JP4014745B2 - Antioxidants and cosmetics - Google Patents
Antioxidants and cosmetics Download PDFInfo
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- JP4014745B2 JP4014745B2 JP35256198A JP35256198A JP4014745B2 JP 4014745 B2 JP4014745 B2 JP 4014745B2 JP 35256198 A JP35256198 A JP 35256198A JP 35256198 A JP35256198 A JP 35256198A JP 4014745 B2 JP4014745 B2 JP 4014745B2
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- antioxidant
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- 0 *c(cc1-c(cc(*)cc2O)c2O)cc(O)c1O Chemical compound *c(cc1-c(cc(*)cc2O)c2O)cc(O)c1O 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、抗酸化剤に関し、詳しくは医薬品、医薬部外品、化粧料、食品等に添加することが可能な優れた安全性、抗酸化能を有する抗酸化剤に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
従来、化粧料、医薬品や食品等にはＢＨＴ、ＢＨＡ等の合成抗酸化剤や、α−トコフェロール、アスコルビン酸等の様々な抗酸化剤が用いられているが、前者は安全性の面において懸念され、後者は安定性の面で難がある。また、種々の植物抽出物の抗酸化能について検討がされているが、抽出物は特有の香り、色、味を有しているものが多いことから、その利用範囲は制約されているのが現状である（食品工業、４月号、２０頁、１９９２年）。
【０００３】
特に皮膚化粧料等への利用に際しては、抗酸化剤の有効成分の多くがフェノール構造を有し、アレルギー性皮膚炎（感作性）を誘発する可能性が高いことや安定性に問題があることから、ほとんど利用されていない。
【０００４】
そこで、本発明者等はフェノール化合物をビフェニル体とすることにより安全性が高まることを確認するとともに、特定のビフェニル化合物が優れた活性酸素消去作用を有することや抗酸化効果を有することを確認している（特開平４−２８３５１３号公報、特開平７−１７９８５３号公報）。
【０００５】
本発明者等は、新たなビフェニル化合物群について鋭意検討を行った結果、後記特定のビフェニル化合物は、ほとんど無味無臭であり、既存のビフェニル化合物に比較してより優れた抗酸化力を有することを見いだし本発明を完成した。
【０００６】
即ち、本発明の目的は、安全性、安定性に優れ、化粧品、食品等に配合するに際しても不快な臭いや味を持たないため不具合のない、優れた抗酸化能を有する抗酸化剤を提供することにある。
【課題を解決するための手段】
上記目的は、特定のビフェニル化合物によって達成される。即ち、本発明は、下記一般式（１）
【０００７】
【化２】
（但し、式中、Ｒは直鎖もしくは分岐鎖状の、飽和もしくは不飽和の、炭素数１〜８である炭化水素基、又はＣＨ2ＯＨ、Ｃ3Ｈ6ＯＨ、ＣＨＯ、ＣＯＣＨ3基）で表されるビフェニル化合物の一種以上からなる抗酸化剤にある。更に、該抗酸化剤を含有することを特徴とする化粧料にある。
【０００９】
【発明の実施の形態】
本発明の用いる上記一般式（１）で表されるビフェニル化合物は、特開平７−１７９８５３号公報記載の製造方法にて得られたビフェニル化合物をジクロロメタン中において三臭素化ホウ素や三塩化ホウ素等のルイス酸を開裂試薬として用いて反応させることにより容易に得ることができる（Ｊ．Ｃｈｅｍ．Ｓｏｃ．，１９６３年 １０１１頁）。
【００１０】
上記一般式（１）で表されるビフェニル化合物の抗酸化剤、化粧料への配合量は目的、対象とするものにより千差万別であり一概に規定できるものではないが、一般的には０．０００１〜５重量％が好ましい。
【００１１】
本発明の抗酸化剤は、上記ビフェニル化合物の一種以上、特に好ましくは二種以上を含有することが好ましい。そして、医薬品、食品等に一般に用いられる賦型剤等を適宜用いて顆粒、粉末状とする他、適当な溶剤等を用い液状、エマルション、クリーム、ペースト等とすることができる。また、必要に応じて抗酸化剤と併用することにより相乗効果を奏することが知られているアスコルビン酸、クエン酸、コハク酸等の相乗剤を含有すると更に好ましい。
【００１２】
