JP2007014866A - Method for preparing oil in water microemulsion composition - Google Patents
Method for preparing oil in water microemulsion composition Download PDFInfo
- Publication number
- JP2007014866A JP2007014866A JP2005198000A JP2005198000A JP2007014866A JP 2007014866 A JP2007014866 A JP 2007014866A JP 2005198000 A JP2005198000 A JP 2005198000A JP 2005198000 A JP2005198000 A JP 2005198000A JP 2007014866 A JP2007014866 A JP 2007014866A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- water
- emulsion composition
- aqueous solvent
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000000034 method Methods 0.000 title abstract description 20
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 53
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- 238000002360 preparation method Methods 0.000 claims description 9
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Abstract
Description
本発明は水中油型微細乳化組成物の製造方法、特にその製剤安定性の改良に関する。 The present invention relates to a method for producing an oil-in-water microemulsion composition, and particularly to improvement of the formulation stability.
非水乳化法は、親水性非イオン界面活性剤を水性溶媒中に添加し、これに油分を添加して水性溶媒中油型エマルションを作成し、この水性溶媒中油型エマルションにさらに水を添加することで水中油型エマルションを得るという方法であり、水性溶媒としては多価アルコール(特に二価グリコール類)が使用されている(例えば、特許文献1参照)。この非水乳化法は、他の乳化法に比べ少ない界面活性剤の量で多量の油分を配合できる。そのため、非水乳化法により製造した乳化組成物を化粧料等の皮膚外用剤として使用したとき、べたつきの少ないものが得られるという利点がある。
しかしながら、従来の非水乳化法では乳化粒子の微細化が十分でなく、乳化組成物の安定性にやや問題があった。また、高温で乳化を行うと乳化粒子径はさらに大きくなり、特に固形もしくは半固形油分を十分に微細化することは難しかった。また、他の手法では、油分量に対して界面活性剤の量が多い、高圧乳化などの特殊で非効率的な製造工程を必要とする、等の問題があった。
本発明は上記課題に鑑みなされたものであり、その目的は簡便な工程で、高温で乳化したときも乳化粒子を十分に微細化することのできる水中油型微細乳化組成物の製造方法を提供することにある。
However, the conventional non-aqueous emulsification method is not sufficient to make the emulsified particles fine, and the stability of the emulsified composition is somewhat problematic. Further, when emulsification is performed at a high temperature, the particle size of the emulsified particles is further increased, and it has been particularly difficult to sufficiently reduce the solid or semi-solid oil content. In addition, other methods have problems such as a large amount of surfactant relative to the amount of oil and a special and inefficient production process such as high-pressure emulsification.
The present invention has been made in view of the above problems, and its object is to provide a method for producing an oil-in-water microemulsion composition capable of sufficiently miniaturizing emulsified particles even when emulsified at a high temperature in a simple process. There is to do.
上記目的を達成するため、本発明者らが鋭意研究を重ねた結果、非水乳化法における水性溶媒としてポリオキシプロピレン・ポリオキシエチレンランダム共重合体ジアルキルエーテルを用いることで、高温でも乳化粒子径を小さく保つことができることを見出し、本発明を完成するに至った。
すなわち、本発明にかかる水中油型微細乳化組成物の製造方法は、(A)水性溶媒と(B)非イオン界面活性剤と(C)油分とを混合攪拌し、水性溶媒中油型乳化組成物を調製する工程と、該水性溶媒中油型乳化組成物に(D)水性処方を添加して水中油型乳化組成物を調製する工程と、を備え、前記(A)水性溶媒中にポリオキシプロピレン・ポリオキシエチレンランダム共重合体ジアルキルエーテルを含むことを特徴とする。
In order to achieve the above object, the present inventors have conducted extensive research, and as a result, polyoxypropylene / polyoxyethylene random copolymer dialkyl ether is used as an aqueous solvent in the non-aqueous emulsification method. Has been found to be small, and the present invention has been completed.
That is, in the method for producing an oil-in-water fine emulsion composition according to the present invention, (A) an aqueous solvent, (B) a nonionic surfactant, and (C) an oil component are mixed and stirred to obtain an oil-in-water emulsion composition in an aqueous solvent. And (D) adding an aqueous formulation to the oil-in-water emulsion composition in an aqueous solvent to prepare an oil-in-water emulsion composition, and (A) polyoxypropylene in the aqueous solvent. -Polyoxyethylene random copolymer dialkyl ether is included.
上記の製造方法において、少なくとも前記水性溶媒中油乳化組成物調製工程で70℃以上の温度で好適に調製を行うことができる。
上記の製造方法において、前記(C)油分として常温で固形もしくは半固形の油分を含むことが好適である。
上記の製造方法において、前記(B)非イオン界面活性剤の量に対する前記(C)油分の量が5倍以上であることが好適である。
上記の製造方法において、前記水中油型微細乳化組成物の乳化粒子径を好適に0.3μm以下とすることができる。
上記の製造方法において、前記(A)水性溶媒中にポリオキシエチレン・ポリオキシプロピレンランダム共重合体ジメチルエーテルを含むことが好適である。
上記の製造方法において、前記(C)油分中に室温で液状である高級アルコールまたは高級脂肪酸を一種まはた二種以上含むことが更に好適である。
In said manufacturing method, it can prepare suitably at the temperature of 70 degreeC or more by the said oil-in-water emulsion composition preparation process at least.
In the above production method, it is preferable that the oil component (C) contains a solid or semi-solid oil component at room temperature.
In said manufacturing method, it is suitable that the quantity of said (C) oil content with respect to the quantity of said (B) nonionic surfactant is 5 times or more.
In said manufacturing method, the emulsion particle diameter of the said oil-in-water type fine emulsion composition can be suitably 0.3 micrometer or less.
In the above production method, it is preferable that the (A) aqueous solvent contains polyoxyethylene / polyoxypropylene random copolymer dimethyl ether.
In the above production method, it is more preferable that the (C) oil contains one or more higher alcohols or higher fatty acids that are liquid at room temperature.
本発明にかかる水中油型微細乳化組成物の製造方法によれば、水性溶媒としてポリオキシプロピレン・ポリオキシエチレンランダム共重合体ジアルキルエーテルを用いているため、高温で乳化したときも微細な乳化粒子径を有する乳化組成物を得ることができる。 According to the method for producing an oil-in-water fine emulsion composition according to the present invention, since a polyoxypropylene / polyoxyethylene random copolymer dialkyl ether is used as an aqueous solvent, fine emulsified particles even when emulsified at a high temperature An emulsified composition having a diameter can be obtained.
