JPH0532531A - Cosmetic - Google Patents

Cosmetic

Info

Publication number
JPH0532531A
JPH0532531A JP20980891A JP20980891A JPH0532531A JP H0532531 A JPH0532531 A JP H0532531A JP 20980891 A JP20980891 A JP 20980891A JP 20980891 A JP20980891 A JP 20980891A JP H0532531 A JPH0532531 A JP H0532531A
Authority
JP
Japan
Prior art keywords
cosmetic
skin
acid
tetraenedicarboxylic
tetraene
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.)
Granted
Application number
JP20980891A
Other languages
Japanese (ja)
Other versions
JP2977961B2 (en
Inventor
Fumiaki Matsuzaki
文昭 松崎
Toshio Hariki
利男 梁木
Michihiro Yamaguchi
道広 山口
Kazuo Komatsu
一男 小松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shiseido Co Ltd
Original Assignee
Shiseido Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shiseido Co Ltd filed Critical Shiseido Co Ltd
Priority to JP3209808A priority Critical patent/JP2977961B2/en
Publication of JPH0532531A publication Critical patent/JPH0532531A/en
Application granted granted Critical
Publication of JP2977961B2 publication Critical patent/JP2977961B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Abstract

PURPOSE:To obtain a cosmetic having high utility, suppressing inflammation of skin caused by ultraviolet rays, preventing blackening of skin resulting from melanism and skin cancer, containing a specific tetraenedicarboxylic acid or a derivative thereof. CONSTITUTION:A cosmetic containing preferably 0.01-10wt.%, based on the whole amount of cosmetic, of a tetraenedicarboxylic acid shown by the formula (R is H, alkyl, alkenyl, aryl, alkali metal, alkaline earth metal or amine) or salt thereof. The compound shown by the formula has the maximum absorption wavelength at approximately 338nm, excellent UV-A screening effects and excellent utility. Having high water solubility, the tetraenedicarboxylic acid is preferably applied to a cosmetic of aqueous solution and an ester thereof to an oily cosmetic because solubility in an oily component is increased by the esterification.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、紫外線遮断効果の高い
化粧料に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic having a high UV blocking effect.

【0002】[0002]

【従来の技術】一般に、戸外において皮膚に対して過度
の紫外線を浴びると、日光暴露後、数時間でサンバーン
が起こり、ひどくなると火ぶくれを起こす。さらに、引
き続いてメラニン色素の沈着が生じ皮膚が黒化する。こ
のように、過度の紫外線暴露は、美的観点からも、また
皮膚の健康上からも極めて有害である。
2. Description of the Related Art Generally, when the skin is exposed to excessive ultraviolet rays outdoors, sunburn occurs several hours after exposure to the sun, and when it becomes severe, it causes blisters. Furthermore, the melanin pigment is subsequently deposited and the skin is blackened. Thus, excessive UV exposure is extremely harmful from the aesthetic point of view and the health of the skin.

【0003】これまでは上記症状の原因として、地上に
到達する紫外線の中でも290〜320nmの中波長紫
外線(以下UV−Bという)が重要視され、これを防ぐ
ためケイ皮酸エステル系、ベンゾフェノン系、サリチル
酸エステル系など多くの紫外線吸収剤が開発されてい
る。
Until now, as the cause of the above-mentioned symptoms, mid-wavelength ultraviolet rays (hereinafter referred to as UV-B) of 290 to 320 nm have been regarded as important among the ultraviolet rays reaching the ground. , Many salicylic acid ester-based UV absorbers have been developed.

【0004】しかし、近年皮膚の黒化、さらには皮膚癌
に対する紫外線の影響に関する研究が進み、UV−Bと
同様に320〜400nmの長波長紫外線(以下UV−
Aという)も上記症状の原因となることが明らかになっ
た。このUV−Aを防ぐために配合される化粧料用紫外
線吸収剤としては、ベンゾフェノン系やジベンゾイルメ
タン系の紫外線吸収剤が一般的である。
However, in recent years, studies on the effects of ultraviolet rays on skin darkening and skin cancer have progressed, and like UV-B, long-wavelength ultraviolet rays of 320 to 400 nm (hereinafter UV-
It is also clear that (A) causes the above symptoms. A benzophenone-based or dibenzoylmethane-based UV absorber is generally used as a UV absorber for cosmetics that is added to prevent UV-A.

