JP2007147342A - Evaluation method of external preparation for skin, and external preparation for skin - Google Patents

Evaluation method of external preparation for skin, and external preparation for skin Download PDF

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JP2007147342A
JP2007147342A JP2005339662A JP2005339662A JP2007147342A JP 2007147342 A JP2007147342 A JP 2007147342A JP 2005339662 A JP2005339662 A JP 2005339662A JP 2005339662 A JP2005339662 A JP 2005339662A JP 2007147342 A JP2007147342 A JP 2007147342A
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skin
frequency
external preparation
elastic modulus
modulus curve
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JP4719558B2 (en
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Hideki Akatsuka
秀貴 赤塚
Hiromichi Sugiyama
拓道 杉山
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Pola Chemical Industries Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a technology capable of evaluating objective feeling of use not requiring a panelist, in evaluation of an external preparation for skin. <P>SOLUTION: In this evaluation method of the external preparation for skin, a storage modulus and a loss modulus to a frequency of the external preparation for skin are measured by using a parallel plate, and a storage modulus curve and a loss modulus curve to the frequency are drawn, and the frequency at an intersection point between the storage modulus curve and the loss modulus curve is determined, and the external preparation for skin is evaluated by using the frequency and existence of an inflection point on the loss modulus curve near the intersection point as indexes. The method has a characteristic wherein, when the frequency at the intersection point is below 0.5 (Angular frequency/rad/s) and the inflection point on the loss modulus curve exists in the periphery within 10% of the intersection point, it is determined to be cosmetics having strong function for providing comfort when used. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は皮膚外用剤の評価方法及び該評価方法で心地よいと判定される皮膚外用剤に関する。   The present invention relates to a method for evaluating a skin external preparation and a skin external preparation determined to be comfortable by the evaluation method.

化粧料などの皮膚外用剤において、使用感は非常に重要な要素となっている。これは、使用に際しての、化粧料の擦過、延展行為が皮膚に対して良好な刺激を与え、この刺激が交感神経を抑え、心身をストレスから開放させると言われている。斯くの如くに重要な品質要素である「使用感」であるが、このものについての客観的な測定法、評価法は乏しく、唯一、化粧行為を行いその前後の唾液中乃至は血中のデヒドロエピアンドロステロンの量変化を指標に評価する方法(例えば、特許文献1を参照)が知られているのみで、官能評価に委ねられているのが現状であった。デヒドロエピアンドロステロンの量変化を指標にする評価方法についても、客観的な数字ははじき出せるものの、パネラーを使用するという点で、客観性については、充分と言えない部分も存する。即ち、パネラーを介しない客観的な使用感を評価できる技術の開発が望まれていた。   In skin external preparations such as cosmetics, the feeling of use is a very important factor. It is said that, when used, the rubbing and spreading of cosmetics gives good stimulation to the skin, and this stimulation suppresses the sympathetic nerve and releases the mind and body from stress. As described above, “usability” is an important quality factor, but there are few objective measurement methods and evaluation methods for this, and it is the only dehydrogenation in saliva or blood before and after applying makeup. There is only known a method for evaluating the change in the amount of epiandrosterone as an index (see, for example, Patent Document 1), and the current situation is left to sensory evaluation. Regarding the evaluation method using the change in the amount of dehydroepiandrosterone as an index, although objective numbers can be ejected, there is a part that cannot be said to be objective in terms of using panelists. That is, development of a technique that can evaluate an objective feeling of use without using a panel has been desired.

一方、皮膚外用剤について、パラレルプレートを用いて化粧料の、貯蔵弾性率や損失弾性率を測定し、物性を評価する方法は既に行われていた。(例えば、特許文献2、特許文献3、特許文献4を参照)しかしながら、かかる物性値と、好ましい使用感との関係についての言及は全く為されていなかった。又、皮膚外用剤の評価法であって、パラレルプレートを用いて、該皮膚外用剤の、周波数に対する貯蔵弾性率と、損失弾性率とを測定し、周波数に対する貯蔵弾性率曲線と損失弾性率曲線を作成し、該貯蔵弾性率曲線と該損失弾性率曲線の交点を周波数を求め、該周波数と交点付近における損失弾性率曲線の変曲点の有無とを指標とする、皮膚外用剤の評価方法も全く知られていなかったし、該評価方法で、前記交点における周波数が0.5(Angular frequency/rad/s)以下であり、該交点の10%以内の近傍に損失弾性率曲線の変曲点が存する皮膚外用剤も全く知られていなかった。   On the other hand, methods for evaluating physical properties of external preparations for skin by measuring the storage elastic modulus and loss elastic modulus of cosmetics using a parallel plate have already been performed. (For example, refer to Patent Document 2, Patent Document 3, and Patent Document 4) However, no mention has been made of the relationship between the physical property value and a preferable feeling of use. In addition, a method for evaluating a skin external preparation, which uses a parallel plate to measure the storage elastic modulus and loss elastic modulus with respect to frequency of the skin external preparation, and stores the storage elastic modulus curve and loss elastic modulus curve with respect to frequency. A method for evaluating an external preparation for skin, using the frequency of the intersection of the storage modulus curve and the loss modulus curve as a frequency, and using the frequency and the presence or absence of an inflection point in the loss modulus curve near the intersection as an index In the evaluation method, the frequency at the intersection is 0.5 (Angular frequency / rad / s) or less, and the inflection of the loss modulus curve is within 10% of the intersection. No topical skin preparation was known at all.

特開平11−35597号公報Japanese Patent Laid-Open No. 11-35597 特開2004−043785号公報JP 2004-043785 A 特開2005−112823号公報JP 2005-112823 A 特開2003−083873号公報JP 2003-038773 A

本発明は、この様な状況下為されたものであり、皮膚外用剤の評価において、パネラーを介しない客観的な使用感を評価できる技術を提供することを課題とする。   The present invention has been made under such circumstances, and an object of the present invention is to provide a technique capable of evaluating an objective feeling of use without using a panel in the evaluation of an external preparation for skin.