本発明の抗酸化剤は、特定のビフェニル化合物を配合した、口紅、乳液、クリーム等の化粧料や医薬品、医薬部外品等だけでなく、魚油、ラード、大豆油、あまに油、コーン油、綿実油、パーム油等の動植物を原料とする油脂類や、バター、マーガリン、マヨネーズ、ハム、ポテトチップ、揚げせんべい、魚肉等の食品等に食味、香り、感触等を損なうことなく広く利用できる。
【００１３】
【実施例】
以下、実施例について説明する。用いたビフェニル化合物及び略称を以下に示す。尚、これらの化合物はほとんど無味無臭であった。
【００１４】
ビフェニル化合物（括弧内に以下、用いる略称を示す。）
【００１５】
2,3,2',3'-テトラヒドロキシ-5,5'-ジメチル-ビフェニル （化合物１）
【００１６】
【化３】
2,3,2',3'-テトラヒドロキシ-5,5'-ジプロピル-ビフェニル （化合物２）
【００１８】
【化４】
2,3,2',3'-テトラヒドロキシ-5,5'-ジアリル-ビフェニル （化合物３）
【００２０】
【化５】
2,3,2',3'-テトラヒドロキシ-5,5'-ジヒドロキシメチル-ビフェニル（化合物４）
【００２２】
【化６】
抗酸化力の試験方法を以下に示す。尚、実施例に示す％は重量％を意味する。
【００２４】
＜抗酸化力試験法＞
不飽和脂肪酸としてリノール酸メチルを試験試料に用い、紫外線照射（東芝製医療用紫外線照射装置Ｍ−ＤＭＲ）を過酸化条件とした。紫外線照射によるリノール酸メチルの過酸化度を過酸化脂質測定用蛍光ラベル化剤ジフェニル−１−ピレニルフォスフィン（以下、ＤＰＰＰと略する。）を用いた赤坂等の方法に従い測定し、本発明に係るビフェニル化合物の抗酸化能を評価した（バイオサイエンス・バイオテクノロジー・バイオケミカル 第５８巻３９６頁、１９９４年）。また、既に抗酸化効果が知られている次の化７（デヒドロジクレオソール）、化８（2,2'-ジヒドロキシ-3,3'-ジメトキシ-5,5'-ジプロピルビフェニル；ＤＨＭＰＢと略する。）を比較試料として用いた。
【００２５】
【化７】
【化８】
実施例１
リノール酸メチル１ｍｌに抗酸化試験試料（化合物１〜２）をそれぞれ０．００５ｇ添加し紫外線照射（ＵＶＢ波）による脂質過酸化度を前記抗酸化試験方法によって測定した。その結果、図１に示すように本発明で用いるビフェニル化合物はデヒドロジクレオソール、ＤＨＭＰＢと比較して優れた抗酸化力を有していることが確認された。
【００２８】
（製法）Ａの油相部とＢの水相部をそれぞれ７０℃に加熱し完全溶解した。次にＡ相にＢ相を加えて、乳化機で乳化した。乳化物を冷却して本発明に係るクリーム状皮膚化粧料を得た。得られた化粧料は、経日安定性に優れていることが確認された。
【００３０】
実施例３
皮膚化粧料（クリーム）
実施例２で用いた化合物３（配合量０．５％）を化合物４（配合量０．１％）に代えた以外は実施例２と同様にして、本発明に係るクリーム状皮膚化粧料を得た。得られた化粧料は、経日安定性に優れていることが確認された。
【００３１】
【発明の効果】
本発明に係る抗酸化剤は、ほとんど無味無臭であり、安全性が極めて高いことから皮膚化粧料を始め各種の化粧料や医薬品、医薬部外品、食品に対しても汎用性が高く、且つ優れた抗酸化能を有するものである。
【図面の簡単な説明】
【図１】リノール酸メチルに対するビフェニル化合物の抗酸化力を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antioxidant, and more particularly to an antioxidant having excellent safety and antioxidant ability that can be added to pharmaceuticals, quasi drugs, cosmetics, foods and the like.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, synthetic antioxidants such as BHT and BHA and various antioxidants such as α-tocopherol and ascorbic acid have been used in cosmetics, pharmaceuticals, foods, etc., but the former is a concern in terms of safety. The latter is difficult in terms of stability. In addition, the antioxidative ability of various plant extracts has been studied, but the extract has many unique fragrances, colors, and tastes, so the range of use is limited. The current situation (Food Industry, April issue, 20 pages, 1992).