【0005】しかしながら、ベンゾフェノン系紫外線吸
収剤はUV−A,B両領域に吸収を持つが、吸収能が小
さくしかもUV−A領域の吸収能は相対的に低い。従っ
て、充分な効果を得るにはかなり多量に配合しなければ
ならないため、安全性上問題があるといわれている。ま
た、ジベンゾイルメタン系の紫外線吸収剤は、UV−A
領域にも比較的高い吸収能を持つが、重金属やアミン類
と反応してこれが衣類に付着すると衣類が黄色く染まる
という化粧品としての使用性に大きな問題がある。
However, the benzophenone type ultraviolet absorber has absorption in both UV-A and B regions, but its absorption capacity is small and its absorption capacity in the UV-A region is relatively low. Therefore, it is said that there is a safety problem because a considerably large amount must be added to obtain a sufficient effect. Further, the dibenzoylmethane-based ultraviolet absorber is UV-A.
It also has a relatively high absorption capacity in the region, but when it reacts with heavy metals and amines and adheres to clothes, the clothes are dyed yellow, which poses a serious problem in terms of usability as a cosmetic product.

【0006】一方、以上述べた問題点を少しでも軽減す
るため、実際の化粧料には上記紫外線吸収剤とともに、
紫外線を物理的に反射・散乱させる酸化チタン等の無機
粉末を使用することが多い。しかしながら、塗布時の使
用感が悪化することや、また特にローションタイプやオ
イルタイプの製品には適用しにくい等、配合し得る剤型
が限定されるという問題がある。
On the other hand, in order to alleviate the above-mentioned problems, the actual cosmetic composition contains the above-mentioned ultraviolet absorber,
Inorganic powder such as titanium oxide that physically reflects and scatters ultraviolet rays is often used. However, there is a problem that the formulation that can be blended is limited, such that the usability during application is deteriorated, and that it is difficult to apply it particularly to lotion type and oil type products.

【0007】以上述べたように、現在、UV−A及びU
V−Bの紫外線遮断効果を有し、しかも安全性、使用性
の高い化粧料が強く望まれている。
As mentioned above, at present, UV-A and U
There is a strong demand for cosmetics that have the UV blocking effect of V-B and are highly safe and easy to use.

【0008】[0008]

【発明が解決しようとする課題】本発明は、高い使用性
を有すと共に、紫外線による皮膚の炎症を抑制し、メラ
ニン生成に起因する皮膚の黒化を予防さらには皮膚癌を
予防し得る新規な化粧料を提供することを目的とする。
DISCLOSURE OF THE INVENTION The present invention has high usability, suppresses skin inflammation caused by ultraviolet rays, prevents skin blackening due to melanin production, and can prevent skin cancer. The purpose is to provide a variety of cosmetics.

【0009】[0009]

【課題を解決するための手段】本発明の第1の要旨は、
下記一般式(I)で示されるテトラエンジカルボン酸ま
たはその誘導体を含むことを特徴とする化粧料に存在す
る。 ROOC-CH=CH-CH=CH-CH=CH-CH=CH-COOR (I) (式中、Rは水素又は直鎖状、分岐状のアルキル基、ア
ルケニル基、アリール基及びアルカリ金属、アルカリ土
類金属、アミン類を表わす。)また第2の要旨は、第1
の要旨において、前記テトラエンジカルボン酸誘導体の
配合量が化粧料全量中0.01〜10重量%であること
を特徴とする化粧料に存在する。
The first gist of the present invention is as follows.
The present invention provides a cosmetic characterized by containing a tetraene dicarboxylic acid represented by the following general formula (I) or a derivative thereof. ROOC-CH = CH-CH = CH-CH = CH-CH = CH-COOR (I) (In the formula, R represents hydrogen or a linear or branched alkyl group, alkenyl group, aryl group and alkali metal, alkali Represents earth metals and amines.) The second gist is the first
In the summary, the present invention is a cosmetic characterized in that the tetraene dicarboxylic acid derivative is contained in an amount of 0.01 to 10% by weight based on the total amount of the cosmetic.

