JP6379472B2 - Sodium hyaluronate function improver - Google Patents
Sodium hyaluronate function improver Download PDFInfo
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本発明は、皮膚に対してヒアルロン酸ナトリウムが有する、保湿機能や、その保持能、使用感等の機能を改善するヒアルロン酸ナトリウムの機能改善剤に関する。 The present invention relates to a function improving agent for sodium hyaluronate which improves functions such as moisturizing function, retention ability and feeling of use, which sodium hyaluronate has on the skin.
従来より、皮膚の乾燥状態を改善するために、優れた保湿剤としてヒアルロン酸ナトリウムが多用されており、化粧料や医薬品分野において重要な成分となっている。しかし、使用時に不快なべたつきを有し、また使用後に水洗いをした場合には保湿効果がなくなってしまうという問題点がある。 Conventionally, sodium hyaluronate has been frequently used as an excellent moisturizing agent in order to improve the dry state of the skin, and has become an important component in the cosmetics and pharmaceutical fields. However, it has an unpleasant stickiness at the time of use, and when it is washed after use, the moisturizing effect is lost.
ヒアルロン酸ナトリウムを用いた具体例としては、例えば、特許文献１に、２−メタクリロイルオキシエチル−２'−（トリメチルアンモニオ）エチルホスフェートのホモポリマーと、ヒアルロン酸ナトリウム等のムコ多糖類とを組み合わせた皮膚外用剤が記載されている。しかし、上記ヒアルロン酸ナトリウムの問題点を解決するには至っていない。また、特許文献２には、２−メタクリロイルオキシエチル−２'−（トリメチルアンモニオ）エチルホスフェート及び（メタ）アクリル酸アルキルエステルの共重合体と、ヒアルロン酸ナトリウム等の酸性ムコ多糖類とを組み合わせた化粧料が記載されている。しかし、水洗い後の保湿効果の低下を減少させるに留まり、ヒアルロン酸ナトリウムの保湿機能を増強させる効果は見出されていない。 As a specific example using sodium hyaluronate, for example, in Patent Document 1, a homopolymer of 2-methacryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate and a mucopolysaccharide such as sodium hyaluronate are combined. Skin external preparations are described. However, the problem of the sodium hyaluronate has not been solved. Patent Document 2 combines 2-methacryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate and a (meth) acrylic acid alkyl ester copolymer with acidic mucopolysaccharides such as sodium hyaluronate. Cosmetics are listed. However, the effect of enhancing the moisturizing function of sodium hyaluronate has not been found, only reducing the decrease in the moisturizing effect after washing with water.
本発明の課題は、皮膚に対してヒアルロン酸ナトリウムが有する、水洗後の保湿機能の低下や、べたつき等の使用感の低下という問題点を解決するに留まらず、ヒアルロン酸ナトリウムの保湿機能をも改善するヒアルロン酸ナトリウムの機能改善剤を提供することにある。 The object of the present invention is not only to solve the problems of sodium hyaluronate on the skin, such as a decrease in moisturizing function after washing with water and a decrease in feeling of use such as stickiness, but also a function of moisturizing sodium hyaluronate. An object of the present invention is to provide a sodium hyaluronate function improving agent that improves.
