JP2009227775A - Antioxidant/active oxygen scavenger, cosmetic perfume composition containing it, and cosmetics - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel antioxidant/active oxygen scavenger, which has high safety and high antioxidant effect, sufficiently removes active oxygen generated in a living body, and is desirably applicable to a cosmetic perfume composition and cosmetics. <P>SOLUTION: The antioxidant/active oxygen scavenger comprises a compound represented by a chemical formula as an active ingredient. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel compound derived from a natural product having an excellent antioxidant ability or active oxygen scavenging ability, an antioxidant or an active oxygen scavenger containing the novel compound as an active ingredient, and a cosmetic containing the same. The present invention relates to a fragrance composition and a cosmetic.

  In aged skin, lipid peroxide increases, softness and elasticity are lost, wrinkles of the skin increase, and dry and rough skin symptoms are not smooth. As one of the causative substances in which these skin symptoms appear, so-called active oxygen is considered that oxygen in the atmosphere is generated under the influence of ultraviolet rays or enzymes. This active oxygen is said to be generated not only by oxygen entering the body by breathing, but also by intense emotions such as smoking, stress, anger, anxiety and fear, violent drinking and eating.

  Active oxygen includes free radicals such as superoxide and hydroxy radicals, and non-radicals such as singlet oxygen and hydrogen peroxide. If this active oxygen is present inside and outside the body more than necessary, it also acts on normal cells, cell membranes, and DNA to destroy them. It also produces lipid peroxides because it oxidizes lipids. This also induces various diseases such as worsening atopy symptoms, cataracts, moderate wind, myocardial infarction, and carcinogenesis. For the living body, it has adverse effects such as cross-linking of collagen fibers, fragmentation of hyaluronic acid, partial cleavage of DNA helix, tissue damage due to generation of chain radicals, resulting in skin wrinkles, loss of elasticity, hair loss, etc. It is said to promote aging of the living body.

  Therefore, suppressing the production of active oxygen is very important in order to improve or prevent skin aging and to keep the skin and tissues in the living body normal. This is an important factor required for anti-aging skin cosmetics. Therefore, the search of the substance which has the effect | action which erase | eliminates the active oxygen conventionally generated in the living body has been performed widely.

Conventionally used substances having such an action include fat-soluble tocopherol (vitamin E) for naturally derived substances, water-soluble ascorbic acid (vitamin C), and BHT (butylhydroxytoluene) for synthetic compounds. , BHA (butylhydroxyanisole) and the like. Some plant extracts have an antioxidative effect, and attempts have been made to prevent skin aging by blending with cosmetics. (For example, see Patent Documents 1 to 4.)
JP 2003-128569 A Japanese Patent Laid-Open No. 2002-97151 JP 2002-205933 A JP 2003-321337 A

  However, there are some plant extracts that are concerned about safety, and the active oxygen scavenging ability is not sufficient, or when it is formulated in a base for external preparations such as cosmetics, it has an effective effect. There are few things that can satisfy all in terms of action effect and stability, such as adding a rather bad odor to the preparation, so that a high concentration must be blended to obtain It was the current situation.

  In the above circumstances, a novel antioxidant, active oxygen, which has high safety, high antioxidant action, has sufficient action to eliminate active oxygen generated in the living body, and has good applicability to cosmetics There was a need for an eraser.

  Accordingly, the object of the present invention is to provide a novel antioxidant or novel active oxygen scavenger excellent in antioxidant effect or active oxygen scavenging effect, or a perfume composition for cosmetics and cosmetics containing them. There is to do.