【0010】[0010]

【作用】以下、本発明の作用及び構成を詳細に説明す
る。
The function and structure of the present invention will be described in detail below.

【0011】本発明者らは化粧料用の紫外線吸収剤を鋭
意研究開発する過程で、350nm付近に吸収極大を有
す物質が良好なUV−A遮断効果を持ち、特にテトラエ
ンジカルボン酸誘導体を配合させると、十分なUV−A
遮断効果と優れた使用性を持つ化粧料が得られることを
発見した。
In the process of earnestly researching and developing an ultraviolet absorber for cosmetics, the present inventors have found that a substance having an absorption maximum near 350 nm has a good UV-A blocking effect, and particularly a tetraenedicarboxylic acid derivative. Sufficient UV-A when blended
It was discovered that a cosmetic having a blocking effect and excellent usability can be obtained.

【0012】本発明に適用されるテトラエンジカルボン
酸及び誘導体は一般式(I)に示される物質であり、
J.Amer.Chem.Soc.,92,5480
(1970)に記載されるように、338nm付近に最
大吸収波長(λmax)を有する化合物である。
The tetraene dicarboxylic acids and derivatives applicable to the present invention are substances represented by the general formula (I),
J. Amer. Chem. Soc. , 92, 5480
As described in (1970), it is a compound having a maximum absorption wavelength (λ max ) near 338 nm.

【0013】本発明において、テトラエンジカルボン酸
は、(I)式で示されるように、酸、塩、またはエステ
ルとして用いられる。
In the present invention, the tetraene dicarboxylic acid is used as an acid, salt or ester as shown by the formula (I).

【0014】テトラエンジカルボン酸の塩は、テトラエ
ンジカルボン酸と塩形成物質と反応させることにより得
られる。ここで、塩形成物質としては、例えば水酸化リ
チウム、水酸化ナトリウム、水酸化カリウム、水酸化カ
ルシウム、水酸化マグネシウム等の無機塩基、例えばア
ルギニン、リジン、ヒスチジン等の塩基性アミノ酸、例
えばモノエタノールアミン、ジエタノールアミン、トリ
エタノールアミン等の有機塩基が用いられる。またこれ
らの塩は以上述べたように予め作製しておいてそれを添
加して用いてもよいし、テトラエンジカルボン酸と塩形
成物質を別々に添加して処方中で反応させて用いてもよ
い。
The salt of tetraene dicarboxylic acid can be obtained by reacting tetraene dicarboxylic acid with a salt-forming substance. Here, examples of the salt-forming substance include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide, basic amino acids such as arginine, lysine, and histidine, such as monoethanolamine. , Organic bases such as diethanolamine and triethanolamine are used. Further, these salts may be prepared in advance as described above and added to them, or they may be used by adding tetraenedicarboxylic acid and a salt-forming substance separately and reacting in the formulation. Good.

【0015】テトラエンジカルボン酸塩は、水への溶解
度が高いため、例えば化粧水等の水溶液系の化粧料に特
に好適に適用される。
Since the tetraene dicarboxylic acid salt has a high solubility in water, it is particularly suitably applied to an aqueous solution type cosmetic such as a lotion.

【0016】テトラエンジカルボン酸エステルは、例え
ばテトラエンジカルボン酸とアルコールの縮合反応等に
より製造することができる。アルコールとしては、例え
ば直鎖状、分岐状、環状のアルキル、アルケニル、アリ
ールアルコールが挙げられる。具体的には、例えばメタ
ノール、エタノール、プロパノール、ヘキシルアルコー
ル、セチルアルコール、アリルアルコール、オレイルア
ルコール、フェニルアルコール等である。
The tetraene dicarboxylic acid ester can be produced, for example, by a condensation reaction of tetraene dicarboxylic acid and alcohol. Examples of alcohols include linear, branched, and cyclic alkyl, alkenyl, and aryl alcohols. Specific examples include methanol, ethanol, propanol, hexyl alcohol, cetyl alcohol, allyl alcohol, oleyl alcohol, phenyl alcohol and the like.