この様な状況に鑑みて、本発明者らは、皮膚外用剤の評価において、パネラーを介しない客観的な使用感を評価できる技術を求めて、鋭意研究努力を重ねた結果、皮膚外用剤の評価法であって、パラレルプレートを用いて、該皮膚外用剤の、周波数に対する貯蔵弾性率と、損失弾性率とを測定し、周波数に対する貯蔵弾性率曲線と損失弾性率曲線を作成し、該貯蔵弾性率曲線と該損失弾性率曲線の交点を周波数を求め、該周波数と交点付近における損失弾性率曲線の変曲点の有無とを指標とする、皮膚外用剤の評価方法を用いて評価することにより、この様な評価が出来ることを見出し、発明を完成させるに至った。即ち、本発明は以下に示すとおりである。
(1)皮膚外用剤の評価法であって、パラレルプレートを用いて、該皮膚外用剤の、周波数に対する貯蔵弾性率と、損失弾性率とを測定し、周波数に対する貯蔵弾性率曲線と損失弾性率曲線を作成し、該貯蔵弾性率曲線と該損失弾性率曲線の交点を周波数を求め、該周波数と交点付近における損失弾性率曲線の変曲点の有無とを指標とすることを特徴とする、皮膚外用剤の評価方法。
(2)前記交点における周波数が0.5(Angular frequency/rad/s)以下であり、該交点の10%以内の近傍に損失弾性率曲線の変曲点が存した場合、使用時に心地よさを提供する作用の高い化粧料であると判定することを特徴とする、(1)に記載の皮膚外用剤の評価方法。
(3)乳化剤形の皮膚外用剤の評価方法であることを特徴とする、(1)又は(2)に記載の皮膚外用剤の評価方法。
(4)皮膚外用剤において、パラレルプレートを用いて、該皮膚外用剤の、周波数に対する貯蔵弾性率と、損失弾性率とを測定し、周波数に対する貯蔵弾性率曲線と損失弾性率曲線を作成し、該貯蔵弾性率曲線と該損失弾性率曲線の交点を周波数を求め、該周波数と交点付近における損失弾性率曲線の変曲点の有無とを調べた時、前記交点における周波数が0.1(Angular frequency/rad/s)以下であり、該交点の10%以内の近傍に損失弾性率曲線の変曲点が存することを特徴とする、皮膚外用剤。
(5)乳化剤形であることを特徴とする、(4)に記載の皮膚外用剤。
(6)有機変性粘土鉱物を含有する皮膚外用剤であることを特徴とする、(4)又は(5)に記載の皮膚外用剤。
(7)前記有機変性粘土鉱物が、ジメチルジステアリルアンモニウムクロリド変性ヘクトライトであることを特徴とする、(4)〜(6)何れか1項に記載の皮膚外用剤。
In view of such a situation, the present inventors have sought for a technique capable of evaluating an objective feeling of use without using a paneler in the evaluation of a topical skin preparation. An evaluation method, using a parallel plate, measuring storage elastic modulus with respect to frequency and loss elastic modulus of the external preparation for skin, creating a storage elastic modulus curve and a loss elastic modulus curve with respect to frequency, and Obtaining the frequency of the intersection of the elastic modulus curve and the loss elastic modulus curve and evaluating the frequency using the skin external preparation evaluation method using the frequency and the presence or absence of an inflection point of the loss elastic modulus curve in the vicinity of the intersection as an index Thus, it was found that such an evaluation can be made, and the present invention has been completed. That is, the present invention is as follows.
(1) Evaluation method of external preparation for skin, measuring storage elastic modulus with respect to frequency and loss elastic modulus of skin external preparation using parallel plate, storage elastic modulus curve with respect to frequency and loss elastic modulus Creating a curve, obtaining the frequency of the intersection of the storage modulus curve and the loss modulus curve, and using the frequency and the presence or absence of an inflection point of the loss modulus curve in the vicinity of the intersection as an index, Evaluation method for external preparation for skin.
(2) When the frequency at the intersection is 0.5 (Angular frequency / rad / s) or less and an inflection point of the loss elastic modulus curve exists in the vicinity of 10% or less of the intersection, The method for evaluating an external preparation for skin according to (1), characterized in that the cosmetic is determined to be a highly effective cosmetic.
(3) The method for evaluating a skin external preparation according to (1) or (2), wherein the method is an evaluation method of an emulsifier type skin external preparation.
(4) In the external preparation for skin, using a parallel plate, the storage elastic modulus with respect to the frequency and the loss elastic modulus of the external preparation for skin are measured, and a storage elastic modulus curve and a loss elastic modulus curve with respect to the frequency are created, When the frequency of the intersection of the storage modulus curve and the loss modulus curve is obtained, and the frequency and the presence or absence of an inflection point of the loss modulus curve near the intersection are examined, the frequency at the intersection is 0.1 (Angular frequency / rad / s), and an inflection point of a loss elastic modulus curve exists in the vicinity of 10% or less of the intersection.
(5) The external preparation for skin according to (4), which is in an emulsifier form.
(6) The external preparation for skin according to (4) or (5), which is an external preparation for skin containing an organically modified clay mineral.
(7) The skin external preparation according to any one of (4) to (6), wherein the organically modified clay mineral is dimethyl distearyl ammonium chloride modified hectorite.

本発明によれば、皮膚外用剤の評価において、パネラーを介しない客観的な使用感を評価できる技術を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, in the evaluation of an external preparation for skin, the technique which can evaluate the objective usability without using a paneler can be provided.