[0003]
In particular, when used in skin cosmetics, many of the active ingredients of antioxidants have a phenolic structure, and there is a high possibility of inducing allergic dermatitis (sensitization), and there is a problem with stability. Therefore, it is hardly used.
[0004]
Accordingly, the present inventors confirmed that the safety is enhanced by making the phenol compound a biphenyl compound, and also confirmed that the specific biphenyl compound has an excellent active oxygen scavenging action and an antioxidant effect. (JP-A-4-283513, JP-A-7-179853).
[0005]
As a result of intensive studies on a new group of biphenyl compounds, the present inventors have found that the specific biphenyl compounds described below are almost tasteless and odorless and have superior antioxidant power compared to existing biphenyl compounds. The present invention has been completed.
[0006]
That is, the object of the present invention is to provide an anti-oxidant having excellent antioxidative ability, which is excellent in safety and stability, and has no unpleasant odor or taste even when blended in cosmetics, foods, etc. There is to do.
[Means for Solving the Problems]
The above objective is accomplished by a specific biphenyl compound. That is, the present invention provides the following general formula (1)
[0007]
[Chemical 2]
(In the formula, R is linear or branched, saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms, or CH 2 OH, C 3 H 6 OH, CHO, COCH 3 group) It exists in the antioxidant which consists of 1 or more types of biphenyl compound represented by these. The cosmetic further comprises the antioxidant.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The biphenyl compound represented by the above general formula (1) used in the present invention is a biphenyl compound obtained by the production method described in JP-A-7-179853, such as boron tribromide or boron trichloride in dichloromethane. It can be easily obtained by reacting using a Lewis acid as a cleavage reagent (J. Chem. Soc., 1963, page 1011).
[0010]
The amount of the biphenyl compound represented by the above general formula (1) to be added to the antioxidant and cosmetics varies widely depending on the purpose and the target and cannot be generally defined. 0.0001-5 weight% is preferable.
[0011]
The antioxidant of the present invention preferably contains one or more of the above biphenyl compounds, particularly preferably two or more. In addition to appropriate use of excipients generally used for pharmaceuticals, foods and the like, granules and powders can be used, and liquids, emulsions, creams, pastes and the like can be obtained using appropriate solvents. Further, it is more preferable to contain a synergist such as ascorbic acid, citric acid, and succinic acid, which is known to produce a synergistic effect when used in combination with an antioxidant as necessary.
[0012]
Antioxidants of the present invention are not only cosmetics such as lipsticks, emulsions and creams, pharmaceuticals, quasi drugs, etc., but also fish oil, lard, soybean oil, linseed oil, corn oil, and the like, which contain a specific biphenyl compound. It can be widely used for fats and oils made from animals and plants such as cottonseed oil and palm oil, and foods such as butter, margarine, mayonnaise, ham, potato chips, fried rice crackers, and fish meat without sacrificing the taste, aroma, touch and the like.
[0013]
【Example】
Examples will be described below. The biphenyl compounds and abbreviations used are shown below. These compounds were almost tasteless and odorless.
[0014]
Biphenyl compound (The abbreviations used are shown in parentheses below.)
[0015]
2,3,2 ', 3'-Tetrahydroxy-5,5'-dimethyl-biphenyl (Compound 1)
[0016]
[Chemical 3]
2,3,2 ', 3'-Tetrahydroxy-5,5'-dipropyl-biphenyl (Compound 2)
[0018]
[Formula 4]
2,3,2 ', 3'-Tetrahydroxy-5,5'-diallyl-biphenyl (Compound 3)
[0020]
[Chemical formula 5]
2,3,2 ', 3'-tetrahydroxy-5,5'-dihydroxymethyl-biphenyl (compound 4)
[0022]
[Chemical 6]
The test method of antioxidant power is shown below. In the examples, “%” means “% by weight”.