本発明によれば、式（１）で表される単量体（以下、単量体(1)と略すことがある）７０〜９０モル％と、式（２）で表される単量体（以下、単量体(2)と略すことがある）１０〜３０モル％とを重合して得た重量平均分子量５００，０００〜５，０００，０００の共重合体（以下、共重合体Ａと略すことがある）からなるヒアルロン酸ナトリウムの機能改善剤、ヒアルロン酸ナトリウム、および水からなり、前記機能改善剤の含有量がヒアルロン酸ナトリウムに対して質量比で１〜５倍量である、ヒアルロン酸ナトリウム含有組成物が提供される。
本発明のヒアルロン酸ナトリウム含有組成物は、上記単量体(1)と単量体(2)を特定の割合で特定の重量平均分子量となるように共重合させた共重合体Ａを含むので、ヒアルロン酸ナトリウムが有する、水洗後の保湿機能の低下や、べたつき等の使用感の低下という問題点を解決すると共に、ヒアルロン酸ナトリウムの保湿機能をも増強して改善することができる。また、機能改善剤として共重合体Ａをヒアルロン酸ナトリウムに対して特定の割合で含有しているので、使用感を変えることなく、最も保湿機能を増強して改善することができる。
The sodium hyaluronate-containing composition of the present invention contains the copolymer A obtained by copolymerizing the monomer (1) and the monomer (2) so as to have a specific weight average molecular weight at a specific ratio. In addition to solving the problems of sodium hyaluronate, such as a decrease in moisturizing function after washing and a decrease in feeling of use such as stickiness, the moisturizing function of sodium hyaluronate can be enhanced and improved. Moreover, since the copolymer A is contained as a function improving agent in a specific ratio with respect to sodium hyaluronate, the moisture retention function can be enhanced and improved most without changing the feeling of use.
以下、発明をさらに詳細に説明する。
本発明の機能改善剤は、上記式（１）で表される単量体と上記式（２）で表される単量体とを特定割合で重合して得た、特定の重量平均分子量を有する共重合体Ａを含む。
Hereinafter, the invention will be described in more detail.
The function improver of the present invention has a specific weight average molecular weight obtained by polymerizing a monomer represented by the above formula (1) and a monomer represented by the above formula (2) at a specific ratio. The copolymer A which has is included.
単量体(1)は、２−メタクリロイルオキシエチル−２'−（トリメチルアンモニオ）エチルホスフェート（以下、ＭＰＣと略す）である。この化合物は、例えば、特開昭５４−６３０２５号公報、特開昭５８−１５４５９１号公報、特開昭６３−２２２１８３号公報、特開平５−１０７５１１号公報、特開平６−４１１５７号公報などに記載された合成方法により得ることができる。 The monomer (1) is 2-methacryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate (hereinafter abbreviated as MPC). This compound is disclosed in, for example, JP-A-54-63025, JP-A-58-154591, JP-A-63-222183, JP-A-5-107511, JP-A-6-41157, and the like. It can be obtained by the described synthesis method.
単量体(2)は、ｎ−ブチルメタクリレート（以下、ＢＭＡと略す）であり、例えば、商品名「ライトエステルNB」（共栄社化学(株)製）を用いることができる。 The monomer (2) is n-butyl methacrylate (hereinafter abbreviated as BMA), and for example, trade name “Light Ester NB” (manufactured by Kyoeisha Chemical Co., Ltd.) can be used.
上記重合体Ａを得るための単量体(1)の仕込み割合は７０〜９０モル％であり、好ましくは７５〜８５モル％である。仕込み割合が７０モル％より少なく、また９０モル％より多くなるとヒアルロン酸ナトリウムや皮膚との相互作用が弱くなり、ヒアルロン酸ナトリウムの機能改善効果が不十分となる。 The charging ratio of the monomer (1) for obtaining the polymer A is 70 to 90 mol%, preferably 75 to 85 mol%. When the preparation ratio is less than 70 mol% and more than 90 mol%, the interaction with sodium hyaluronate and the skin becomes weak, and the function improving effect of sodium hyaluronate becomes insufficient.
共重合体Ａの重量平均分子量は５００，０００〜５，０００，０００であり、好ましくは１，０００，０００〜２，０００，０００である。重量平均分子量が５００，０００より小さいとヒアルロン酸ナトリウムや皮膚との相互作用が弱くなり、また５，０００，０００より大きいとハンドリング性が悪くなる。 The weight average molecular weight of the copolymer A is 500,000 to 5,000,000, preferably 1,000,000 to 2,000,000. When the weight average molecular weight is less than 500,000, the interaction with sodium hyaluronate and the skin becomes weak, and when it exceeds 5,000,000, the handling property is deteriorated.