(1)本発明の皮膚外用剤の評価方法
本発明の皮膚外用剤の評価方法は、パラレルプレートを用いて、該皮膚外用剤の、周波数に対する貯蔵弾性率と、損失弾性率とを測定し、周波数に対する貯蔵弾性率曲線と損失弾性率曲線を作成し、該貯蔵弾性率曲線と該損失弾性率曲線の交点を周波数を求め、該周波数と交点付近における損失弾性率曲線の変曲点の有無とを指標とすることを特徴とする。パラレルプレートは粘動力学的測定法では一般的な方法であり、これを用いて貯蔵弾性率、損失弾性率を測定し、この2つの指標の関係から被測定対象の粘動力学的特徴を捉えるのに用いられている。この様なパラレルプレート型の粘動力学的特性の測定装置は、一般的にはレオメーターと称されており、その市販品が存し、その様な市販品を利用して前記貯蔵弾性率、損失弾性率は測定することが出来る。この様なレオメータとしては、例えば、レオロジカ社製の「DAR型ユニバーサルレオメーター」、TAインスツルメンツ社製の「ストレス制御式レオメーターAR500」等が好ましく例示できる。この様な貯蔵弾性率、損失弾性率の測定は周波数を変えて、それに対するこれらの値の変化を求め、これをX軸を周波数、Y軸を貯蔵弾性率(G’)乃至は損失弾性率(G’’)とした座標にプロットし、貯蔵弾性率曲線及び/又は損失弾性率曲線を描く。本発明では、この周波数に対する貯蔵弾性率の応答と、損失弾性率の応答の関係をもとに皮膚外用剤を評価する。
(1) Evaluation method for external preparation for skin of the present invention The evaluation method for external preparation for skin of the present invention uses a parallel plate to measure the storage elastic modulus with respect to frequency and loss elastic modulus of the external preparation for skin, A storage elastic modulus curve and a loss elastic modulus curve with respect to a frequency are created, a frequency is obtained from an intersection of the storage elastic modulus curve and the loss elastic modulus curve, and the presence or absence of an inflection point of the loss elastic modulus curve near the intersection. As an index. The parallel plate is a general method for measuring viscodynamics, and uses it to measure storage elastic modulus and loss elastic modulus, and capture the viscodynamic characteristics of the object to be measured from the relationship between these two indices. It is used for Such a parallel plate type viscodynamic property measuring apparatus is generally called a rheometer, and there is a commercially available product, and the storage elastic modulus, Loss modulus can be measured. As such a rheometer, for example, “DAR type universal rheometer” manufactured by Rheologicala, “stress control type rheometer AR500” manufactured by TA Instruments, etc. can be preferably exemplified. Such storage elastic modulus and loss elastic modulus are measured by changing the frequency and determining the change of these values. The X axis is the frequency and the Y axis is the storage elastic modulus (G ′) or the loss elastic modulus. Plot the coordinates (G ″) and draw a storage modulus curve and / or loss modulus curve. In the present invention, the external preparation for skin is evaluated based on the relationship between the response of the storage elastic modulus to this frequency and the response of the loss elastic modulus.

この貯蔵弾性率曲線及び損失弾性率曲線の関係と、皮膚外用剤の評価の関係は、前記2つの曲線の交点がどこにあるかと、損失弾性率曲線の形状における変曲点の有無と変曲点の位置を指標として行われる。即ち、2曲線の交点のX座標、即ち、周波数が小さく、具体的には0.5以下であった場合には、その皮膚外用剤の構造は安定で、擦過において崩れにくく、長時間摩擦係数が変わることなく、擦過が続けることが出来、これによって得られる心地よさは増大する。又、損失弾性率曲線が前記交点付近に極大値、即ち、変曲点を持つことにより、擦過の最終点において動粘性が増し、終点を明らかに認識でき、かかる終点がフィット感として認識される。即ち、この様な粘動力学的特性を有する皮膚外用剤は、長時間安定した擦過刺激を与えつつ、最後にフィットする感触の皮膚外用剤となる。かかる長時間安定した擦過刺激は、被擦過対象に心地よさを形成する。又、副次的なこれらの曲線の特徴は、高周波数側から交点までの間、G’、G’’ともに100〜2000Paにおさまる、なだらかな曲線を描くことが好ましい。これは応力に対して、常に一定した抵抗値を示すことを意味する。又、周波数が100〜1Angular frequency/rad/sの間、G’−G’’の値は少なくとも200Pa、より好ましくは300Pa存することが好ましい。この差がある程度存することにより、擦過行為時に使用感に「こく」を感じる。尚、損失弾性率曲線は低周波数側と高周波数側では傾きが大きく異なっており、この傾きが大きく変わる点が変曲点と定義できるが、この数値は次のような手法により簡易的に求めることが出来る。即ち、以下の工程に示すとおりである。
工程1:周波数1〜10Angular frequency/rad/sの曲線上の数点をサンプリングし、この座標を用いて一次相関式Y1を作成する。
工程2:周波数0.01〜0.1Angular frequency/rad/sの曲線上の数点をサンプリングし、この座標を用いて一次相関式Y2を作成する。
工程3:Y1とY2の交点を求め、そのx座標を変曲点の周波数とする。
The relationship between the storage elastic modulus curve and the loss elastic modulus curve, and the relationship between the evaluation of the external preparation for skin, the location of the intersection of the two curves, the presence or absence of an inflection point in the shape of the loss elastic modulus curve, and the inflection point The position of is used as an index. That is, when the X-coordinate of the intersection of two curves, that is, when the frequency is small, specifically 0.5 or less, the structure of the external preparation for skin is stable, is not easily collapsed by rubbing, and has a long-time coefficient of friction. The rubbing can continue without changing, and this increases the comfort. Further, since the loss elastic modulus curve has a maximum value, that is, an inflection point in the vicinity of the intersection, the kinematic viscosity increases at the final point of abrasion, and the end point can be clearly recognized, and the end point is recognized as a fit. . That is, the external preparation for skin having such viscodynamic properties is a skin external preparation that feels fit last while giving a stable irritation for a long time. Such a stable scratching stimulus for a long time forms comfort for the object to be scratched. Moreover, it is preferable to draw a gentle curve in which these secondary curves are characterized by both G ′ and G ″ falling between 100 and 2000 Pa from the high frequency side to the intersection. This means that the resistance value is always constant with respect to the stress. Further, it is preferable that the value of G′−G ″ is at least 200 Pa, more preferably 300 Pa, when the frequency is 100 to 1 Angular frequency / rad / s. When this difference exists to some extent, the feeling of use is felt during the rubbing action. Note that the slope of the loss modulus curve is greatly different between the low frequency side and the high frequency side, and the point at which this slope changes greatly can be defined as the inflection point, but this numerical value can be easily obtained by the following method. I can do it. That is, as shown in the following steps.
Step 1: Sample several points on a curve with a frequency of 1 to 10 Angular frequency / rad / s, and create a primary correlation equation Y1 using these coordinates.
Step 2: Sampling several points on a curve having a frequency of 0.01 to 0.1 Angular frequency / rad / s, and using these coordinates, a primary correlation equation Y2 is created.
Step 3: Find the intersection of Y1 and Y2, and use the x coordinate as the frequency of the inflection point.