本発明にかかる水中油型微細乳化組成物の製造方法は、(A)水性溶媒と(B)非イオン界面活性剤と(C)油分とを混合攪拌し、水性溶媒中油型乳化組成物を調製する工程と、該水性溶媒中油型乳化組成物に(D)水性処方を添加して水中油型乳化組成物を調製する工程と、を備え、前記(A)水性溶媒中にポリオキシプロピレン・ポリオキシエチレンランダム共重合体ジアルキルエーテルを含むことを特徴とする。そして、少なくとも前記水性溶媒中油型乳化組成物調整工程で常温より高い温度(例えば、70℃以上)で乳化を行っても十分微細な乳化粒子径を有する水中油型微細乳化組成物を得ることができる。なお、「常温」とは15〜25℃のことを意味する。 The method for producing an oil-in-water fine emulsion composition according to the present invention comprises (A) an aqueous solvent, (B) a nonionic surfactant, and (C) an oil component mixed and stirred to prepare an oil-in-water emulsion composition in an aqueous solvent. And (D) adding an aqueous formulation to the oil-in-water emulsion composition in an aqueous solvent to prepare an oil-in-water emulsion composition, and (A) the polyoxypropylene-polyethylene in the aqueous solvent. An oxyethylene random copolymer dialkyl ether is included. And even if it emulsifies at the temperature higher than normal temperature (for example, 70 degreeC or more) at least by the said oil-in-water-type emulsion composition adjustment process in the said aqueous solvent, the oil-in-water type fine emulsion composition which has a sufficiently fine emulsion particle diameter can be obtained. it can. In addition, "normal temperature" means 15-25 degreeC.
(A)水性溶媒としては、ポリオキシプロピレン・ポリオキシエチレンランダム共重合体ジアルキルエーテルのうち、親水性のもの(油分と相溶性が低いもの)が好ましく、特にポリオキシプロピレン・ポリオキシエチレンランダム共重合体ジメチルエーテルが好ましい。また、組み合わされる油分、非イオン界面活性剤の種類にもよるが、ポリオキシプロピレンの平均付加モル数は2〜50、ポリオキシエチレンの平均付加モル数は8〜100、ポリオキシエチレンとポリオキシプロピレンの平均付加モル数の合計に対するポリオキシエチレンの平均付加モル数の割合[POE/(POE+POP)]は0.5以上であることが好ましい。ここで、POE及びPOPは、それぞれポリオキシエチレン、ポリオキシプロピレンの略であり、以下、このように略して記載することがある。
また、ポリオキシプロピレン・ポリオキシエチレンランダム共重合体ジアルキルエーテルは公知の方法で製造することができる。例えば、水酸基を有している化合物にエチレンオキシドおよびプロピレンオキシドを付加重合した後、ハロゲン化アルキルをアルカリ触媒の存在下にエーテル反応させることによって得られる。
(A) As the aqueous solvent, among polyoxypropylene / polyoxyethylene random copolymer dialkyl ethers, hydrophilic ones (low compatibility with oil components) are preferable, especially polyoxypropylene / polyoxyethylene random copolymers. Polymer dimethyl ether is preferred. Also, depending on the type of oil and nonionic surfactant to be combined, the average added mole number of polyoxypropylene is 2 to 50, the average added mole number of polyoxyethylene is 8 to 100, polyoxyethylene and polyoxy The ratio [POE / (POE + POP)] of the average number of moles of polyoxyethylene to the total number of moles of propylene added is preferably 0.5 or more. Here, POE and POP are abbreviations for polyoxyethylene and polyoxypropylene, respectively, and may be abbreviated as follows.
The polyoxypropylene / polyoxyethylene random copolymer dialkyl ether can be produced by a known method. For example, it can be obtained by addition-polymerizing ethylene oxide and propylene oxide to a compound having a hydroxyl group, and then ether-reacting an alkyl halide in the presence of an alkali catalyst.
なお、水性溶媒中油型乳化組成物を調製する工程において用いる水性溶媒中のPOP・POEランダム共重合体ジアルキルエーテルの含有量は30質量%以上であることが好ましい。例えば水性溶媒としてPOP・POE共重合体ジアルキルエーテルと水を用いる場合、水性溶媒中の水の量はPOP・POEランダム共重合体ジアルキルエーテルの0.5倍から2倍(質量比)であることが望ましい。また、水性溶媒中には水以外のその他の水性溶媒を含有してもよい。 The content of the POP / POE random copolymer dialkyl ether in the aqueous solvent used in the step of preparing the oil-in-water emulsion composition in the aqueous solvent is preferably 30% by mass or more. For example, when POP / POE copolymer dialkyl ether and water are used as the aqueous solvent, the amount of water in the aqueous solvent should be 0.5 to 2 times (mass ratio) of the POP / POE random copolymer dialkyl ether. Is desirable. The aqueous solvent may contain other aqueous solvents other than water.
本発明に用いられる(B)非イオン界面活性剤としては、親水性のもの(例えば、HLBが12以上)が好ましく、例えば、ポリオキシエチレン(40〜100モル)硬化ヒマシ油、ポリオキシエチレン(10〜30モル)フィトステロール、ポリオキシエチレン(20〜30モル)コレステロール、ポリオキシエチレン(16〜30モル)オクチルドデカノール、ポリオキシエチレン(20〜30)ベヘニルアルコール等が挙げられる。
また(C)油分の種類は特に限定されないが、本発明の製造方法によれば高温で乳化しても十分微細な乳化粒子径を得ることができるため、常温で固形もしくは半固形の油分に対して特に好適に適用される。具体的にはモクロウ、蜜ロウ、カルナウバロウ、キャンデリラロウ等のロウ類;セタノール、ミリスチルアルコール、ステアリルアルコール、ベヘニルアルコール等の高級アルコール類;コレステロール、フィトステロール、フィトステロールアルキルエーテル、セラミド等の脂質類およびそれらの誘導体;固形パラフィン、ワセリン、マイクロクリスタリンワックス等の炭化水素類;ラウロイルグルタミン酸(フィトステリル/オクチルドデシル)、ラウロイルグルタミン酸(フィトステリル/オクチルドデシル/ベヘニル)、硬化ヒマシ油、ステアリン酸硬化ヒマシ油、テトラ(エチルヘキサン酸/安息香酸)ペンタエリスリチル、テトラ(エチルヘキサン酸/安息香酸/ベヘニン酸)ペンタエリスリチル等のエステル油分などが挙げられる。
The nonionic surfactant (B) used in the present invention is preferably a hydrophilic one (for example, HLB is 12 or more). For example, polyoxyethylene (40 to 100 mol) hydrogenated castor oil, polyoxyethylene ( 10-30 mol) phytosterol, polyoxyethylene (20-30 mol) cholesterol, polyoxyethylene (16-30 mol) octyldodecanol, polyoxyethylene (20-30) behenyl alcohol and the like.
