JP4162835B2 - Cosmetics - Google Patents

Description

【０００９】
（式中、Ｘは−ＣＨ（ＯＨ）−又は−ＣＯ−である。）
【００１０】
【発明の実施の形態】
以下、本発明の実施形態について詳述する。
【００１１】
一般式（１）で示される化合物は、ピペリルとピペロインである。
【００１２】
ピペロインは、次の式で示される化合物であり、別名ピペロニロイン、ピペロノイン、３，４，３’，４’−ジメチレンジオキシベンゾインとも言い、ピペロナールをシアン化カリウムと希アルコール中で煮沸することにより容易に得られる。
【００１３】
【化３】

【００１４】
ピペリルは、次の式で示される化合物であり、別名ピペロイルとも言い、ピペロインをフェーリング液と加熱するか、空気を通じながら水酸化カリウム水溶液と煮沸することにより容易に得られる。
【００１５】
【化４】

【００１６】
上記一般式（１）で示される化合物の化粧料中への配合量は、化粧料総量を基準として、好ましくは、０．０１〜５．０質量％（以下、単に％と記する）であり、更に好ましくは０．０５〜３．０％である。
【００１７】
配合量が０．０１％未満では本発明の目的とする効果が十分に得られない場合があり、配合量が５．０％を超えても、その増加分に見合った効果の向上は望めない場合があり、使用時の感触が悪くなり易く、個々の剤型を保持し難くなる場合がある。
【００１８】
本発明の化粧料は、一般に皮膚に塗布する形の化粧料であれば特に限定されず、通常の皮膚化粧料の他、下地化粧料やファンデーションとしても利用可能であり、入浴剤として用いてもよい。剤型としては、一般に用いられる、水溶液、Ｗ／Ｏ型又はＯ／Ｗ型エマルション、適当な賦形剤等を用いて顆粒剤その他の粉末、錠剤等とすることが考えられ、具体的にはクリーム、乳液、化粧水、パック、ジェル、スティック、シート、パップ等が挙げられる。この化粧料は、例えば、乳液等の場合、油相及び水相をそれぞれ加熱溶解し、乳化分散して冷却する通常の方法により製造することができる。
【００１９】
尚、本発明の化粧料には、上記の他、タール系色素、酸化鉄等の着色顔料、パラベン等の防腐剤、脂肪酸セッケン、セチル硫酸ナトリウム等の陰イオン性界面活性剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン多価アルコール脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油、多価アルコール脂肪酸エステル、ポリグリセリン脂肪酸エステル等の非イオン性界面活性剤、テトラアルキルアンモニウム塩等の陽イオン性界面活性剤、ベタイン型、スルホベタイン型、スルホアミノ酸型、Ｎ−ステアロイル−Ｌ−グルタミン酸ナトリウム等の両イオン性界面活性剤、レシチン、リゾフォスファチジルコリン等の天然系界面活性剤、ゼラチン、カゼイン、デンプン、アラビアガム、カラヤガム、グアガム、ローカストビーンガム、ドラガカントガム、クインスシード、ペクチン、カラギーナン、アルギン酸ソーダ等の天然高分子、メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロースナトリウム、エチルセルロース等の半合成高分子、ポリビニルアルコール、ポリビニルメチルエーテル及びコーポリマー、ポリビニルピロリドン、ポリアクリル酸ソーダ、カルボキシビニルポリマー、ポリエチレンオキシドポリマー等の合成高分子、キサンテンガム等の増粘剤、酸化チタン等の顔料、ジブチルヒドロキシトルエン等の抗酸化剤等を、本発明の目的を損なわない範囲内で適宜配合することができる。
【００２０】
【実施例】
以下、実施例、製造例及び比較例に基づいて本発明を詳細に説明する。尚、本発明はこれらに限定されるものではない。
【００２１】
（１）メラニン生成抑制試験
Ｂ１６メラノーマ細胞を３×１０⁴個／ｗｅｌｌで２４穴プレートに播き、２４時間後、各試料化合物を含有したＴｈｅｏｐｈｙｌｌｉｎｅ入り培地に交換した。７２時間培養を行い細胞数を求めた後、続いて細胞を１０％ＴＣＡ，エタノール／ジエチルエーテル（＝１／１）で処理した。続いて、１０％ジメチルスルホキシドを含有する１ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解後のＯＤ４７５値を求めてメラニン量とし、細胞あたりのメラニン生成の抑制率（％）を求めた。表１に試験結果を示した。
【００２２】

【００２３】
後記の実施例及び比較例の化粧料に関して実施した美白実用試験の試験法は次の通りである。
【００２４】
・美白実用試験
夏期の太陽光に３時間（１日１．５時間で２日間）曝された被試験者２０名の前腕屈側部皮膚を対象として、左前腕屈側部皮膚には太陽光に曝された日より試料を、右前腕屈側部皮膚には太陽光に曝された日よりベースを朝夕１回ずつ１３週連続塗布した。尚、評価は、専門官による目視によりベース塗布部より試料塗布部において美白効果を確認された被験者の人数で示した。
【００２５】
実施例６〜７、比較例３（スキンローション）
表２の原料組成において、表３に記載の有効成分を配合して、スキンローションを調製し、前記の美白実用試験を実施した。
【００２６】
・調製法
表２に記載のＢ成分をＣ成分中に、均一に溶解した後、Ａ成分とＣ成分を均一に混合攪拌、分散し次いで容器に充填した。
【００２７】