Thus, as a result of intensive studies in view of the above circumstances, the present inventors have found that a compound represented by the following chemical formula has an excellent antioxidant effect or active oxygen scavenging effect, and completed the present invention.
That is, the present invention has the following chemical formula:

で表される化合物２−ｈｙｄｒｏｘｙ−３，５，５−ｔｒｉｍｅｔｈｙｌ−２−ｃｙｃｌｏｈｅｘｅｎｏｎｅ（以下、本発明の化合物ともいう）を有効成分とする抗酸化剤または活性酸素消去剤である。また本発明は、前記の抗酸化剤または活性酸素消去剤が配合された香粧品用香料組成物である。さらに本発明は、前記の抗酸化剤または活性酸素消去剤が配合された、あるいは前記香粧品用香料組成物が配合された化粧料である。

Is an antioxidant or active oxygen scavenger comprising as an active ingredient the compound 2-hydroxy-3,5,5-trimethyl-2-cyclohexone (hereinafter also referred to as the compound of the present invention). Moreover, this invention is the fragrance | flavor composition for cosmetics by which the said antioxidant or active oxygen scavenger was mix | blended. Furthermore, the present invention is a cosmetic containing the antioxidant or active oxygen scavenger described above, or the cosmetic perfume composition.

  The compound of the present invention has an excellent antioxidant effect and active oxygen scavenging effect. The antioxidant or active oxygen scavenger of the present invention is isolated from a plant extract, has high safety, and exhibits a very excellent antioxidant effect / active oxygen scavenging effect. Therefore, it is useful for preventing or reducing various problems of living bodies involving oxidation and active oxygen. Moreover, the fragrance composition for cosmetics of the present invention containing the antioxidant or active oxygen scavenger can exhibit a wide variety of attractive fragrances in addition to safety, antioxidant effect, active oxygen scavenging effect, etc. It is excellent. Furthermore, the cosmetic of the present invention containing the antioxidant, active oxygen scavenger or cosmetic fragrance composition can greatly reduce the amount of conventional antioxidant used. In addition, it prevents oxidation of various raw materials to suppress deterioration of quality and has an excellent active oxygen scavenging effect. Therefore, when applied to the skin, it is excellent in so-called skin aging preventing effects such as preventing rough skin, maintaining skin gloss, elasticity, brightness and improving wrinkles.

The compound of the present invention can be isolated by separating and purifying from the whole saffron flower or pistil extract which is a genus plant. It can also be obtained as a synthetic product. The method for extracting a compound of the present invention includes, for example, extracting an entire saffron flower extract with various solvents, that is, liquefied gas (liquid carbonic acid, liquefied propane, liquefied butane, etc.), water, lower alcohols having 1 to 5 carbon atoms (methyl). Alcohol, ethyl alcohol, propyl alcohol, etc.), hydrous lower alcohols, esters of lower alcohols having 1 to 5 carbon atoms and fatty acids having 1 to 5 carbon atoms (methyl acetate, ethyl acetate, butyl acetate, etc.), ketones ( Acetone, methyl ethyl ketone, etc.), hydrates of the esters and ketones, halogenated hydrocarbons (chloroform, dichloromethane, dichloroethane, trichloroethane, etc.), ethers (methyl ether, ethyl ether, tetrahydrofuran, dioxane, etc.), hydrocarbons (Petroleum ether, hexane, etc.) or a mixture of the above solvents The extract obtained out, acid, alkali treatment, column chromatography, distillation, can be obtained by concentration or the like.

  Crocus sativus L. containing the compounds of the present invention. Is commonly referred to as saffron, and its extract has a unique medicinal odor. Therefore, Crocus sativus L. In the use of the extract or the like, the medicinal odor causes unpleasant odor characteristics to the final product, so that it cannot be used in cosmetics or the like, or has been a major hindrance factor. Therefore, it is necessary to use a small amount for blending, and in the first place Crocus sativus L. This extract was not effective as compared with the compound of the present invention, and thus the expected antioxidant ability and active oxygen scavenging ability were not obtained.

  On the other hand, since the compound of the present invention has almost no fragrance and has an extremely high antioxidant effect and active oxygen scavenging effect, the above-mentioned problems do not occur at all and the object of the present invention can be achieved. .

  In order to use the compound of the present invention industrially, it is not always necessary to purify the compound to be completely free of impurities, and 0.00001 mass of the compound of the present invention is contained in the antioxidant or active oxygen scavenger of the present invention. % (Hereinafter simply expressed as%) may be contained.