(2)本発明の皮膚外用剤
本発明の皮膚外用剤は、前記評価方法に於いて、前記交点における周波数が0.1(Angular frequency/rad/s)以下であり、該交点の10%以内の近傍に損失弾性率曲線の変曲点が存することを特徴とする。この様な粘動力学的特性を示すためには、水中油乳化剤形のような、延展途中で転相する形態の剤形は好ましくなく、予め作られた油性ゲルの構造中に水相を分散せしめた形態の乳化剤形が好ましく、具体的には、有機変性粘土鉱物と多価アルコールの作るゲル構造に、水性成分を油中水乳化剤形の形になるように、ポリオキシアルキレン変性メチルポリシロキサンなどの界面活性剤の力を借りて分散せしめたものが好ましい。
(2) Skin external preparation of the present invention The skin external preparation of the present invention has a frequency at the intersection of 0.1 (Angular frequency / rad / s) or less in the evaluation method, and within 10% of the intersection The inflection point of the loss elastic modulus curve exists in the vicinity of. In order to exhibit such viscodynamic properties, a dosage form in the form of phase inversion during spreading, such as an oil-in-water emulsifier, is not preferred, and the aqueous phase is dispersed in the structure of a pre-made oily gel. The emulsified form of the emulsified form is preferable. Specifically, the polyoxyalkylene-modified methylpolysiloxane has a gel structure formed by an organically modified clay mineral and a polyhydric alcohol so that the aqueous component is in the form of a water-in-oil emulsifier. Those dispersed with the aid of a surfactant such as are preferred.

1)有機変性粘土鉱物
本発明の皮膚外用剤は有機変性粘土鉱物を必須成分として含有することを特徴とする。ここで有機変性とは、粘土鉱物の一部に有機化合物の一部を共有結合乃至はイオン結合を介して強固乃至は緩やかな結合を生ぜしめ、有機化合物の性質の一部乃至は全部を粘土鉱物に付与させることを意味し、この様な変性としては4級アミン基と粘土鉱物のアニオン部分を結合させる方法、カルボキシル基と粘土鉱物のカチオン部分を結合させる方法等が例示でき、4級アミン基と粘土鉱物のアニオン部分を結合させる方法が特に好ましく例示できる。
1) Organically modified clay mineral The external preparation for skin of the present invention is characterized by containing an organically modified clay mineral as an essential component. Here, organic modification means that a part or all of the properties of an organic compound is made into a clay mineral by causing a part of the organic compound to form a strong or loose bond via a covalent bond or an ionic bond. This means that it is imparted to minerals. Examples of such modifications include a method of binding a quaternary amine group and an anion portion of a clay mineral, and a method of binding a carboxyl group and a cation portion of a clay mineral. A method of combining the group and the anion portion of the clay mineral is particularly preferable.

粘土鉱物を変性させる4級アミノ基を有する化合物としては、特に限定されるわけではないが、クオタニウムと称される化合物が例示される。クオタニウムとは、低分子の置換第4級アンモニウム塩であって、国際基準化粧品原材料(INCI)に登録された化粧料原料が好ましい。さらに、粘土鉱物を変性させる4級アミノ基を有する化合物は、クオタニウム化合物のなかでも、従来の皮膚外用剤に含有されるクオタニウム化合物であることが好ましい。従来の皮膚外用剤で使用されているクオタニウム化合物としては、ステアリルトリメチルアンモニウムクロリド、ジメチルジステアリルアンモニウムクロリド等が好ましく例示される。ステアリルトリメチルアンモニウムクロリド、ジメチルジステアリルアンモニウムクロリド等は、粘土鉱物とともに安定な油中水乳化構造を形成することができるので好ましい。   Although it does not necessarily limit as a compound which has a quaternary amino group which modifies a clay mineral, The compound called quaternium is illustrated. Quotanium is a low molecular weight substituted quaternary ammonium salt, and is preferably a cosmetic raw material registered in International Standard Cosmetic Ingredients (INCI). Furthermore, the compound having a quaternary amino group that modifies the clay mineral is preferably a quaternium compound contained in a conventional external skin preparation among quaternium compounds. Preferred examples of the quaternium compound used in conventional external preparations for skin include stearyl trimethyl ammonium chloride and dimethyl distearyl ammonium chloride. Stearyl trimethyl ammonium chloride, dimethyl distearyl ammonium chloride and the like are preferable because they can form a stable water-in-oil emulsion structure together with clay minerals.

一方、4級アミノ基を有する化合物で変性される粘土鉱物(未変性粘土鉱物)としては、従来の皮膚外用剤に含有される粘土鉱物であれば特段の限定無く使用することができる。従来の皮膚外用剤に含有される粘土鉱物としては、スメクタイト系のヘクトライト、ベントナイトやモンモリロナイト;カオリナイト;イライト;マリーン粘土鉱物(海泥);デザートローズ粘土鉱物;パスカライトなどが好ましく挙げられる。これらのうち、油中水乳化構造を安定化させることができるベントナイト、ヘクトライト、モンモリロナイト又はカオリナイトが好ましく例示される。   On the other hand, as a clay mineral (unmodified clay mineral) modified with a compound having a quaternary amino group, any clay mineral contained in a conventional skin external preparation can be used without any particular limitation. Preferred clay minerals contained in conventional skin external preparations include smectite-type hectorite, bentonite and montmorillonite; kaolinite; illite; marine clay mineral (sea mud); desert rose clay mineral; Among these, bentonite, hectorite, montmorillonite or kaolinite which can stabilize the water-in-oil emulsion structure is preferably exemplified.