In addition, the type of oil component (C) is not particularly limited, but according to the production method of the present invention, a sufficiently fine emulsified particle diameter can be obtained even when emulsified at a high temperature. And particularly preferably applied. Specifically, waxes such as mole, beeswax, carnauba wax, candelilla wax; higher alcohols such as cetanol, myristyl alcohol, stearyl alcohol, behenyl alcohol; lipids such as cholesterol, phytosterol, phytosterol alkyl ether, ceramide, and the like Derivatives; hydrocarbons such as solid paraffin, petrolatum, microcrystalline wax; lauroyl glutamic acid (phytosteryl / octyldodecyl), lauroyl glutamic acid (phytosteryl / octyldodecyl / behenyl), hydrogenated castor oil, stearic acid hydrogenated castor oil, tetra (ethylhexane) Acid / benzoic acid) pentaerythrityl, tetra (ethylhexanoic acid / benzoic acid / behenic acid) pentaerythrityl and the like. That.
さらに(C)油分中に、室温で液状を呈する高級アルコールまたは高級脂肪酸を一種または二種以上配合することが好適である。油分中にこれらを配合することで乳化粒子が更に微細化され、より安定性の高い水中油型乳化物が得られる。室温で液状を呈する高級アルコールとしては、例えば、オレイルアルコール、リノリルアルコール、リノレニルアルコール等の不飽和高級アルコール類;イソステアリルアルコール、オクチルドデシルアルコール、デシルテトラデカノール等の分岐飽和高級アルコール類が挙げられる。常温で液状を呈する高級脂肪酸としては、例えば、オレイン酸、リノール酸、リノレン酸などの不飽和脂肪酸、イソステアリン酸、イソパルミチン酸、イソミリスチン酸等が挙げられる。 Furthermore, it is preferable to blend one or two or more higher alcohols or higher fatty acids that are liquid at room temperature in (C) the oil. By blending these in the oil, the emulsified particles are further refined, and a more stable oil-in-water emulsion is obtained. Examples of higher alcohols that are liquid at room temperature include unsaturated higher alcohols such as oleyl alcohol, linoleyl alcohol, and linolenyl alcohol; branched saturated higher alcohols such as isostearyl alcohol, octyldodecyl alcohol, and decyltetradecanol. Is mentioned. Examples of the higher fatty acid that is liquid at room temperature include unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid, isostearic acid, isopalmitic acid, and isomyristic acid.
(C)油分の量は(B)非イオン界面活性剤の量に対して、5〜15倍(質量比)程度であることが好ましい。5倍以上であれば非イオン界面活性剤の量がそれほど多くないため、得られる水中油型乳化組成物はべたつきが少なく使用感の良いものとなる。また、15倍以下であれば、十分に微細な乳化粒子径の水中油型乳化組成物を好適に得ることができる。
また、油分中における、室温で液状を呈する高級アルコールまたは高級脂肪酸の量は、全油分量に対して5質量%〜60質量%であることが望ましく、特に好適には15質量%〜40質量%である。この範囲であると、安定性が高く、かつ使用感の良い水中油型乳化組成物を好適に得ることができる。
(C) The amount of oil is preferably about 5 to 15 times (mass ratio) with respect to the amount of (B) nonionic surfactant. If it is 5 times or more, the amount of the nonionic surfactant is not so large, so that the resulting oil-in-water emulsion composition has little stickiness and good usability. Moreover, if it is 15 times or less, the oil-in-water-type emulsion composition of a sufficiently fine emulsion particle diameter can be obtained suitably.
Further, the amount of the higher alcohol or higher fatty acid which is liquid at room temperature in the oil component is desirably 5% by mass to 60% by mass, particularly preferably 15% by mass to 40% by mass with respect to the total oil content. It is. Within this range, an oil-in-water emulsion composition having high stability and good usability can be suitably obtained.
また、上記の(D)水性処方とは、水あるいは水性溶媒を主な媒体としてなる処方であれば、特に限定されるものではなく、水あるいは水性溶媒の他、通常、化粧品、医薬品等に用いられる成分を安定性に影響が出ない範囲の配合量で配合していても構わない。
また、水性溶媒中油型乳化組成物の調製工程において、(A)水性溶媒としてPOP・POEランダム共重合体ジアルキルエーテルを0.1〜50質量%および水分0.05〜50質量%、(B)非イオン界面活性剤を0.01〜10質量%、(C)油分を0.05〜80質量%、配合することが好ましい。
また、水中油型乳化組成物の調製工程において、水性溶媒中油乳化組成物の量に対する(D)水性処方の量は特に限定されるものではないが、3〜150倍であることが好ましい。
In addition, the above (D) aqueous formulation is not particularly limited as long as it is a formulation having water or an aqueous solvent as a main medium. In addition to water or an aqueous solvent, it is usually used for cosmetics, pharmaceuticals, and the like. You may mix | blend the component by the compounding quantity of the range which does not affect stability.
In the preparation process of the oil-in-water emulsion composition in an aqueous solvent, (A) 0.1 to 50% by mass of a POP / POE random copolymer dialkyl ether as an aqueous solvent and 0.05 to 50% by mass of water, (B) It is preferable to blend 0.01 to 10% by mass of the nonionic surfactant and 0.05 to 80% by mass of the oil component (C).
Moreover, in the preparation process of the oil-in-water emulsion composition, the amount of the (D) aqueous formulation relative to the amount of the oil-in-water emulsion composition is not particularly limited, but is preferably 3 to 150 times.