[0024]
<Antioxidant test method>
As an unsaturated fatty acid, methyl linoleate was used as a test sample, and ultraviolet irradiation (medical ultraviolet irradiation apparatus M-DMR manufactured by Toshiba) was used as a peroxidation condition. The degree of peroxidation of methyl linoleate by ultraviolet irradiation was measured according to a method such as Akasaka using a fluorescent labeling agent diphenyl-1-pyrenylphosphine (hereinafter abbreviated as DPPP) for lipid peroxide measurement. The anti-oxidant ability of the biphenyl compound was evaluated (Bioscience, Biotechnology, Biochemical, Vol. 58, page 396, 1994). Further, the following chemical formulas 7 (dehydrodicreole) and chemical formulas 8 (2,2′-dihydroxy-3,3′-dimethoxy-5,5′-dipropylbiphenyl), which have already been known to have an antioxidant effect; Was used as a comparative sample.
[0025]
[Chemical 7]
[Chemical 8]
Example 1
0.005 g of each antioxidant test sample (compounds 1 and 2) was added to 1 ml of methyl linoleate, and the degree of lipid peroxidation by ultraviolet irradiation (UVB wave) was measured by the above antioxidant test method. As a result, as shown in FIG. 1, it was confirmed that the biphenyl compound used in the present invention has an excellent antioxidant power compared to dehydrodichloroeosol and DHMPB.
[0028]
(Manufacturing method) The oil phase part of A and the aqueous phase part of B were each heated to 70 ° C. and completely dissolved. Next, B phase was added to A phase, and it emulsified with the emulsifier. The emulsion was cooled to obtain a creamy skin cosmetic according to the present invention. It was confirmed that the obtained cosmetic was excellent in stability over time.
[0030]
Example 3
Skin cosmetic (cream)
A creamy skin cosmetic according to the present invention was prepared in the same manner as in Example 2 except that Compound 3 (blending amount 0.5%) used in Example 2 was replaced with Compound 4 (blending amount 0.1%). Obtained. It was confirmed that the obtained cosmetic was excellent in stability over time.
[0031]
【The invention's effect】
The antioxidant according to the present invention is almost tasteless and odorless and has extremely high safety, so it is highly versatile for various cosmetics and pharmaceuticals, quasi-drugs, foods including skin cosmetics, and It has excellent antioxidant ability.
[Brief description of the drawings]
FIG. 1 is a graph showing the antioxidant power of a biphenyl compound against methyl linoleate.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35256198A JP4014745B2 (en) | 1998-12-11 | 1998-12-11 | Antioxidants and cosmetics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35256198A JP4014745B2 (en) | 1998-12-11 | 1998-12-11 | Antioxidants and cosmetics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000169846A JP2000169846A (en) | 2000-06-20 |
| JP4014745B2 true JP4014745B2 (en) | 2007-11-28 |
Family
ID=18424912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35256198A Expired - Lifetime JP4014745B2 (en) | 1998-12-11 | 1998-12-11 | Antioxidants and cosmetics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4014745B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4812232B2 (en) * | 2003-02-27 | 2011-11-09 | 花王株式会社 | Emulsified composition |
| US8425881B2 (en) | 2005-03-18 | 2013-04-23 | Colgate-Palmolive Company | Antibacterial 3′,5-disubstituted 2,4′-dihydroxybiphenyl compounds, derivatives and related methods |
| RU2381793C2 (en) | 2005-03-18 | 2010-02-20 | Колгейт-Палмолив Компани | Antibacterial 5,5т-disubstituted compounds of 3,3'-dialkoxy-2,2'-hydroxide'-biphenyl and methods of application thereof |
| US20090087461A1 (en) * | 2007-10-01 | 2009-04-02 | Thomas James Boyd | Anti-bacterial pyrocatechols and related methods |
-
1998
- 1998-12-11 JP JP35256198A patent/JP4014745B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JP2000169846A (en) | 2000-06-20 |
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