本発明の皮膚外用剤に含有される4級アミノ基を有する化合物で変性された粘土鉱物の製造方法の一例を以下に説明する。
前記未変性粘土鉱物を分散媒に分散させる。該分散剤は水系の溶媒であることが好ましく、水であってもよい。分散未変性粘土鉱物を含む分散液に、さらに4級アミノ基を有する化合物を加え、よく撹拌する。4級アミノ基を有する化合物は、水に溶解されて加えられてもよい。加えられる4級アミノ基を有する化合物の量は、分散未変性粘土鉱物の量に対して0.1〜20質量%であることが好ましく、0.5〜15質量%であることがより好ましい。この様な構成を取ることにより、乳化系において、好ましい使用感を呈するためである。撹拌後、分散質を濾取し、脱水、乾固することにより本発明における変性粘土鉱物を得ることができる。あるいは、分散質を濾取することなく、減圧濃縮することにより分散剤を除去して乾固させることにより、本発明における変性粘土鉱物を得ることもできる。得られた変性粘土鉱物は、好ましくは所望のサイズ(粒径が1〜1000μmであることが好ましい)に粉砕され、本発明の皮膚外用剤に含有される。
An example of a method for producing a clay mineral modified with a compound having a quaternary amino group contained in the external preparation for skin of the present invention will be described below.
The unmodified clay mineral is dispersed in a dispersion medium. The dispersant is preferably an aqueous solvent, and may be water. A compound having a quaternary amino group is further added to the dispersion containing the dispersed unmodified clay mineral and stirred well. The compound having a quaternary amino group may be added after being dissolved in water. The amount of the compound having a quaternary amino group to be added is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15% by mass with respect to the amount of the dispersed unmodified clay mineral. This is because by taking such a configuration, a preferable feeling of use is exhibited in the emulsification system. After stirring, the dispersoid is filtered, dehydrated and dried to obtain the modified clay mineral in the present invention. Or the modified clay mineral in this invention can also be obtained by removing a dispersing agent by concentrating under reduced pressure without filtering a dispersoid, and making it dry. The obtained modified clay mineral is preferably pulverized to a desired size (preferably having a particle size of 1 to 1000 μm) and contained in the skin external preparation of the present invention.

本発明における変性粘土鉱物は、前述したように調製して使用されることもできるが、市販されているものを使用することもできる。市販されている変性粘土鉱物には、化粧料などの皮膚外用剤などとして用いられているものもある。市販されている変性粘土鉱物としては、例えば、エレメンティス社より「ベントン38V」の名称で販売されている、ジメチルジステアリルアンモニウム変性ヘクトライトなどが好ましく例示される。   The modified clay mineral in the present invention can be prepared and used as described above, but a commercially available one can also be used. Some modified clay minerals on the market are used as external preparations for skin such as cosmetics. Preferable examples of commercially available modified clay minerals include dimethyl distearyl ammonium modified hectorite sold under the name “Benton 38V” by Elementis.

本発明の皮膚外用剤においては、かかる成分は0.5〜10質量%好ましく含有され、より好ましくは1〜5質量%含有される。かかる成分は、前記の含有量の範囲において、乳化剤として働くと同時に、その塗布時の使用感において、N−アシルグルタミン酸ジエステルとともに働き、塗布されている人に心地よさを感じせしめ、以て、リラックスさせ、ストレスを緩和する作用を有する。これにより、ストレスによる肌への悪影響を還元、緩和することが出来る。   In the skin external preparation of this invention, this component is contained preferably 0.5-10 mass%, More preferably, 1-5 mass% is contained. Such an ingredient works as an emulsifier within the above-mentioned content range, and at the same time, works together with N-acyl glutamic acid diester in the feeling of use at the time of application, making the person being applied feel comfortable and relaxing. And has the effect of relieving stress. Thereby, the bad influence to the skin by stress can be reduced and relieved.

2)ポリオキシアルキレン変性メチルポリシロキサン
かかる成分の内、特に好ましいものは、ポリオキシアルキレン変性メチルポリシロキサンであり、中でも架橋構造を有するポリオキシアルキレン変性メチルポリシロキサンである。架橋構造はビニルメチルジメトキシシロキサンを重合時に添加し、重合後ビニル基を重合させ架橋を構築することにより製造することが出来る。かかるポリオキシアルキレン変性メチルポリシロキサンを構成するポリエーテル構造としては、ポリエチレングリコール残基やポリプロピレングリコール残基が好ましく例示でき、ポリエチレングリコール残基が特に好ましい。この様なポリオキシアルキレン変性メチルポリシロキサンには市販品が存し、かかる市販品を購入して利用することが出来る。好ましい市販品としては、信越化学株式会社より販売されている「シリコーンKF6017」(架橋型ポリエチレングリコール変性メチルポリシロキサン)が好適に例示できる。かかる成分は、前記必須成分である有機変性粘土鉱物が作る乳化構造をより安定化し、塗布における皮膚上での擦過時に水相が漏出する使用感を軽減する作用を有し、以て使用感を向上せしめる。この様な効果を奏するためには、ポリオキシアルキレン変性メチルポリシロキサンは、1〜10質量%含有することが好ましく、より好ましくは、2〜7質量%がより好ましい。
2) Polyoxyalkylene-modified methyl polysiloxane Among these components, polyoxyalkylene-modified methyl polysiloxane is particularly preferable, and among them, polyoxyalkylene-modified methyl polysiloxane having a crosslinked structure. The crosslinked structure can be produced by adding vinylmethyldimethoxysiloxane at the time of polymerization and polymerizing the vinyl group after polymerization to construct a crosslinked structure. As the polyether structure constituting such polyoxyalkylene-modified methylpolysiloxane, a polyethylene glycol residue or a polypropylene glycol residue can be preferably exemplified, and a polyethylene glycol residue is particularly preferred. Such polyoxyalkylene-modified methyl polysiloxane has a commercial product, and such a commercial product can be purchased and used. Preferable examples of commercially available products include “silicone KF6017” (crosslinked polyethylene glycol-modified methylpolysiloxane) sold by Shin-Etsu Chemical Co., Ltd. This component has the effect of further stabilizing the emulsified structure formed by the organically modified clay mineral, which is the essential component, and reducing the feeling of use when the aqueous phase leaks out during rubbing on the skin during application. Improve. In order to achieve such an effect, the polyoxyalkylene-modified methyl polysiloxane is preferably contained in an amount of 1 to 10% by mass, more preferably 2 to 7% by mass.