水性溶媒中油型乳化組成物調製工程では、図1(a)に示すように、(A)POP・POEランダム共重合体ジアルキルエーテル高濃度水溶液10中に非イオン界面活性剤14と油分12が添加され、水性溶媒中油型エマルションが形成される。このとき、POP・POEランダム共重合体ジアルキルエーテル分子18は非イオン界面活性剤14の親水基16(ポリオキシエチレン鎖)近傍に多く分配されていると考えられる。そのため、各非イオン界面活性剤14の親水基16間の距離が広がり、エマルションに対して油分12に向う曲率を大きくする方向に力が働く。その結果、小さな乳化粒子径のエマルションが得られると考えられる。そして、水性溶媒中油乳化組成物を図1(b)のように水相に添加すると、親水基16近傍に分配されていたPOP・POEジメチルエーテル分子18の多くは水中へ拡散していき、微細な乳化粒子径の水中油型エマルションを得ることができる。
In the preparation process of the oil-in-water emulsion composition in the aqueous solvent, as shown in FIG. 1A, (A) the
ここで、乳化時の温度が高い場合を考えると、非イオン性界面活性剤14の親水基16は温度が上がるにつれて、その親油度が高まる。すると、非イオン界面活性剤の親水基部分の有効断面積は小さくなるため、乳化粒子径は大きくなる傾向がある。しかしながら、POP・POEジアルキルエーテル18の親油度も同様に高まるため、温度が上がったときも、POP・POEジアルキルエーテル分子18は非イオン性界面活性剤14の親水基16部分に多数分配される。その結果、上記の機構(POP・POEジアルキルエーテル分子18による非イオン界面活性剤14の親水基部分の有効断面積の増大)が高温時でも機能し、微細な乳化粒子径の水中油型エマルションを得ることができると考えられる。
Here, considering the case where the temperature at the time of emulsification is high, the lipophilicity of the
このように本発明にかかる製造方法によれば、少量の界面活性剤で、高温で乳化したときも微細な乳化粒子径を有する乳化組成物を得ることができる。また、本発明にかかる製造方法によって製造した水中油型乳化組成物は、化粧料などの皮膚外用剤に好適に使用することができる。特に、低粘度基材に配合した場合でも安定なものが得られるため、例えば、乳化化粧料、ローション状乳液、ローション状サンスクリーン等の製造に好適に適用することができる。 Thus, according to the production method of the present invention, an emulsified composition having a fine emulsified particle diameter can be obtained even when emulsified at a high temperature with a small amount of a surfactant. Moreover, the oil-in-water emulsion composition manufactured by the manufacturing method concerning this invention can be used conveniently for skin external preparations, such as cosmetics. In particular, since a stable product can be obtained even when blended in a low-viscosity base material, it can be suitably applied to the production of emulsified cosmetics, lotion-like emulsions, lotion-like sunscreens, and the like.
以下に本発明をさらに具体的に説明するが、本発明は以下の例に限定されるものではない。
まず、初めに表1、2で示す組成(質量%)で水中油型乳化組成物を調製し、室温で乳化したときの乳化粒子径、70℃以上で乳化したときの乳化粒子径、乳化組成物の安定性、組成物の使用感触について調べた。
First, an oil-in-water emulsion composition is first prepared with the composition (mass%) shown in Tables 1 and 2, and the emulsion particle diameter when emulsified at room temperature, the emulsion particle diameter when emulsified at 70 ° C. or higher, and the emulsion composition The stability of the product and the feel of use of the composition were examined.
製造方法
(1)表1、2の(B)非イオン界面活性剤、(C)油分を混合し、室温もしくは70℃でホモミキサーにかけながら(A)水性溶媒を徐々に添加し、水性溶媒中油型乳化組成物を調製した。
(2)この水性溶媒中油型エマルションを(D)水性処方に添加し、水中油型エマルションを得た。
乳化粒子径
得られた水中油型乳化組成物の乳化粒子径の測定は光散乱法により行った。装置はF−PAR−1000(大塚電子株式会社製)を用いた。
Production method (1) (B) Nonionic surfactant in Tables 1 and 2 and (C) Oil component are mixed, and (A) Aqueous solvent is gradually added while being applied to a homomixer at room temperature or 70 ° C. A mold emulsion composition was prepared.
(2) This oil-in-water emulsion in an aqueous solvent was added to (D) the aqueous formulation to obtain an oil-in-water emulsion.
Measurement of the emulsified particle diameter of emulsion particle size resulting oil-in-water emulsion composition was carried out by a light scattering method. The apparatus used was F-PAR-1000 (Otsuka Electronics Co., Ltd.).
安定性
得られた水中油型乳化組成物の安定性は、組成物を0℃、室温、37℃および50℃の温度試験条件下に一ヶ月保存した後、以下の基準により判定した。
◎:各試験温度において、分離や外観変化などの異常が全く認められない
○:試験温度50℃の組成物のみ、外観の変化が認められる
△:試験温度37℃の組成物についても、外観の変化が認められる
×:試験温度が室温、0℃の組成物についても、分離や外観の変化等の異常が認められる
Stability The stability of the obtained oil-in-water emulsion composition was determined according to the following criteria after the composition was stored for 1 month under temperature test conditions of 0 ° C., room temperature, 37 ° C. and 50 ° C.
A: No abnormality such as separation or change in appearance is observed at each test temperature. O: Only the composition at the test temperature of 50.degree. C. has a change in appearance. .DELTA .: The appearance of the composition at the test temperature of 37.degree. Change is observed ×: Abnormalities such as separation and changes in appearance are observed even in the composition where the test temperature is room temperature and 0 ° C.
使用感触
得られた水中油型乳化組成物の使用感触を以下のように試験した。女子パネル20名に、調製直後の組成物の使用性について官能評価してもらい、次の基準に従って評価した。
◎:べたつきや油っぽさのない使用感触であると評価したパネルが16名以上
○:べたつきや油っぽさのない使用感触であると評価したパネルが10〜15名
△:べたつきや油っぽさのない使用感触であると評価したパネルが6〜9名
×:べたつきや油っぽさのない使用感触であると評価したパネルが5名以下
表1、2に示すように、従来の非水乳化法で使用されてきた水性溶媒を用いた試験例1−1〜1−9は、乳化粒子径の微細化が十分でなく安定性が十分でないことが分かった。また高温で乳化した際には室温時と比較してさらに乳化粒子径が大きくなることも分かった。また、使用感触についても良好な結果は得られなかった。
The feeling of use of the obtained oil-in-water emulsion composition was tested as follows. Twenty women's panels evaluated the usability of the composition immediately after preparation, and evaluated it according to the following criteria.
◎: More than 16 panelists evaluated as having no stickiness or oily feel ○: 10 to 15 panels evaluated as having a feel without stickiness or oiliness △: Stickiness or oil 6 to 9 panels evaluated to have a feeling of use without a stickiness ×: 5 or less panels evaluated to have a feeling of use without stickiness or oiliness As shown in Tables 1 and 2, It was found that Test Examples 1-1 to 1-9 using an aqueous solvent that had been used in the non-aqueous emulsification method described above were not sufficiently refined in emulsion particle diameter and not sufficiently stable. It was also found that when emulsified at a high temperature, the particle size of the emulsified particles was larger than that at room temperature. Also, good results were not obtained for the feeling of use.