共重合体Ａの重合条件は、本発明の特徴を妨げない範囲で適宜選択でき、また公知の溶液重合、塊状重合、乳化重合、懸濁重合等のいかなる重合方法を使用することができる。好ましい重合方法としては、通常のラジカル反応が用いられ、好ましくは溶液重合により３０〜９０℃で重合を行うのが良い。
重合の際に使用する溶媒としては特に限定されず、例えば、メタノール、エタノール、イソプロパノール等のアルコールや、水、あるいはこれらの混合溶媒を用いることができる。
ラジカル重合の際の重合開始剤としては、通常使用されるものであれば特に限定されず、例えば、アゾビスイソブチロニトリル、アゾビスバレロニトリル等の有機アゾ系開始剤；過酸化ラウロイル、過酸化ベンゾイル、ｔ−ブチルペルオキシネオデカノエート、ｔ−ブチルペルオキシピバレート、コハク酸ジアシルペルオキシド等の有機過酸化物；過硫酸アンモニウム、過硫酸カリウム、過酸化水素等の無機過酸化物などが用いられる。ラジカル重合開始剤の使用量は適宜選択して良いが、原料の全単量体１００質量部に対して０．０１〜３０質量部の割合が好ましい。
The polymerization conditions for the copolymer A can be appropriately selected within the range not impairing the characteristics of the present invention, and any known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like can be used. As a preferable polymerization method, a normal radical reaction is used, and the polymerization is preferably performed at 30 to 90 ° C. by solution polymerization.
The solvent used in the polymerization is not particularly limited, and for example, alcohol such as methanol, ethanol, isopropanol, water, or a mixed solvent thereof can be used.
The polymerization initiator used in radical polymerization is not particularly limited as long as it is usually used. For example, organic azo initiators such as azobisisobutyronitrile and azobisvaleronitrile; lauroyl peroxide, peroxide Organic peroxides such as benzoyl oxide, t-butylperoxyneodecanoate, t-butylperoxypivalate, and diacyl peroxide succinate; inorganic peroxides such as ammonium persulfate, potassium persulfate, and hydrogen peroxide are used. . Although the usage-amount of a radical polymerization initiator may be selected suitably, the ratio of 0.01-30 mass parts is preferable with respect to 100 mass parts of all the monomers of a raw material.
本発明の機能改善剤は、ヒアルロン酸ナトリウムを含有する化粧品等に配合する場合、該ヒアルロン酸ナトリウムに対し、共重合体Ａ量として質量比で０．２〜１０倍量使用することが好ましく、特に、１〜５倍量の使用が、ヒアルロン酸ナトリウムの有する保湿機能を増強して改善する効果が最大となり好ましい。 When the functional improver of the present invention is blended in cosmetics containing sodium hyaluronate, it is preferable to use 0.2 to 10 times as much copolymer A as the amount of copolymer A relative to the sodium hyaluronate. In particular, the use of 1 to 5 times the amount is preferable because the effect of enhancing and improving the moisturizing function of sodium hyaluronate is maximized.
次に本発明について実施例を挙げて説明するが本発明はこれらに限定されない。
合成例１；（共重合体Ａ−１の合成）
ＭＰＣ１６．５８ｇ（７０モル％）、ＢＭＡ３．４２ｇ（３０モル％）をガラス製重合管に秤量し、エタノール１００ｍＬに溶解した。この溶液に窒素を２時間吹き込み、系の温度を６０℃に設定し、重合開始剤としてｔ−ブチルペルオキシネオデカノエートを６ｍｍｏｌ/Lとなるように添加した。引き続いて、６０℃で３時間撹拌後、７０℃で１時間撹拌し、室温に冷却した。反応溶液をエーテル中に滴下し、沈殿した共重合体をろ別し、減圧乾燥することで共重合体Ａ−１を得た。得られた共重合体はゲルパーミエーションクロマトグラフィー（ＧＰＣ）により標準ポリエチレングリコールを用いて分子量を求めた。結果を表１に示す。
Next, although an Example is given and this invention is demonstrated, this invention is not limited to these.