【００２８】

【００２９】
・特性
試験を実施した結果を表３に記載した。表３に示す如く、本発明の化粧料である実施例６及び７は明らかに良好な結果を示した。尚、皮膚刺激反応又は皮膚感作反応を示した被試験者は生じなかった。
【００３０】
実施例８〜９、比較例４（スキンクリーム）
表４の原料組成において、表５に記載の如く有効成分を配合して、スキンクリームを調製し、前記美白実用試験を実施した。
【００３１】
・調製法
表４に記載のＡ成分と、Ｂ成分をＣ成分に混合したものとを、それぞれ均一に加熱溶解して温度を８０℃にする。次いで、Ａ成分中にＣ成分を注入乳化した後、攪拌しながら３０℃まで冷却した。
【００３２】

【００３３】

【００３４】
（２）特性
結果を表５に記載した。表５に示す如く、実施例８及び９は、明らかに良好な結果を示した。尚、皮膚刺激反応又は皮膚感作反応を示した被試験者は生じなかった。
【００３５】
【発明の効果】
以上記載の如く、本発明のピペロイン及び／又はピペリルを含有する化粧料は、メラニン色素の産生抑制効果に優れ、皮膚刺激が無い等、安全性及び使用感に優れた化粧料として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cosmetic, and more particularly to a cosmetic having an effect of suppressing skin blackening due to ultraviolet rays and a high safety and usability.
[0002]
[Prior art]
When ultraviolet rays are exposed to the skin, the skin is affected in various ways. At that time, active oxygen, lipid peroxide, and the like generated in the skin cause inflammation and cause great damage to the skin tissue. These damages cause loss of moisture, texture, texture, etc. of the skin, and further affect the dermis, forming wrinkles and the like and causing light aging. In addition, as one of the causes of skin color change and darkening, active oxygen generated by ultraviolet rays and various factors released from surrounding cells activate melanocytes and increase tyrosinase activity, resulting in excessive production of melanin. It is thought to be delivered to epidermal cells. Melanin is produced by oxidation of tyrosine, and as a result, the skin tone is changed and blackened.
[0003]
Therefore, in order to show the whitening effect, it is important to suppress melanin production. Conventionally, whitening cosmetics containing kojic acid, arbutin, hydroquinone monobenzyl ether, hydrogen peroxide and the like have been proposed in order to prevent darkening, blotches and freckles in the skin and to keep the original white skin. Moreover, vitamin C etc. are proposed in order to suppress the inflammation by ultraviolet rays.
[0004]
[Problems to be solved by the invention]
When arbutin, kojic acid, hydroquinone monobenzyl ether, etc. are blended, there is an effect of slightly fading the skin of dark black, but it does not reach the desired level. There may also be problems with the safety of the skin. As a compound similar to the compound used in the present invention, sesamol having an antioxidative ability and a whitening effect can be mentioned, but it exhibits strong sensitization and is unsuitable for use as a cosmetic. As described above, it is extremely difficult to obtain a cosmetic having an excellent whitening effect, high skin safety, and sufficient storage stability.
[0005]
Under such circumstances, an object of the present invention is to provide a cosmetic material that has an excellent whitening effect, a high skin safety in the preparation, and an excellent usability.
[0006]
[Means for Solving the Problems]
In light of such circumstances, the present inventors have conducted extensive research to improve the difficulties of the prior art, and as a result, found that the specific compound used in the present invention has a remarkably excellent whitening effect, It was possible to provide cosmetics with high skin safety and excellent usability.
[0007]
In order to achieve the above object, the cosmetic of the present invention has the following configuration. That is, it is a cosmetic characterized by containing piperoin and / or piperyl represented by the following general formula (1).
[0008]
[Chemical 2]

[0009]
(In the formula, X is —CH (OH) — or —CO—).
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0011]
The compounds represented by the general formula (1) are piperyl and piperoin.
[0012]
Piperoin is a compound represented by the following formula, also known as piperoniloin, piperonoin, 3,4,3 ′, 4′-dimethylenedioxybenzoin, and is easily obtained by boiling piperonal in potassium cyanide and dilute alcohol. It is done.
[0013]
[Chemical 3]

[0014]
Piperyl is a compound represented by the following formula, which is also called piperoyl, and is easily obtained by heating piperoin with a Feling solution or boiling with an aqueous potassium hydroxide solution through the air.
[0015]
[Formula 4]