一方、水性溶媒としてPOP(4)POE(17)ランダム共重合体ジメチルエーテルを用いた試験例1−10〜1−12は、乳化粒子径が十分微細化されており安定性もよく、高温で乳化しても乳化粒子径は室温のときとほとんど変わらなかった。また、油分に対する界面活性剤が少なくても、0.3μm以下の十分微細な粒子径とすることができた。さらに、使用感触についても良好な結果を示した。
また試験例1−11と1−12を比較すると分かるように、本製法において、油分中にイソステアリン酸のような常温で液状の高級アルコールまたは高級脂肪酸を加えておくと、乳化粒子がより微細になることにより、安定性の更なる向上のみならず、肌へ塗布した際の油っぽさを低減させることができた。
On the other hand, Test Examples 1-10 to 1-12 using POP (4) POE (17) random copolymer dimethyl ether as an aqueous solvent have a sufficiently fine emulsion particle size and good stability, and are emulsified at high temperatures. Even so, the emulsified particle size was almost the same as at room temperature. Moreover, even if there was little surfactant with respect to an oil component, it was able to be set as the sufficiently fine particle diameter of 0.3 micrometer or less. Furthermore, good results were shown for the feeling of use.
In addition, as can be seen by comparing Test Examples 1-11 and 1-12, in this production method, when a higher alcohol or higher fatty acid that is liquid at room temperature such as isostearic acid is added to the oil, the emulsified particles become finer. As a result, not only was the stability improved, but also the oiliness when applied to the skin could be reduced.
次に、常温で半固形もしくは固形のものを含む油分に対して、70℃で乳化を行った際の乳化粒子径と得られる水中油型乳化組成物の安定性を調べた。表3にその結果を示す。
製造方法
(1)表3の(B)非イオン界面活性剤、(C)油分を混合し、70℃でホモミキサーにかけながら(A)水性溶媒を徐々に添加し、水性溶媒中油型乳化組成物を調製した。
(2)この水性溶媒中油型エマルションを(D)水性処方に添加し、水中油型エマルションを得た。
乳化粒子径
得られた水中油型エマルションの乳化粒子径の測定は光散乱法により行った。装置はFPAR−1000(大塚電子株式会社製)を用いた。
Production method (1) (B) Nonionic surfactant in Table 3 and (C) Oil component are mixed, and (A) Aqueous solvent is gradually added while applying to homomixer at 70 ° C., and oil-in-water emulsion composition in aqueous solvent Was prepared.
(2) This oil-in-water emulsion in an aqueous solvent was added to (D) the aqueous formulation to obtain an oil-in-water emulsion.
Measurement of the emulsified particle diameter of emulsion particle size resulting oil-in-water emulsion was carried out by a light scattering method. The apparatus used was FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
安定性
得られた水中油型乳化組成物の安定性は、組成物を0℃、室温、37℃および50℃の温度試験条件下に一ヶ月保存した後、以下の基準により判定した。
◎:各試験温度において、分離や透明度の変化などの外観異常が全く認められない
○:試験温度50℃の組成物のみ、僅かなの外観の変化が認められる
△:試験温度37℃の組成物についても、外観の変化等の異常が認められる
×:試験温度が室温、0℃の組成物についても、外観の変化等の異常が認められる
表3から分かるように、従来の非水乳化法で乳化した試験例2−5〜2〜8では、常温で半固形、固形の油分に対して十分に微細な乳化粒子径とすることができなかった。一方、水性溶媒としてPOP(4)POE(17)ランダム共重合体を用いた試験例2−1〜2−4では0.3μm以下の十分微細な乳化粒子径とすることができた。
Stability The stability of the obtained oil-in-water emulsion composition was determined according to the following criteria after the composition was stored for 1 month under temperature test conditions of 0 ° C., room temperature, 37 ° C. and 50 ° C.
◎: No abnormality in appearance such as separation or change in transparency is observed at each test temperature. ○: Only a composition having a test temperature of 50 ° C. has a slight change in appearance. △: About a composition having a test temperature of 37 ° C. In addition, an abnormality such as a change in appearance is observed. ×: An abnormality such as a change in appearance is observed even for a composition having a test temperature of room temperature and 0 ° C. As can be seen from Table 3, emulsification by a conventional non-aqueous emulsification method. In Test Examples 2-5 to 2-8, it was not possible to obtain a sufficiently fine emulsified particle diameter with respect to a semi-solid or solid oil component at room temperature. On the other hand, in Test Examples 2-1 to 2-4 using the POP (4) POE (17) random copolymer as the aqueous solvent, it was possible to obtain a sufficiently fine emulsified particle size of 0.3 μm or less.
次にPOP・POEランダム共重合体ジメチルエーテルにおけるPOPとPOEの和に対するPOEの割合(POE/POP+POE)について好適な範囲を調べるため次の試験を行った。
安定性
得られた水中油型乳化組成物の安定性は、組成物を0℃、室温、37℃および50℃の温度試験条件下に一ヶ月保存した後、以下の基準により判定した。
◎:各試験温度において、分離や透明度の変化などの外観異常が全く認められない
○:試験温度50℃の組成物のみ、僅かなの外観の変化が認められる
△:試験温度37℃の組成物についても、外観の変化等の異常が認められる
×:試験温度が室温、0℃の組成物についても、外観の変化等の異常が認められる
表4の結果から、特にPOPとPOEの付加モル数の和に対するPOEの付加モル数の割合が0.5以上であることが特に好適であることが分かった。
以下により具体的に本発明にかかる実施例を示す。なお、処方中の数値は完成した水中油型組成物に対する質量%である。ただし、本発明は以下に限定されるものではない。
Stability The stability of the obtained oil-in-water emulsion composition was determined according to the following criteria after the composition was stored for 1 month under temperature test conditions of 0 ° C., room temperature, 37 ° C. and 50 ° C.
◎: No abnormality in appearance such as separation or change in transparency is observed at each test temperature. ○: Only a composition having a test temperature of 50 ° C. has a slight change in appearance. △: About a composition having a test temperature of 37 ° C. In addition, an abnormality such as a change in appearance is observed. ×: An abnormality such as a change in appearance is also observed for a composition having a test temperature of room temperature and 0 ° C. From the results shown in Table 4, in particular, the number of moles of POP and POE added. It was found that the ratio of the added mole number of POE to the sum is particularly preferably 0.5 or more.
Examples according to the present invention will be specifically described below. In addition, the numerical value in prescription is the mass% with respect to the completed oil-in-water type composition. However, the present invention is not limited to the following.