Synthesis Example 1; (Synthesis of Copolymer A-1)
16.58 g (70 mol%) of MPC and 3.42 g (30 mol%) of BMA were weighed in a glass polymerization tube and dissolved in 100 mL of ethanol. Nitrogen was blown into this solution for 2 hours, the temperature of the system was set to 60 ° C., and t-butylperoxyneodecanoate was added as a polymerization initiator so as to be 6 mmol / L. Subsequently, the mixture was stirred at 60 ° C. for 3 hours, then stirred at 70 ° C. for 1 hour, and cooled to room temperature. The reaction solution was dropped into ether, and the precipitated copolymer was filtered off and dried under reduced pressure to obtain copolymer A-1. The molecular weight of the obtained copolymer was determined by gel permeation chromatography (GPC) using standard polyethylene glycol. The results are shown in Table 1.
合成例２〜５；（共重合体Ａ−２〜Ａ−５の合成）
ＭＰＣ量、ＢＭＡ量、重合開始剤量、反応温度及び時間をそれぞれ表１に示す条件に変更し、合成例１と同様に重合を行って、共重合体Ａ−２〜Ａ−５の合成及び分子量の測定を行った。結果を表１に示す。
Synthesis Examples 2 to 5; (Synthesis of Copolymers A-2 to A-5)
The amount of MPC, the amount of BMA, the amount of polymerization initiator, the reaction temperature and the time were changed to the conditions shown in Table 1, respectively, and polymerization was carried out in the same manner as in Synthesis Example 1 to synthesize copolymers A-2 to A-5 and The molecular weight was measured. The results are shown in Table 1.
参考例１〜５：（重合体Ｂ−１、共重合体Ｂ−２〜Ｂ−５の合成）
ＭＰＣ量、ＢＭＡ量、重合開始剤量、反応温度及び時間をそれぞれ表２に示す条件に変更し、合成例１と同様に重合を行って、重合体Ｂ−１、共重合体Ｂ−２〜Ｂ−５の合成及び分子量の測定を行った。結果を表２に示す。
Reference Examples 1 to 5: (Synthesis of polymer B-1 and copolymers B-2 to B-5)
The amount of MPC, the amount of BMA, the amount of polymerization initiator, the reaction temperature and the time were changed to the conditions shown in Table 2, respectively, and polymerization was carried out in the same manner as in Synthesis Example 1 to obtain a polymer B-1, a copolymer B-2 to Synthesis of B-5 and measurement of molecular weight were performed. The results are shown in Table 2.
実施例１−１
合成例１で得られた共重合体Ａ−１ ０．１ｇ、水８９．９ｇを２５０ｍＬのガラスビーカーにとり、室温にて３０分間スターラー撹拌し、溶解させ、ヒアルロン酸ナトリウムの機能改善剤を調製した。この機能改善剤に、１％ヒアルロン酸ナトリウム水溶液(BIO- SODIUM HYALURONATE １％ SOLUTION, Bioland社製）１０ｇを添加し、３０分間スターラー撹拌して水溶液を得た。得られた水溶液を用いて、下記に示す保湿性、耐洗性の評価、並びに塗布時のべたつきの評価を行った。結果を表３に示す。
Example 1-1
0.1 g of copolymer A-1 obtained in Synthesis Example 1 and 89.9 g of water were placed in a 250 mL glass beaker, stirred at room temperature for 30 minutes with a stirrer, and dissolved to prepare a function improving agent for sodium hyaluronate. . To this function improver, 10 g of 1% sodium hyaluronate aqueous solution (BIO-SODIUM HYALURONATE 1% SOLUTION, manufactured by Bioland) was added, and stirred for 30 minutes to obtain an aqueous solution. Using the obtained aqueous solution, the following evaluations of moisture retention and washing resistance and evaluation of stickiness during coating were performed. The results are shown in Table 3.