[0016]
The amount of the compound represented by the general formula (1) in the cosmetic is preferably 0.01 to 5.0% by mass (hereinafter simply referred to as%) based on the total amount of the cosmetic. More preferably, it is 0.05 to 3.0%.
[0017]
If the blending amount is less than 0.01%, the intended effect of the present invention may not be sufficiently obtained, and even if the blending amount exceeds 5.0%, improvement in the effect commensurate with the increase cannot be expected. In some cases, the feel during use tends to be poor, and it is difficult to maintain individual dosage forms.
[0018]
The cosmetic of the present invention is not particularly limited as long as it is generally applied to the skin, and can be used as a base cosmetic or foundation in addition to normal skin cosmetics, and can be used as a bath agent. Good. As the dosage form, it is possible to use a commonly used aqueous solution, W / O type or O / W type emulsion, appropriate excipients, etc. to form granules or other powders, tablets, etc., specifically Examples include creams, emulsions, lotions, packs, gels, sticks, sheets, and pops. For example, in the case of a milky lotion, this cosmetic can be produced by an ordinary method in which an oil phase and an aqueous phase are heated and dissolved, emulsified and dispersed, and then cooled.
[0019]
In addition to the above, the cosmetics of the present invention include tar dyes, colored pigments such as iron oxide, preservatives such as parabens, anionic surfactants such as fatty acid soap, sodium cetyl sulfate, and polyoxyethylene alkyl. Ether, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene hydrogenated castor oil, polyhydric alcohol fatty acid ester, polyglycerin fatty acid ester and other nonionic surfactants, tetraalkylammonium salt and other positive ions Ionic surfactants, betaine types, sulfobetaine types, sulfoamino acid types, amphoteric surfactants such as sodium N-stearoyl-L-glutamate, natural surfactants such as lecithin and lysophosphatidylcholine, gelatin , Casein, starch, gum arabic, karayaga , Guar gum, locust bean gum, dragagacanto gum, quince seed, pectin, carrageenan, sodium alginate, etc., semi-synthetic polymers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, polyvinyl methyl Synthetic polymers such as ethers and copolymers, polyvinylpyrrolidone, polyacrylic acid soda, carboxyvinyl polymer, polyethylene oxide polymer, thickeners such as xanthene gum, pigments such as titanium oxide, antioxidants such as dibutylhydroxytoluene, etc. , And can be appropriately blended within a range not impairing the object of the present invention.
[0020]
【Example】
Hereinafter, the present invention will be described in detail based on examples, production examples, and comparative examples. In addition, this invention is not limited to these.
[0021]
(1) Melanin production inhibition test B16 melanoma cells were seeded on a 24-well plate at 3 × 10 ⁴ cells / well, and after 24 hours, the medium was replaced with a theophylline-containing medium containing each sample compound. After culturing for 72 hours to determine the number of cells, the cells were subsequently treated with 10% TCA, ethanol / diethyl ether (= 1/1). Subsequently, the OD475 value after dissolution in a 1 mol / L sodium hydroxide aqueous solution containing 10% dimethyl sulfoxide was determined to obtain the amount of melanin, and the inhibition rate (%) of melanin production per cell was determined. Table 1 shows the test results.
[0022]

[0023]
The test methods of the whitening practical test conducted on the cosmetics of Examples and Comparative Examples described later are as follows.
[0024]
・ Whitening Practical Test Sunlight was applied to the left forearm bent side skin of 20 test subjects exposed to the sun in summer for 3 hours (1.5 hours per day for 2 days). The sample was applied to the right forearm flexor side skin from the day exposed to the sun, and the base was applied once a morning and evening for 13 weeks continuously from the day exposed to sunlight. The evaluation was shown by the number of subjects whose whitening effect was confirmed in the sample application part from the base application part by visual inspection by a specialist.
[0025]
Examples 6-7, Comparative Example 3 (skin lotion)
In the raw material composition shown in Table 2, the active ingredients shown in Table 3 were blended to prepare a skin lotion, and the whitening practical test was conducted.
[0026]
Preparation Method After the B component described in Table 2 was uniformly dissolved in the C component, the A component and the C component were uniformly mixed and stirred, dispersed, and then filled into a container.
[0027]

[0028]

[0029]
The results of the characteristic test are shown in Table 3. As shown in Table 3, the cosmetics of the present invention, Examples 6 and 7, clearly showed good results. In addition, the test subject who showed skin irritation reaction or skin sensitization reaction did not occur.
[0030]
Examples 8-9, comparative example 4 (skin cream)
In the raw material composition shown in Table 4, active ingredients were blended as shown in Table 5 to prepare a skin cream, and the whitening practical test was conducted.
[0031]
Preparation method A component described in Table 4 and a mixture of B component and C component are heated and dissolved uniformly to bring the temperature to 80 ° C. Next, the component C was injected into the component A and emulsified, and then cooled to 30 ° C. with stirring.
[0032]

[0033]

[0034]
(2) The characteristic results are shown in Table 5. As shown in Table 5, Examples 8 and 9 clearly showed good results. In addition, the test subject who showed skin irritation reaction or skin sensitization reaction did not occur.
[0035]
【The invention's effect】
As described above, the cosmetics containing piperoin and / or piperyl of the present invention are useful as cosmetics having excellent safety and feeling of use, such as excellent melanin pigment production inhibitory effect and no skin irritation.

Claims (1)

A cosmetic comprising piperoin and / or piperyl represented by the following general formula (1).

(In the formula, X is —CH (OH) — or —CO—).