claims

In an aqueous composition in which an oil-soluble substance (hereinafter referred to as component B) is solubilized or dispersed in an aqueous medium (hereinafter referred to as component C) by a solubilizer or dispersant (hereinafter referred to as component A), A As for the component, 70% by weight or more of the constituent fatty acid is a saturated fatty acid having 12 to 14 carbon atoms , the average degree of polymerization of the constituent polyglycerol is 6 to 12, and the concentration is 1% by weight in a 10% by weight sodium sulfate aqueous solution. It consists of polyglycerin fatty acid ester having a cloud point measured at 20 ° C. or higher, and the aqueous composition contains 1 to 10 parts by weight of A component with respect to 1 part by weight of B component. An aqueous composition comprising an oil-soluble substance solubilized or dispersed in an aqueous medium.

The aqueous composition obtained by solubilizing or dispersing an oil-soluble substance according to claim 1 in an aqueous medium, wherein the pH is 5 or less.

The aqueous composition obtained by solubilizing or dispersing an oil-soluble substance according to claim 1 or 2 in an aqueous medium, wherein the aqueous medium does not contain a polyhydric alcohol.

The aqueous composition obtained by solubilizing or dispersing the oil-soluble substance according to any one of claims 1 to 3, wherein the content of component B is 100 to 5000 ppm.

More than 70% by weight of the constituent fatty acid is a saturated fatty acid having 12 to 14 carbon atoms, the average degree of polymerization of the constituent polyglycerol is 6 to 12, and haze measured at a concentration of 1% by weight in a 10% by weight sodium sulfate aqueous solution. Polyglycerin fatty acid ester (hereinafter referred to as A component) having a point of 20 ° C. or higher and oil-soluble substance (hereinafter referred to as B component) are 1 to 10 parts by weight of A component per 1 part by weight of B component. The method for producing an aqueous composition obtained by solubilizing or dispersing an oil-soluble substance according to any one of claims 1 to 4, wherein the mixture is mixed with an aqueous medium. .

More than 70% by weight of the constituent fatty acid is a saturated fatty acid having 12 to 14 carbon atoms, the average degree of polymerization of the constituent polyglycerol is 6 to 12, and haze measured at a concentration of 1% by weight in a 10% by weight sodium sulfate aqueous solution. It is a mixture of a polyglycerin fatty acid ester (hereinafter referred to as component A) having a point of 20 ° C. or higher and an oil-soluble substance (hereinafter referred to as component B), and the ratio of the two components is 1 part by weight of component B. A mixture for preparing an aqueous composition wherein B component is solubilized or dispersed by A component by mixing with an aqueous medium, characterized in that it is 1 to 10 parts by weight.