  The blending amount of the antioxidant or active oxygen scavenger in the fragrance composition for cosmetics of the present invention varies depending on the purpose and type of use of the fragrance composition for cosmetics, but the content of the compound of the present invention is a cosmetic product. It is 0.0001 to 20% in a fragrance composition for use, preferably 0.001 to 5%. Within this range, the expected antioxidant effect and active oxygen scavenging effect can be obtained, and it is also preferable in terms of odor and safety.

  The fragrance composition for cosmetics of the present invention has an effective antioxidant effect and can express a wide variety of attractive fragrances. In addition to the antioxidant and active oxygen scavenger of the present invention, known fragrance materials and solvents are used in the fragrance composition for cosmetics of the present invention. For example, various hydrocarbons such as limonene, caryophyllene, and pinene; various aldehydes such as acetaldehyde, α-cinnamic aldehyde, citral; various ketones such as maltol, benzylacetone, and damasenone; butanol, benzylalcohol Various alcohols such as quinol and linalol; various ether oxides such as geranyl ethyl ether, rose oxide and furfural; ethyl acetate, benzyl acetate, linalyl acetate Various esters such as γ-decalactone, coumarin and sclareolide; various hetero compounds such as indole, 2-isopropyl-4-methylthiazol and phenylacetonitrile; jasmine absolute, fern -Wood oil, Oris concrete, etc. Various natural materials are listed. Examples of the solvent to be used include ethanol, dipropylene glycol (also referred to as DPG), benzyl benzoate, water, triacetin, triethyl citrate and the like.

When the antioxidant or active oxygen scavenger of the present invention or the perfume composition for cosmetics of the present invention is blended in cosmetics, the blending amount varies depending on the purpose and type of cosmetics used, but the compound of the present invention The content of is preferably 0.00001 to 20%, more preferably 0.0001 to 5%. Within this range, the expected antioxidant effect and active oxygen scavenging effect can be obtained, and it is also preferable in terms of odor and safety.

  In the cosmetics of the present invention, oils, waxes, hydrocarbons, higher fatty acids, higher alcohols, esters, other oily raw materials, polyhydric alcohols such as glycerin, surfactants, thickeners and the like are usually used. The known ingredients for cosmetics and the antioxidants, active oxygen scavengers or fragrance compositions for cosmetics of the present invention can be used to obtain them by ordinary production methods. Moreover, you may use together well-known antioxidant (vitamin C, vitamin E, etc.), an active oxygen scavenger, etc. as needed.

  The dosage form of the cosmetic is also arbitrary, and examples include a solution system, a solubilization system, an emulsification system, and an aerosol. Furthermore, the use of cosmetics is also optional, for example, facial cosmetics such as lotions, emulsions, creams and packs, makeup cosmetics such as foundations, lipsticks and eye shadows, cosmetics for hair washing such as aromatic cosmetics and shampoos. , Hair finishing cosmetics, body cosmetics, oral cosmetics, bath cosmetics, and the like. Since the cosmetics of the present invention have high antioxidant properties, the addition of antioxidants that have been added to conventional cosmetics can be greatly reduced. Accordingly, it is possible to reduce the irritation caused by the blending of the synthetic antioxidants in some cosmetic users who have sensitive skin. In addition, the skin lotion and bathing agent of the present invention are excellent in the effects of preventing rough skin, maintaining skin gloss, elasticity, brightness, and improving wrinkles. Can be expected.

  Hereinafter, although the compound etc. of this invention are demonstrated based on an isolation example, a test example, and an Example, this invention is not limited to these.

(Isolation)
Crocus sativus L. 100 grams of dried pistil was soaked in 1 liter of ethyl alcohol at room temperature to transfer the fragrance component and antioxidant component, and then the pistil was removed. Next, the solvent was distilled off to obtain 10 grams of an extract. This extract had a medicinal odor.
Next, 10 grams of the above extract was subjected to silica gel column chromatography using a mobile phase of n-hexane / ethyl acetate = 1: 1 (V / V) to ethyl acetate / methanol = 1: 1 (V / V) according to a conventional method. The compound 2-hydroxy-3,5,5-trimethyl-2-cyclohexenone was obtained by performing chromatography and purification. This smell had a much sweeter and weaker spicy scent.
The MS spectrum data is as follows.