<化粧水>
(配合成分)
(1)POE(25)オクチルドデカノール 0.045
(2)セスキイソステアリン酸ソルビタン 0.015
(3)スクワラン 0.4
(4)オレイン酸 0.1
(5)パルミチン酸レチノール 0.02
(6)香料 0.01
(7)POP(07)POE(14)ジメチルエーテル(ランダム共重合体)0.4
(8)イオン交換水 0.4
(9)エタノール 6.0
(10)ジプロピレングリコール 3.0
(11)1,3−ブチレングリコール 6.0
(12)ポリエチレングリコール1500 2.0
(13)ベタイン 1.0
(14)クエン酸 0.01
(15)クエン酸ナトリウム 0.09
(16)エデト酸ナトリウム 0.1
(17)パラベン 0.15
(18)イオン交換水 残余
(製法)
(1)〜(6)を混合し、常温でホモミキサーにかけながら(7)と(8)の混合物を添加した。得られた水性溶媒中油型乳化物を、あらかじめ均一に溶解した(9)〜(18)の水性処方部に加えた。
得られた化粧水状の水中油型乳化組成物は平均粒子径が0.14μmであり、経時による安定性が良好で、使用感触もべたつきのないみずみずしいものであった。
<Lotion>
(Compounding ingredients)
(1) POE (25) Octyldodecanol 0.045
(2) Sorbitan sesquiisostearate 0.015
(3) Squalane 0.4
(4) Oleic acid 0.1
(5) Retinol palmitate 0.02
(6) Fragrance 0.01
(7) POP (07) POE (14) dimethyl ether (random copolymer) 0.4
(8) Ion exchange water 0.4
(9) Ethanol 6.0
(10) Dipropylene glycol 3.0
(11) 1,3-butylene glycol 6.0
(12) Polyethylene glycol 1500 2.0
(13) Betaine 1.0
(14) Citric acid 0.01
(15) Sodium citrate 0.09
(16) Sodium edetate 0.1
(17) Paraben 0.15
(18) Ion exchange water Residue (Production method)
(1)-(6) was mixed and the mixture of (7) and (8) was added, applying to a homomixer at normal temperature. The obtained oil-in-water emulsion in an aqueous solvent was added to the aqueous formulation part of (9) to (18), which was uniformly dissolved in advance.
The obtained lotion-like oil-in-water emulsion composition had an average particle size of 0.14 μm, good stability over time, and a fresh, non-sticky feel.
<美白化粧水>
(配合成分)
(1)POE(30)フィトステロール 0.045
(2)セスキイソステアリン酸ソルビタン 0.015
(3)α−オレフィンオリゴマー 0.25
(4)ラウロイルグルタミン酸(フィトステリル/オクチルドデシル) 0.05
(5)テトラ(エチルヘキサン酸/安息香酸/ベヘニン酸)ペンタエリスリチル0.05
(6)ヒドロキシステアリン酸硬化ヒマシ油 0.05
(7)イソステアリン酸 0.1
(8)香料 0.01
(9)POP(4)POE(17)ジメチルエーテル(ランダム共重合体) 0.4
(10)イオン交換水 0.5
(11)エタノール 5.0
(12)1,3−ブチレングリコール 3.0
(13)エリスリトール 2.0
(14)キシリトール 0.5
(15)トリラウレス−4−リン酸 0.02
(16)アスコルビン酸グルコシド 2.0
(17)クエン酸 0.02
(18)クエン酸ナトリウム 0.18
(19)エデト酸ナトリウム 0.1
(20)水酸化カリウム 0.38
(21)パラベン 0.1
(22)フェノキシエタノール 0.2
(23)イオン交換水 残余
(製法)
(1)〜(8)を混合し、70℃でホモミキサーにかけながら(9)と(10)の混合物を添加した。得られた水性溶媒中油型乳化物を、あらかじめ均一に溶解した(11)〜(23)の水性処方部に加えた。
得られた化粧水状の水中油型乳化組成物は平均粒子径が0.16μmであり、経時による安定性が良好で、使用感触もべたつきのないみずみずしいものであった。
<Whitening lotion>
(Compounding ingredients)
(1) POE (30) phytosterol 0.045
(2) Sorbitan sesquiisostearate 0.015
(3) α-olefin oligomer 0.25
(4) Lauroyl glutamic acid (phytosteryl / octyldodecyl) 0.05
(5) Tetra (ethylhexanoic acid / benzoic acid / behenic acid) pentaerythrityl 0.05
(6) Hydroxy stearic acid hydrogenated castor oil 0.05
(7) Isostearic acid 0.1
(8) Fragrance 0.01
(9) POP (4) POE (17) dimethyl ether (random copolymer) 0.4
(10) Ion exchange water 0.5
(11) Ethanol 5.0
(12) 1,3-butylene glycol 3.0
(13) Erythritol 2.0
(14) Xylitol 0.5
(15) Trilaureth-4-phosphate 0.02
(16) Ascorbic acid glucoside 2.0
(17) Citric acid 0.02
(18) Sodium citrate 0.18
(19) Sodium edetate 0.1
(20) Potassium hydroxide 0.38
(21) Paraben 0.1
(22) Phenoxyethanol 0.2
(23) Ion exchange water Residue (Production method)
(1) to (8) were mixed, and the mixture of (9) and (10) was added while applying to a homomixer at 70 ° C. The obtained oil-in-water emulsion in an aqueous solvent was added to the aqueous formulations of (11) to (23), which were uniformly dissolved in advance.
The obtained lotion-like oil-in-water emulsion composition had an average particle size of 0.16 μm, good stability over time, and a fresh and non-sticky feel.