【0017】エステルとすることにより、油性成分に対
する溶解度が向上するため、化粧用オイル等の油性化粧
料に特に好適に適用される。また、エステル化により最
大吸収波長(λmax)が長波長側にシフトし、UV−A
に対する吸収能は増加する。アルキルエステルの場合
は、炭素数が2以上のアルキル基がより好ましい。
The use of an ester improves the solubility in oily components, and thus is particularly suitably applied to oily cosmetics such as cosmetic oils. Also, the maximum absorption wavelength (λ max ) shifts to the long wavelength side due to esterification, and UV-A
The absorption capacity for is increased. In the case of an alkyl ester, an alkyl group having 2 or more carbon atoms is more preferable.

【0018】本発明の化粧料において、上記のテトラエ
ンジカルボン酸及びその誘導体よりなる群から任意の一
種または二種以上を配合する。その配合量は、化粧料全
体に対して0.01〜10重量%が好ましく、0.1〜
10重量%がより好ましい。0.1%以上とすること
で、化粧料の紫外線遮断効果はより一層向上する。ま
た、10重量%を越える量を配合しても、効果的にはほ
とんど変化はみられず、配合量として10重量%を超え
る必要はない。
In the cosmetic of the present invention, any one kind or two or more kinds are selected from the group consisting of the above-mentioned tetraene dicarboxylic acid and its derivative. The blending amount thereof is preferably 0.01 to 10% by weight with respect to the entire cosmetic,
10% by weight is more preferred. When the content is 0.1% or more, the ultraviolet blocking effect of the cosmetic material is further improved. Further, even if the amount exceeds 10% by weight, almost no change is effectively seen, and it is not necessary to exceed 10% by weight.

【0019】本発明の化粧料に用いられる化粧料基剤は
通常化粧料に使用し得る基剤であればいずれも用いるこ
とができ、例えばクリーム、軟膏、乳液、化粧水、オイ
ル、口紅、エアゾールなどの剤型をとることが可能とな
る。さらにこれらの基剤を構成する原料は、化粧品に通
常使用される原料であればいずれでもよく、特に限定さ
れない。
As the cosmetic base used in the cosmetic of the present invention, any base can be used as long as it can be usually used in cosmetics, for example, cream, ointment, emulsion, lotion, oil, lipstick, aerosol. It is possible to take a dosage form such as. Further, the raw materials constituting these bases may be any raw materials commonly used in cosmetics, and are not particularly limited.

【0020】尚、上記の化粧料基剤に対して、必要に応
じテトラエンジカルボン酸及びその誘導体以外の紫外線
吸収剤、微粒子酸化チタンに代表される紫外線散乱剤、
保湿、坑酸化、賦活などの薬効を有する成分、その他の
増粘剤、顔料、キレート剤、香料などを本発明の効果を
損なわない範囲で添加しても良い。
In addition to the above cosmetic base, if necessary, an ultraviolet absorber other than tetraenedicarboxylic acid and its derivative, an ultraviolet scattering agent typified by particulate titanium oxide,
Ingredients having medicinal effects such as moisturizing, antioxidation, activation, etc., other thickeners, pigments, chelating agents, fragrances, etc. may be added within a range not impairing the effects of the present invention.

【0021】以上述べたように、テトラエンジカルボン
酸及びその誘導体を配合することにより、高い使用感及
び使用性を保ちつつ、UV−A及びUV−Bの紫外線を
遮断し、皮膚の黒化及び皮膚癌を予防することが可能と
なる。
As described above, by blending tetraenedicarboxylic acid and its derivative, UV-A and UV-B ultraviolet rays are blocked while keeping high usability and usability, and skin blackening and It becomes possible to prevent skin cancer.