3)N−アシルグルタミン酸ジエステル
交点の10%以内の近傍に損失弾性率曲線の変曲点が存する様に調整するためには、前記有機変性粘土鉱物と、油性成分に対してともに親和性を有する成分を含有せしめ、内相が擦過によって消失し、ゲル構造が壊れようとする際に、内相と有機変性粘土鉱物との架橋となり、乳化構造が崩壊するのに抵抗する成分を含有せしめることが好ましい。この様な成分としてはN−アシルグルタミン酸ジエステルが好ましく例示できる。かかる成分を構成するアシル基としては、飽和でも、不飽和でも良く、例えば、2−エチルヘキサノイル基、ラウロイル基、ミリストイル基、パルミトイル基、ステアロイル基、ベヘノイル基、オレオイル基、イソステアロイル基、リノレノイル基などが好適に例示でき、特に好ましいものはラウロイル基である。又、ジアルキルエステルを構成するアルキル基としては、分岐でも、直鎖でも、環状構造を有するものでも良く、例えば、オクチル基、ラウリル基、セチル基、ステアリル基、イソステアリル基、ベヘニル基、オクチルドデシル基、カンペステリル基やシトステリル基等のフィトステリル基、コレステリル基などが好適に例示できる。具体的な化合物例としては、N−ラウロイル−L−グルタミン酸ジ(コレステリル/ベヘニル/オクチルドデシル)、N−ラウロイル−L−グルタミン酸ジ(コレステリル/オクチルドデシル)、N−ラウロイル−L−グルタミン酸ジ(フィトステリル/ベヘニル/オクチルドデシル)、N−ラウロイル−L−グルタミン酸ジ(フィトステリル/オクチルドデシル)等が好適に例示でき、N−ラウロイル−L−グルタミン酸ジ(コレステリル/オクチルドデシル)が特に好適に例示できる。かかるN−アシル化グルタミン酸ジエステルは、グルタミン酸とアシルクロリドをアルカリ存在下縮合させ、N−アシルグルタミン酸と為し、しかる後、塩基又は酸の存在下、所望により溶剤を存在させ、対応するアルコールと脱水縮合せしめ製造することが出来る。N−アシル化グルタミン酸のジエステルはこの様に合成したものを使用することも出来るが、既に化粧料原料などとして市販されているものも存し、この様な市販品を購入し利用することも出来る。特に好ましい市販品としては味の素株式会社より販売されている「エルデュウPS203」(N−ラウロイル−L−グルタミン酸ジ(コレステリル/オクチルドデシル))が例示できる。かかる成分は唯一種含有させることも出来るし、二種以上を組み合わせて含有させることも出来る。好ましい含有量は、総量で、皮膚外用剤全量に対し、0.1〜10質量%であり、より好ましくは1〜5質量%である。
3) N-acyl glutamic acid diester In order to adjust so that the inflection point of the loss modulus curve exists in the vicinity of 10% or less of the intersection point, it has affinity for both the organically modified clay mineral and the oil component. When the internal phase disappears due to abrasion and the gel structure is about to be broken, the internal phase and the organically modified clay mineral are cross-linked, and the component that resists the collapse of the emulsified structure may be included. preferable. Preferred examples of such components include N-acyl glutamic acid diesters. The acyl group constituting the component may be saturated or unsaturated, for example, 2-ethylhexanoyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, behenoyl group, oleoyl group, isostearoyl group, A linolenoyl group etc. can be illustrated suitably, A lauroyl group is especially preferable. In addition, the alkyl group constituting the dialkyl ester may be branched, straight chain, or cyclic, for example, octyl group, lauryl group, cetyl group, stearyl group, isostearyl group, behenyl group, octyldodecyl. Preferred examples include phytosteryl groups such as campesteryl group and sitosteryl group, and cholesteryl group. Specific examples of the compound include N-lauroyl-L-glutamate di (cholesteryl / behenyl / octyldodecyl), N-lauroyl-L-glutamate di (cholesteryl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl). / Behenyl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl / octyldodecyl) and the like can be preferably exemplified, and N-lauroyl-L-glutamate di (cholesteryl / octyldodecyl) can be particularly suitably exemplified. Such an N-acylated glutamic acid diester is obtained by condensing glutamic acid and acyl chloride in the presence of an alkali to form N-acyl glutamic acid, and then in the presence of a base or acid, optionally in the presence of a solvent, and dehydrating with the corresponding alcohol. It can be produced by condensation. N-acylated glutamic acid diesters can be synthesized in this way, but some are already commercially available as cosmetic raw materials, and such commercial products can be purchased and used. . As a particularly preferred commercial product, “Eldue PS203” (N-lauroyl-L-glutamate di (cholesteryl / octyldodecyl)) sold by Ajinomoto Co., Inc. can be exemplified. These components can be contained alone or in combination of two or more. The preferred content is 0.1 to 10% by mass, more preferably 1 to 5% by mass, based on the total amount of the external preparation for skin.

かかる成分に適宜、製剤化のための任意成分を加えて、常法に従って処理することにより、本発明の皮膚外用剤は製造化することが出来る。得られた皮膚外用剤は、前記の評価方法に従って、粘動力学的特性を測定し、本発明の皮膚外用剤として適当か、否かを判断される。   The external preparation for skin of the present invention can be produced by appropriately adding an optional component for formulation to such a component and treating it according to a conventional method. The obtained external preparation for skin is measured for viscodynamic properties according to the above evaluation method, and it is judged whether or not it is suitable as an external preparation for skin of the present invention.