<乳液>
(1)べへネス−30 0.96
(2)トリ(エチルヘキサン酸)グリセリド 2.0
(3)スクワラン 2.0
(4)ジメチルポリシロキサン(6cs) 1.0
(5)ワセリン 2.0
(6)脱臭ポリイソブテン 0.2
(7)ベヘニルアルコール 0.5
(8)バチルアルコール 0.1
(9)フィトステロール 0.02
(10)酢酸トコフェロール 0.05
(11)イソステアリルアルコール 2.0
(12)POP(28)POE(55)ジメチルエーテル(ランダム共重合体)6.4
(13)イオン交換水 8.0
(14)グリセリン 4.0
(15)1,3−ブチレングリコール 5.0
(16)メチルグルセス−10 0.5
(17)ユキノシタ抽出液 0.2
(18)カルボマー 0.1
(19)キサンタンガム 0.05
(20)エデト酸ナトリウム 0.03
(21)パラベン 0.3
(22)水酸化カリウム 0.02
(23)イオン交換水 残余
(製法)
(1)〜(11)を混合し、70℃でホモミキサーにかけながら(12)と(13)の混合物を添加した。得られた水性溶媒中油型乳化物を、あらかじめ均一に混合した(14)〜(21)および(23)の水性処方部に加えた。(22)を加えて中和した。
得られた乳液状の水中油型乳化組成物は平均粒子径が0.25μmであり、経時による安定性が良好で、肌の保湿効果および柔軟効果に優れていた。
<Emulsion>
(1) Beheness-30 0.96
(2) Tri (ethylhexanoic acid) glyceride 2.0
(3) Squalane 2.0
(4) Dimethylpolysiloxane (6cs) 1.0
(5) Vaseline 2.0
(6) Deodorized polyisobutene 0.2
(7) Behenyl alcohol 0.5
(8) Batyl alcohol 0.1
(9) Phytosterol 0.02
(10) Tocopherol acetate 0.05
(11) Isostearyl alcohol 2.0
(12) POP (28) POE (55) dimethyl ether (random copolymer) 6.4
(13) Ion exchange water 8.0
(14) Glycerin 4.0
(15) 1,3-butylene glycol 5.0
(16) Methyl Gluces-10 0.5
(17) Yukinoshita extract 0.2
(18) Carbomer 0.1
(19) Xanthan gum 0.05
(20) Sodium edetate 0.03
(21) Paraben 0.3
(22) Potassium hydroxide 0.02
(23) Ion exchange water Residue (Production method)
(1) to (11) were mixed, and the mixture of (12) and (13) was added while applying to a homomixer at 70 ° C. The obtained oil-in-water emulsion in an aqueous solvent was added to the aqueous formulations of (14) to (21) and (23) which were uniformly mixed in advance. (22) was added to neutralize.
The obtained emulsion oil-in-water emulsion composition had an average particle size of 0.25 μm, good stability over time, and excellent skin moisturizing and softening effects.
<サンスクリーン>
(1)POE(30)フィトステロール 1.0
(2)POE(30)オクチルドデカノール 0.4
(3)セスキイソステアリン酸ソルビタン 0.5
(4)オクチルメトキシシンナメート 5.0
(5)セチルイソオクタン酸 5.0
(6)4−t−ブチル−4´−メトキシジベンゾイルメタン 0.8
(7)オクトクリレン 1.5
(8)イソステアリン酸 1.0
(9)イソステアリルアルコール 1.0
(10)オクチルドデカノール 0.5
(11)香料 0.03
(12)POP(28)POE(55)ジメチルエーテル(ランダム共重合体) 12.9
(13)イオン交換水 9.0
(14)エタノール 7.0
(15)ジプロピレングリコール 5.0
(16)フェニルベンゾイミダゾールスルホン酸 3.0
(17)クエン酸 0.01
(18)クエン酸ナトリウム 0.04
(19)エデト酸ナトリウム 0.05
(20)フェノキシエタノール 0.5
(21)水酸化ナトリウム 0.45
(22)イオン交換水 残余
(製法)
(1)〜(11)を混合し、70℃でホモミキサーにかけながら(12)と(13)の混合物を添加した。得られた水性溶媒中油型乳化物を、あらかじめ均一に溶解した(14)〜(22)の水性処方部に加えた。
得られたローション状サンスクリーンは平均粒子径が0.18μmであり、経時による安定性が良好であった。紫外線吸収剤を含む油性成分が微細化されているために、肌に塗布する際にムラ付きせず、高い紫外線防御効果を示した。
<Sunscreen>
(1) POE (30) Phytosterol 1.0
(2) POE (30) octyldodecanol 0.4
(3) Sorbitan sesquiisostearate 0.5
(4) Octyl methoxycinnamate 5.0
(5) Cetylisooctanoic acid 5.0
(6) 4-t-butyl-4'-methoxydibenzoylmethane 0.8
(7) Octocrylene 1.5
(8) Isostearic acid 1.0
(9) Isostearyl alcohol 1.0
(10) Octyldodecanol 0.5
(11) Perfume 0.03
(12) POP (28) POE (55) dimethyl ether (random copolymer) 12.9
(13) Ion exchange water 9.0
(14) Ethanol 7.0
(15) Dipropylene glycol 5.0
(16) Phenylbenzimidazolesulfonic acid 3.0
(17) Citric acid 0.01
(18) Sodium citrate 0.04
(19) Sodium edetate 0.05
(20) Phenoxyethanol 0.5
(21) Sodium hydroxide 0.45
(22) Residual ion exchange water (Production method)
(1) to (11) were mixed, and the mixture of (12) and (13) was added while applying to a homomixer at 70 ° C. The obtained oil-in-water emulsion in an aqueous solvent was added to the aqueous formulations of (14) to (22), which were uniformly dissolved in advance.
The obtained lotion-shaped sunscreen had an average particle size of 0.18 μm and good stability over time. Since the oily component containing the ultraviolet absorber is miniaturized, it does not become uneven when applied to the skin, and exhibits a high ultraviolet protection effect.
<ヘアミスト>
(1)POE(30)フィトステロール 0.05
(2)ポリオキシエチレン・メチルポリシロキサン共重合体 0.01
(3)メチルポリシロキサン(6cs) 0.4
(4)メチルポリシロキサン(20cs) 0.2
(5)メチルフェニルポリシロキサン 0.2
(6)イソステアリン酸 0.2
(7)香料 0.05
(8)トコフェロール 0.01
(9)POP(4)POE(17)ジメチルエーテル(ランダム共重合体) 0.4
(10)イオン交換水 0.4
(11)1,3−ブチレングリコール 7.0
(12)グリセリン 4.0
(13)フェノキシエタノール 0.5
(14)塩化ベヘニルトリメチルアンモニウム 0.2
(15)エタノール 3.0
(16)イオン交換水 残余
(製法)
(1)〜(8)を混合し、70℃でホモミキサーにかけながら(9)と(10)の混合物を添加した。得られた水性溶媒中油型乳化物を、あらかじめ70℃で均一に溶解した(11)〜(14)および(16)の水性処方部に加えて撹拌した。室温まで冷却した後、(15)を添加した。
得られた化粧水状のヘアミストは平均粒子径が0.15μmであり、経時による安定性が良好であった。髪に塗布すると、べたつかず伸びが良く、乾いた後には髪を滑らかにする効果が大きかった。
<Hair mist>
(1) POE (30) phytosterol 0.05
(2) Polyoxyethylene / methylpolysiloxane copolymer 0.01
(3) Methyl polysiloxane (6cs) 0.4
(4) Methyl polysiloxane (20 cs) 0.2
(5) Methylphenylpolysiloxane 0.2
(6) Isostearic acid 0.2
(7) Fragrance 0.05
(8) Tocopherol 0.01
(9) POP (4) POE (17) dimethyl ether (random copolymer) 0.4
(10) Ion exchange water 0.4
(11) 1,3-butylene glycol 7.0
(12) Glycerin 4.0
(13) Phenoxyethanol 0.5
(14) Behenyltrimethylammonium chloride 0.2
(15) Ethanol 3.0
(16) Residual ion exchange water (Production method)
(1) to (8) were mixed, and the mixture of (9) and (10) was added while applying to a homomixer at 70 ° C. The obtained oil-in-water emulsion in an aqueous solvent was added to the aqueous formulation parts (11) to (14) and (16) which were uniformly dissolved in advance at 70 ° C. and stirred. After cooling to room temperature, (15) was added.