＜保湿性の評価＞
２０〜６５歳の男女２０人を対象として、恒温・恒湿環境下に十分馴化させた。その後、前腕内側部に調製した水溶液を塗布し、１時間後に皮表角層水分量測定装置(SKICON- 200EX,アイ・ビイ・エス(株)製）を用いて角層水分量を測定した。塗布前の値を１とした相対値を算出し、２０名の平均をとり判定した。値が大きいほど角層水分量の向上率が高く、保湿性に優れる。
<Evaluation of moisture retention>
Twenty men and women between the ages of 20 and 65 were fully acclimatized in a constant temperature and humidity environment. Then, the prepared aqueous solution was applied to the inner side of the forearm, and after 1 hour, the stratum corneum moisture content was measured using a skin surface stratum corneum moisture measuring device (SKICON-200EX, manufactured by IBI S Co., Ltd.). A relative value was calculated with a value before application being 1, and an average of 20 persons was determined. The larger the value, the higher the stratum corneum moisture content improvement rate, and the better the moisture retention.
＜耐洗性の評価＞
２０〜６５歳の男女２０人を対象として、恒温・恒湿環境下に十分馴化させた。その後、前腕内側部に調製した水溶液を塗布し、１時間後に水洗した。乾燥させ、１時間後に皮表角層水分量測定装置(SKICON- 200EX,アイ・ビイ・エス(株)製）を用いて角層水分量を測定した。塗布前の値を１とした相対値を算出し、２０名の平均をとり判定した。値が大きいほど角層水分量が高く、耐洗性に優れる。
<Evaluation of washing resistance>
Twenty men and women between the ages of 20 and 65 were fully acclimatized in a constant temperature and humidity environment. Then, the prepared aqueous solution was apply | coated to the forearm inner side part, and it washed with water after 1 hour. After drying, the stratum corneum moisture content was measured after 1 hour using a skin surface stratum corneum moisture measuring device (SKICON-200EX, manufactured by IBS Co., Ltd.). A relative value was calculated with a value before application being 1, and an average of 20 persons was determined. The larger the value, the higher the stratum corneum moisture content and the better the washing resistance.
＜べたつきの評価＞
２０〜６５歳の男女２０人を対象として、下記の評価基準に従い、水溶液塗布時のべたつきについて評価した。平均値を結果とした。
５：非常に良好、４：良好、３：普通、２：不良、１：非常に不良。
<Evaluation of stickiness>
Twenty men and women aged 20 to 65 years old were evaluated for stickiness during application of an aqueous solution according to the following evaluation criteria. The average value was the result.
5: Very good, 4: Good, 3: Normal, 2: Poor, 1: Very bad.
実施例１−２〜１−８
共重合体Ａとして表３に示す各共重合体Ａ−１〜Ａ−５を用い、表中の各割合にて実施例１−１と同様な方法でヒアルロン酸ナトリウムの機能改善剤を調製した。得られた機能改善剤に、表３に示す量の１％ヒアルロン酸ナトリウム水溶液を添加し、実施例１−１と同様に水溶液を得た。得られた水溶液について実施例１−１と同様に各評価を行った。結果を表３に示す。
Examples 1-2 to 1-8
Using each of the copolymers A-1 to A-5 shown in Table 3 as the copolymer A, a function improving agent for sodium hyaluronate was prepared in the same manner as in Example 1-1 at each ratio in the table. . To the obtained function improver, 1% aqueous sodium hyaluronate solution in the amount shown in Table 3 was added to obtain an aqueous solution in the same manner as in Example 1-1. Each evaluation was performed similarly to Example 1-1 about the obtained aqueous solution. The results are shown in Table 3.
比較例１−１〜１−５
表４に示す組成で水にヒアルロン酸ナトリウム水溶液を添加した水溶液を用いて、実施例１−１と同様に各評価を行った。結果を表４に示す。
Comparative Examples 1-1 to 1-5
Each evaluation was performed in the same manner as in Example 1-1 using an aqueous solution in which a sodium hyaluronate aqueous solution was added to water with the composition shown in Table 4. The results are shown in Table 4.