以下に、実施例を挙げて、本発明について、更に詳細に説明を加えるが、本発明が、かかる実施例にのみ限定されないことは言うまでもない。   Hereinafter, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to such examples.

以下に示す処方に従って、皮膚外用剤である化粧料を作成した。即ち、イ、ロ、ハ、ニの成分を80℃に加熱し、イの成分とニの成分を良く混練りし、これにハを加えて希釈し、攪拌下これにニを徐々に加え、乳化し、攪拌冷却し、皮膚外用剤である油中水剤形の化粧料1(抗炎症医薬部外品)を得た。   In accordance with the formulation shown below, a cosmetic that is an external preparation for skin was prepared. That is, the ingredients (a), (b), (c), and (d) are heated to 80 ° C., the ingredients (a) and (d) are thoroughly kneaded, added to (c), diluted, and gradually added to the mixture with stirring. The mixture was emulsified, stirred and cooled to obtain a water-in-oil cosmetic 1 (anti-inflammatory pharmaceutical quasi-drug) as a skin external preparation.

Figure 2007147342
Figure 2007147342

以下に示す表2に従って、水中油乳化剤形の皮膚外用剤である、水中油乳化化粧料2を製造した。即ち、イ、ロ、ハの成分をそれぞれ80℃に加熱し、イにロを加え中和してゲルを作成し、これに攪拌下ハを徐々に加え乳化し、攪拌冷却して水中油乳化剤形の化粧料2を得た。   According to Table 2 shown below, an oil-in-water emulsified cosmetic 2 which is an oil-in-water emulsifier type skin external preparation was produced. That is, the components of A, B, and C are heated to 80 ° C., respectively, neutralized by adding B to A, and the mixture is gradually emulsified with stirring and emulsified, cooled with stirring and oil-in-water emulsifier. Shaped cosmetic 2 was obtained.

Figure 2007147342
Figure 2007147342

<試験例1>
化粧料1と化粧料2について、TAインスツルメンツ社製の「ストレス制御式レオメーターAR500」を用いて、貯蔵弾性率と損失弾性率とを計測し、貯蔵弾性率曲線及び損失弾性率曲線を作成した。この結果を図1に示す。これより、化粧料1は交点における周波数が、簡易的計算で0.098(Angular frequency/rad/s)で0.5(Angular frequency/rad/s)以下であり、該交点の10%以内の近傍に損失弾性率曲線の変曲点が存し、高周波数側から交点までの間、G’、G’’ともに100〜2000Paにおさまる、なだらかな曲線を描くことが好ましい。これは応力に対して、常に一定した抵抗値を示すことを意味する。又、周波数が100〜1Angular frequency/rad/sの間、G’−G’’の値は少なくとも200Pa存することが判る。化粧料2は簡易的計算で変曲点は計算できず、この要件を満たさない。従って、化粧料1は本発明の化粧料であると鑑別され、化粧料2は本発明の化粧料に属さないと鑑別される。
<Test Example 1>
For cosmetics 1 and 2, the storage elastic modulus and loss elastic modulus were measured using a “stress control rheometer AR500” manufactured by TA Instruments, and a storage elastic modulus curve and a loss elastic modulus curve were prepared. . The result is shown in FIG. Thus, in cosmetic 1, the frequency at the intersection is 0.098 (Angular frequency / rad / s) or less at 0.5 (Angular frequency / rad / s) by simple calculation, and is within 10% of the intersection. It is preferable to draw a gentle curve in which there is an inflection point of the loss elastic modulus curve in the vicinity and both G ′ and G ″ fall between 100 and 2000 Pa from the high frequency side to the intersection. This means that the resistance value is always constant with respect to the stress. Further, it can be seen that the value of G′−G ″ is at least 200 Pa when the frequency is 100 to 1 Angular frequency / rad / s. The cosmetic 2 cannot calculate the inflection point by simple calculation and does not satisfy this requirement. Therefore, cosmetic 1 is identified as the cosmetic of the present invention, and cosmetic 2 is identified as not belonging to the cosmetic of the present invention.

<試験例2>
無作為に選抜した40名のパネラーを、属性に偏りが生じないように20名ずつ2群に群分けし、1群は化粧料1を用いてマッサージを行い、1群は化粧料2を用いてマッサージを行って、マッサージの前後に唾液を採取し、唾液中のプラステロン硫酸の量を定量した。プラステロン硫酸の定量はサンドウィッチ抗体を用いた方法で外部委託試験機関に痛くした。定量結果より、(マッサージ後のプラステロン硫酸の量−マッサージ前のプラステロン硫酸の量)/(マッサージ前のプラステロン硫酸の量)×100の計算式より、プラステロン硫酸の増加率(%)を算出した。結果を表3に示す。これより本発明の化粧料は、優れた使用感を有し、心地よさを感じせしめることが判る。
<Test Example 2>
40 panelists selected at random are grouped into 2 groups of 20 people so that there is no bias in the attributes, 1 group massages with cosmetic 1 and 1 group uses cosmetic 2 The saliva was collected before and after the massage, and the amount of plasterone sulfate in the saliva was quantified. Plasterone sulfate was quantified by an outsourced laboratory using a sandwich antibody method. From the quantification result, the rate of increase in plasterone sulfate (%) from the formula of (amount of plasterone sulfate after massage-amount of plasterone sulfate before massage) / (amount of plasterone sulfate before massage) x 100 Was calculated. The results are shown in Table 3. From this, it can be seen that the cosmetic of the present invention has an excellent feeling of use and makes it feel comfortable.