【0022】[0022]

【実施例】以下に本発明の実施例を示す。 (実施例1及び比較例1)表1に示した化粧水を各々調
合した。これをパネラーに塗布し日光を照射し、試料塗
布部の紅班形成最小照射量と無塗布部の紅班形成最小照
射量を求め、これらの比からSPF(sun protection f
actor)を算出した。結果もあわせて表1にまとめた。
EXAMPLES Examples of the present invention will be shown below. (Example 1 and Comparative Example 1) Each lotion shown in Table 1 was prepared. Apply this to a panel and irradiate it with sunlight to obtain the minimum amount of erythema formation in the sample application area and the minimum amount of erythema formation in the non-application area. From these ratios, SPF (sun protection f
actor) was calculated. The results are also summarized in Table 1.

【0023】[0023]

【表1】 表1から明らかなように、2−ヒドロキシ−4−メ
トキシベンゾフェノンー5ースルホン酸ナトリウムを配
合した比較例1の化粧水は、SPFが2.0であったの
に対し、デカテトラエンジカルボン酸ジナトリウムを配
合した実施例1の化粧水はSPFが5.0となり、優れ
た紫外線遮断効果を示した。また、皮膚刺激もなかっ
た。
[Table 1] As is clear from Table 1, the cosmetic lotion of Comparative Example 1 containing sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate had an SPF of 2.0, whereas decatetraenedicarboxylic acid diester The lotion of Example 1 containing sodium had an SPF of 5.0 and showed an excellent ultraviolet blocking effect. There was also no skin irritation.

【0024】(実施例2及び3)表2に示すクリームを
調合し、これをパネラーに塗布し5時間日光に当てた後
日焼けの状態を調べた。
(Examples 2 and 3) The creams shown in Table 2 were prepared, applied to a panel and exposed to sunlight for 5 hours, and then the state of sunburn was examined.

【0025】[0025]

【表2】 比較例2のクリームを塗布したパネラーの皮膚は、薄
く日焼けがみられたのに対し、実施例2及び3のクリー
ムを塗布したパネラーの皮膚は日光に照射後も変化はな
く、日光が当たらない皮膚との違いはみられなかった。
尚、クリームを塗布しない皮膚は赤く日焼けした。 (実施例4)以下に示す組成のファンデーションを調合
し、実施例1と同様にして紫外線遮断効果を評価した。
本実施例のクリームを塗布したパネラーの皮膚は日光が
当たらない皮膚と同様変化はみられなかった。
[Table 2] The skin of the panelist to which the cream of Comparative Example 2 was applied had a thin tan, whereas the skin of the panelist to which the cream of Examples 2 and 3 was applied had no change even after irradiation with sunlight and was not exposed to sunlight. No difference was seen with the skin.
The skin to which the cream was not applied was red and sunburned. (Example 4) A foundation having the following composition was prepared, and the ultraviolet blocking effect was evaluated in the same manner as in Example 1.
The skin of the panelists to which the cream of this example was applied did not show the same change as the skin not exposed to sunlight.