比較例１−６〜１−１０
表４に示す組成で実施例１−１と同様にヒアルロン酸ナトリウムの機能改善剤を調製した。この機能改善剤のみを用いて、実施例１−１と同様に各評価を行った。結果を表４に示す。
Comparative Examples 1-6 to 1-10
A function improving agent for sodium hyaluronate having the composition shown in Table 4 was prepared in the same manner as in Example 1-1. Each evaluation was performed in the same manner as in Example 1-1 using only this function improver. The results are shown in Table 4.
比較例１−１１〜１−１５
表４に示す組成で実施例１−１と同様に重合体Ｂ−１、共重合体Ｂ−２〜Ｂ−５を水に溶解させ、重合体水溶液を調製した。得られた重合体水溶液に、実施例１−１と同様に表４に示した量の１％ヒアルロン酸ナトリウム水溶液を添加して水溶液を得た。得られた水溶液について、実施例１−１と同様に各評価を行った。結果を表４に示す。
Comparative Examples 1-11 to 1-15
Polymer B-1 and copolymers B-2 to B-5 having the composition shown in Table 4 were dissolved in water in the same manner as in Example 1-1 to prepare a polymer aqueous solution. 1% sodium hyaluronate aqueous solution in the amount shown in Table 4 was added to the obtained polymer aqueous solution in the same manner as in Example 1-1 to obtain an aqueous solution. Each evaluation was performed similarly to Example 1-1 about the obtained aqueous solution. The results are shown in Table 4.
比較例１−１６〜１−２０
表５に示す組成でグリセリン（ＲＧ・コ・Ｐ, 日油(株)製）と水を混合し、グリセリン水溶液を調製した。得られたグリセリン水溶液に、実施例１−１と同様に表５に示した量の１％ヒアルロン酸ナトリウム水溶液を添加して水溶液を得た。得られた水溶液について、実施例１−１と同様に各評価を行った。結果を表５に示す。
Comparative Examples 1-16 to 1-20
Glycerin (RG · Co · P, manufactured by NOF Corporation) and water were mixed with the composition shown in Table 5 to prepare an aqueous glycerin solution. 1% sodium hyaluronate aqueous solution in the amount shown in Table 5 was added to the obtained glycerin aqueous solution in the same manner as in Example 1-1 to obtain an aqueous solution. Each evaluation was performed similarly to Example 1-1 about the obtained aqueous solution. The results are shown in Table 5.
表３〜５より、実施例で用いた水溶液は比較例で用いた水溶液と比較して、保湿性、耐洗性、べたつきのなさのいずれの評価項目においても優れていた。従って、本発明の機能改善剤が、皮膚に対してヒアルロン酸ナトリウムが有する、水洗後の保湿機能の低下や、べたつき等の使用感の低下という問題点を解決すると共に、ヒアルロン酸ナトリウムの保湿機能をも増強して改善することがわかった。特に、本発明の機能改善剤を、ヒアルロン酸ナトリウムに対して共重合体Ａ換算で、１〜５倍の質量比で使用することにより、保湿機能の増強効果が最大となることが明らかになった。 From Tables 3-5, compared with the aqueous solution used by the comparative example, the aqueous solution used by the Example was excellent in all the evaluation items of moisture retention, washing resistance, and non-stickiness. Therefore, the function improving agent of the present invention solves the problems of lowering the moisturizing function after washing with water and lowering the feeling of use such as stickiness, which sodium hyaluronate has on the skin, and also moisturizing function of sodium hyaluronate. It has been found that the improvement is also enhanced. In particular, it becomes clear that the effect of enhancing the moisturizing function is maximized by using the function improver of the present invention in a mass ratio of 1 to 5 times in terms of copolymer A with respect to sodium hyaluronate. It was.
Claims (1)
ヒアルロン酸ナトリウム、および
水からなり、前記機能改善剤の含有量がヒアルロン酸ナトリウムに対して質量比で１〜５倍量である、ヒアルロン酸ナトリウム含有組成物。
Sodium hyaluronate, and
A sodium hyaluronate-containing composition comprising water and having a function ratio of 1 to 5 times the mass ratio of sodium hyaluronate .
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