Figure 2007147342
Figure 2007147342

実施例1の化粧料1と同様に、下記の表4に従って、化粧料3を作成した。このものの貯蔵弾性率と損失弾性率を測定し、貯蔵弾性率曲線と、損失弾性率曲線とを作成した。これを図2に示す。簡易的に計算した変曲点は0.23であり、この化粧料3も本発明の化粧料であることが判った。このものを試験例2と同様の手技で評価したところ(n=3)、プラステロン硫酸の増加率は39.1±8%であり、本発明の化粧料の効果が確認された。ポリオキシアルキレン変性メチルポリシロキサンを用いて、構造を強固にした方が好ましいことが判る。   In the same manner as cosmetic 1 in Example 1, cosmetic 3 was prepared according to Table 4 below. The storage elastic modulus and loss elastic modulus of this were measured, and a storage elastic modulus curve and a loss elastic modulus curve were prepared. This is shown in FIG. The inflection point calculated simply was 0.23, and it was found that this cosmetic 3 was also the cosmetic of the present invention. When this was evaluated by the same procedure as in Test Example 2 (n = 3), the rate of increase in plasterone sulfate was 39.1 ± 8%, confirming the effect of the cosmetic of the present invention. It can be seen that it is preferable to use polyoxyalkylene-modified methylpolysiloxane to strengthen the structure.

Figure 2007147342
Figure 2007147342

本発明は、化粧料の評価、設計に応用できる。   The present invention can be applied to the evaluation and design of cosmetics.

実施例1の化粧料1及び化粧料2のレオメーターの測定結果を示す図である。It is a figure which shows the measurement result of the rheometer of the cosmetics 1 and 2 of Example 1. FIG. 実施例2の化粧料3のレオメーターの測定結果を示す図である。It is a figure which shows the measurement result of the rheometer of the cosmetics 3 of Example 2. FIG.

Claims (7)

皮膚外用剤の評価法であって、パラレルプレートを用いて、該皮膚外用剤の、周波数に対する貯蔵弾性率と、損失弾性率とを測定し、周波数に対する貯蔵弾性率曲線と損失弾性率曲線を作成し、該貯蔵弾性率曲線と該損失弾性率曲線の交点を周波数を求め、該周波数と交点付近における損失弾性率曲線の変曲点の有無とを指標とすることを特徴とする、皮膚外用剤の評価方法。 This is a method for evaluating external preparations for skin, and measures the storage elastic modulus and loss elastic modulus with respect to frequency of the external preparation for skin using a parallel plate, and creates a storage elastic modulus curve and a loss elastic modulus curve with respect to frequency. Wherein the frequency of the intersection of the storage modulus curve and the loss modulus curve is obtained, and the frequency and the presence or absence of an inflection point of the loss modulus curve near the intersection are used as indices. Evaluation method. 前記交点における周波数が0.5(Angular frequency/rad/s)以下であり、該交点の10%以内の近傍に損失弾性率曲線の変曲点が存した場合、使用時に心地よさを提供する作用の高い化粧料であると判定することを特徴とする、請求項1に記載の皮膚外用剤の評価方法。 When the frequency at the intersection is 0.5 (Angular frequency / rad / s) or less and an inflection point of the loss elastic modulus curve exists in the vicinity of 10% or less of the intersection, an effect of providing comfort during use The skin external preparation evaluation method according to claim 1, wherein the skin external preparation is determined to be a high cosmetic. 乳化剤形の皮膚外用剤の評価方法であることを特徴とする、請求項1又は2に記載の皮膚外用剤の評価方法。 The method for evaluating a skin external preparation according to claim 1 or 2, wherein the method is an evaluation method for an emulsifier-type skin external preparation. 皮膚外用剤において、パラレルプレートを用いて、該皮膚外用剤の、周波数に対する貯蔵弾性率と、損失弾性率とを測定し、周波数に対する貯蔵弾性率曲線と損失弾性率曲線を作成し、該貯蔵弾性率曲線と該損失弾性率曲線の交点を周波数を求め、該周波数と交点付近における損失弾性率曲線の変曲点の有無とを調べた時、前記交点における周波数が0.5(Angular frequency/rad/s)以下であり、該交点の10%以内の近傍に損失弾性率曲線の変曲点が存することを特徴とする、皮膚外用剤。 In the external preparation for skin, the storage elastic modulus with respect to the frequency and the loss elastic modulus of the external preparation for skin are measured using a parallel plate, and the storage elastic modulus curve and the loss elastic modulus curve with respect to the frequency are prepared. The frequency at the intersection of the modulus curve and the loss modulus curve is obtained, and when the frequency and the presence or absence of the inflection point of the loss modulus curve near the intersection are examined, the frequency at the intersection is 0.5 (Angular frequency / rad / s), wherein the inflection point of the loss elastic modulus curve exists in the vicinity of 10% or less of the intersection. 乳化剤形であることを特徴とする、請求項4に記載の皮膚外用剤。 The external preparation for skin according to claim 4, which is in an emulsifier form. 有機変性粘土鉱物を含有する皮膚外用剤であることを特徴とする、請求項4又は5に記載の皮膚外用剤。 The skin external preparation according to claim 4 or 5, wherein the skin external preparation contains an organically modified clay mineral. 前記有機変性粘土鉱物が、ジメチルジステアリルアンモニウムクロリド変性ヘクトライトであることを特徴とする、請求項4〜6何れか1項に記載の皮膚外用剤。 The skin external preparation according to any one of claims 4 to 6, wherein the organically modified clay mineral is dimethyl distearyl ammonium chloride modified hectorite.
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JP2009035512A (en) * 2007-08-02 2009-02-19 Pola Chem Ind Inc Emulsion-form skincare preparation for external use
JP2009286770A (en) * 2008-06-02 2009-12-10 Noevir Co Ltd Method for evaluating effect of liquid oil on skin softening, and skin-care preparation for external use containing the liquid oil, and method for producing the skin-care preparation for external use

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JPH0848618A (en) * 1994-05-11 1996-02-20 Huels Ag Visco-elastic surfactant aqueous solution to clean hair and skin
JP2002249417A (en) * 2001-02-21 2002-09-06 Shiseido Co Ltd Two-layer separative type cosmetic
JP2003121342A (en) * 2001-10-10 2003-04-23 Kao Corp Rodlike cosmetic
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009035512A (en) * 2007-08-02 2009-02-19 Pola Chem Ind Inc Emulsion-form skincare preparation for external use
JP2009286770A (en) * 2008-06-02 2009-12-10 Noevir Co Ltd Method for evaluating effect of liquid oil on skin softening, and skin-care preparation for external use containing the liquid oil, and method for producing the skin-care preparation for external use

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