【0026】ファンデーション テトラエンジカルボン酸ジセチル 5.0 硫水性微粒子酸化チタン 7.0 イソステアリン酸トリグリセライド 2.0 2−オクテイルドデシルオレート 8.0 流動パラフィン 3.0 セチルアルコール 5.0 キャンデリラワックス 2.0 POE(25)モノステアレート 2.0 ソルビタンモノステアレート 1.0 黄色酸化鉄 1.3 ベンガラ 0.8 ポリエチレングリコール 4.0 香料 0.1 精製水 残 余 (実施例5)実施例1と同様にして、以下に示す組成の
化粧水を得た。この化粧水の紫外線遮断効果を、実施例
1と同様にして評価した。本発明の化粧水を塗布したパ
ネラーの皮膚は日光に当たらない皮膚と同様変化がみら
れなかった。また、皮膚刺激等もなかった。 デカテトラエンジカルボン酸 0.1 プロピレングリコール 10 エチルアルコール 20 流動パラフィン 2.0 POE(30)硬化ヒマシ油 1.0 ポリエチレングリコール 5.0 クエン酸Na 0.2 リン酸Na 0.3 EDTA−2Na 0.05 香料 0.1 精製水 残 余
Foundation Dicetyl tetraene dicarboxylate 5.0 Sulfuric acid fine particles titanium oxide 7.0 Triglyceride isostearic acid 2.0 2-Octylated decyl oleate 8.0 Liquid paraffin 3.0 Cetyl alcohol 5.0 Candelilla wax 2. 0 POE (25) monostearate 2.0 sorbitan monostearate 1.0 yellow iron oxide 1.3 red iron oxide 0.8 polyethylene glycol 4.0 perfume 0.1 purified water balance (Example 5) Example 1 and Similarly, a lotion having the following composition was obtained. The effect of blocking the ultraviolet rays of this lotion was evaluated in the same manner as in Example 1. The skin of the panelist to which the lotion of the present invention was applied did not show the same change as the skin not exposed to sunlight. There was no skin irritation. Decatetraene dicarboxylic acid 0.1 Propylene glycol 10 Ethyl alcohol 20 Liquid paraffin 2.0 POE (30) hydrogenated castor oil 1.0 Polyethylene glycol 5.0 Citrate Na 0.2 Phosphate Na 0.3 EDTA-2Na 0 .05 Fragrance 0.1 Purified water Residue

【0027】[0027]

【発明の効果】本発明により、即ち化粧料にテトラエン
ジカルボン酸及びその誘導体を配合することにより、高
い使用性を有すると共に、紫外線による皮膚の炎症を抑
制し、メラニン生成に起因する皮膚の黒化を予防さらに
は皮膚癌を予防し得る新規な化粧料を提供することが可
能となる。
EFFECTS OF THE INVENTION According to the present invention, that is, by adding tetraenedicarboxylic acid and its derivative to cosmetics, it has high usability, suppresses inflammation of the skin due to ultraviolet rays, and darkens skin caused by melanin formation. It is possible to provide a novel cosmetic that can prevent aging and further prevent skin cancer.

フロントページの続き (72)発明者 小松 一男 神奈川県横浜市港北区新羽町1050番地株式 会社資生堂研究所内Continued front page    (72) Inventor Kazuo Komatsu             Stock at 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa             Shiseido Research Institute

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 下記一般式(I)で示されるテトラエン
ジカルボン酸またはその誘導体 ROOC-CH=CH-CH=CH-CH=CH-CH=CH-COOR (I) (式中、Rは水素又は直鎖状、分岐状のアルキル基、ア
ルケニル基、アリール基またはアルカリ金属、アルカリ
土類金属、アミン類を表わす)を含むことを特徴とする
化粧料。
1. A tetraene dicarboxylic acid represented by the following general formula (I) or a derivative thereof ROOC-CH = CH-CH = CH-CH = CH-CH = CH-COOR (I) (wherein R is hydrogen. Or a linear or branched alkyl group, alkenyl group, aryl group or alkali metal, alkaline earth metal, amines).
【請求項2】 前記テトラエンジカルボン酸誘導体の配
合量が化粧料全量中0.01〜10重量%であることを
特徴とする請求項1記載の化粧料。
2. The cosmetic material according to claim 1, wherein the compounding amount of the tetraene dicarboxylic acid derivative is 0.01 to 10% by weight based on the total amount of the cosmetic material.
JP3209808A 1991-07-26 1991-07-26 Cosmetics Expired - Lifetime JP2977961B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3209808A JP2977961B2 (en) 1991-07-26 1991-07-26 Cosmetics

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3209808A JP2977961B2 (en) 1991-07-26 1991-07-26 Cosmetics

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JPH0532531A true JPH0532531A (en) 1993-02-09
JP2977961B2 JP2977961B2 (en) 1999-11-15

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