The obtained skin lotion-like hair mist had an average particle size of 0.15 μm and good stability over time. When applied to the hair, it was non-sticky and stretched well, and after drying it had a great effect of smoothing the hair.
10 高濃度水性溶媒水溶液
12 油分
14 非イオン界面活性剤
16 非イオン界面活性剤の親水基部分
18 POPPOEジアルキルエーテル分子
10 High Concentration
Claims (7)
少なくとも前記水性溶媒中油乳化組成物調製工程で70℃以上の温度で調製を行うことを特徴とする水中油型微細乳化組成物の製造方法。 In the manufacturing method of Claim 1,
A method for producing an oil-in-water fine emulsion composition, wherein the preparation is carried out at a temperature of 70 ° C. or higher in at least the oil emulsion composition preparation step in the aqueous solvent.
前記(C)油分として常温で固形もしくは半固形の油分を含むことを特徴とする水中油型微細乳化組成物の製造方法。 In the manufacturing method of Claim 1 or 2,
(C) A method for producing an oil-in-water microemulsion composition, which comprises a solid or semi-solid oil at room temperature as the oil.
前記(B)非イオン界面活性剤の量に対する前記(C)油分の量が5倍以上であることを特徴とする水中油型微細乳化組成物の製造方法。 In the manufacturing method in any one of Claim 1 to 3,
The method for producing an oil-in-water fine emulsion composition, wherein the amount of the oil component (C) is 5 times or more with respect to the amount of the (B) nonionic surfactant.
前記水中油型微細乳化組成物の乳化粒子径が0.3μm以下であることを特徴とする水中油型微細乳化組成物の製造方法。 In the manufacturing method in any one of Claim 1 to 4,
The method for producing an oil-in-water fine emulsion composition, wherein the oil-in-water fine emulsion composition has an emulsified particle diameter of 0.3 μm or less.
前記(A)水性溶媒中にポリオキシエチレン・ポリオキシプロピレンランダム共重合体ジメチルエーテルを含むことを特徴とする水中油型微細乳化組成物の製造方法。 In the manufacturing method in any one of Claim 1 to 5,
(A) The manufacturing method of the oil-in-water type fine emulsion composition characterized by including the polyoxyethylene polyoxypropylene random copolymer dimethyl ether in the aqueous solvent.
前記(C)油分中に、室温で液状である高級アルコールまたは高級脂肪酸を一種または二種以上含むことを特徴とする水中油型微細乳化組成物の製造方法。 In the manufacturing method in any one of Claim 1 to 6,
(C) The method for producing an oil-in-water fine emulsion composition, wherein the oil component contains one or more higher alcohols or higher fatty acids that are liquid at room temperature.
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| JP2005198000A JP2007014866A (en) | 2005-07-06 | 2005-07-06 | Method for preparing oil in water microemulsion composition |
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| JP2005198000A JP2007014866A (en) | 2005-07-06 | 2005-07-06 | Method for preparing oil in water microemulsion composition |
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| JP2007014866A true JP2007014866A (en) | 2007-01-25 |
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| JP2005198000A Pending JP2007014866A (en) | 2005-07-06 | 2005-07-06 | Method for preparing oil in water microemulsion composition |
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| JP2007015972A (en) * | 2005-07-07 | 2007-01-25 | Shiseido Co Ltd | One-phase microemulsion composition and method for producing O / W ultrafine emulsion external preparation |
| JP2009234985A (en) * | 2008-03-27 | 2009-10-15 | Shiseido Co Ltd | Hair cosmetic |
| JP2009242281A (en) * | 2008-03-31 | 2009-10-22 | Shiseido Co Ltd | External preparation comprising ultrafine oil-in-water emulsion comprising high-polarity oil and production method thereof |
| WO2010086948A1 (en) * | 2009-02-02 | 2010-08-05 | 株式会社 資生堂 | Liquid cosmetic |
| US20100196429A1 (en) * | 2007-07-27 | 2010-08-05 | Shiseido Company Ltd. | Oil-In-Water Emulsion Composition And Method For Producing The Same |
| JP2010280632A (en) * | 2009-06-05 | 2010-12-16 | Shiseido Co Ltd | Oil in water type emulsified hair cosmetic |
| JP2011136963A (en) * | 2009-12-28 | 2011-07-14 | Lion Corp | Oil-in-water skin cosmetic |
| WO2011099422A1 (en) * | 2010-02-10 | 2011-08-18 | 富士フイルム株式会社 | Emulsion and cosmetic containing same |
| WO2011122072A1 (en) * | 2010-03-30 | 2011-10-06 | 株式会社 資生堂 | O/w emulsion composition |
| WO2013047204A1 (en) * | 2011-09-27 | 2013-04-04 | 株式会社資生堂 | Translucent oil-in-water emulsion cosmetic |
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| JP2007015972A (en) * | 2005-07-07 | 2007-01-25 | Shiseido Co Ltd | One-phase microemulsion composition and method for producing O / W ultrafine emulsion external preparation |
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| JP2009234985A (en) * | 2008-03-27 | 2009-10-15 | Shiseido Co Ltd | Hair cosmetic |
| JP2009242281A (en) * | 2008-03-31 | 2009-10-22 | Shiseido Co Ltd | External preparation comprising ultrafine oil-in-water emulsion comprising high-polarity oil and production method thereof |
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| WO2013047204A1 (en) * | 2011-09-27 | 2013-04-04 | 株式会社資生堂 | Translucent oil-in-water emulsion cosmetic |
| JP2013082687A (en) * | 2011-09-27 | 2013-05-09 | Shiseido Co Ltd | Transparent oil-in-water emulsion cosmetic |
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