(Fine products)
MS (m / z): 154 (M +), 154, 70, 98, 139, 55, 111, 41, 83

(Test Example 1: Active oxygen scavenging effect test (DPPH method))
There are various methods for measuring the effect of scavenging active oxygen, but this time, the ability to scavenge 1,1-diphenyl-2-picrylhydrazyl (DPPH), an organic radical, was measured. The method is as follows. That is, 100 μl / L Tris buffer solution (pH 7.5, Wako Pure Chemical Industries, Ltd.) in a 96-well microplate was adjusted to a concentration of 80 μl and 99.5% methanol (Pure Chemical). After adding 100 μl of 0.5 mmol / L DPPH (Wako Pure Chemical Industries), whose concentration was adjusted by (Pure Chemical), the mixture was stirred and incubated at room temperature for 20 minutes in the dark. Then, the absorbance A at 517 nm was measured with a spectrophotometer (Multi-Spectrophotometer Vient XS / Dainippon Sumitomo Pharma). On the other hand, the same operation was performed with a sample without DPPH (blank) and a sample without control (control), and the obtained absorbance (B and C, respectively) was measured to obtain an active oxygen elimination rate (%). .

(IC ₅₀ calculation formula)
Active oxygen elimination rate (%) = {1− (A−B) / C} × 100
(However, A: Absorbance of sample, B: Absorbance of blank, C: Absorbance of control)

Similarly, each sample shown in Table 1 was tested. A graph was prepared by plotting the concentration on the horizontal axis and the active oxygen elimination rate on the vertical axis, and from this graph, the concentration at which active oxygen was suppressed by 50% (hereinafter referred to as IC ₅₀ ) was determined.

The results are shown in Table 1.
Active oxygen scavenging effect test (DPPH method) and IC ₅₀ results

  From the above results, the antioxidant or active oxygen scavenger of the present invention is said to have a high antioxidant property among DL-α-tocopherol and fragrance, which are natural antioxidants that are widely used. It can be seen that it has an excellent antioxidant ability comparable to that of Marie Oil Absolute.

Formulation Example 1 (Fragrance Formulation Example 1, Fragrance Comparison Example 1)
An antioxidant (which is also an active oxygen scavenger) of the present invention was blended to prepare a herbal blended fragrance having the following formulation.

得られた香料組成物である香料処方例1は、本発明の抗酸化剤を添加しても香りのバランスを崩すことなく、従来のハーブ系調合香料組成物である香料比較例1と同様に優れた匂い特性を有している。

Perfume Formulation Example 1 which is the obtained perfume composition is the same as Perfume Comparative Example 1 which is a conventional herb-based blended perfume composition without destroying the fragrance balance even when the antioxidant of the present invention is added. Has excellent odor characteristics.

Formulation Example 2 (Fragrance Formulation Example 2, Fragrance Comparison Example 2)
The antioxidant of the present invention (which is also an active oxygen scavenger) was blended to produce a floral blended fragrance having the following formulation.

得られた香料組成物である香料処方例２は、抗酸化剤を添加しても香りのバランスを崩すことなく、従来のフローラル系調合香料組成物である香料比較例２と同様に優れた匂い特性を有している。

Perfume Formulation Example 2, which is the obtained perfume composition, has the same excellent odor as Perfume Comparative Example 2, which is a conventional floral blended perfume composition, without losing the balance of the fragrance even when an antioxidant is added. It has characteristics.

Examples 3-5 and Comparative Examples 3-5 (Skin Lotion)
Skin lotions having the compositions described in Table 4 were prepared according to the following method.
(Skin lotion preparation method)
The aqueous phase and the alcohol phase are uniformly dissolved, and the aqueous phase and the alcohol phase are mixed, stirred and dispersed to effect solubilization, and then filled into a container. In use, the contents are uniformly shaken and dispersed.

  A use test was conducted using the skin lotion prepared above, and the anti-skin aging effect was examined. The test method is as shown below.

(Test method)
The face of 60 female subjects is divided into left and right, one of the above examples 3 to 5, the other is the skin lotion of comparative example 3 for example 3, and the skin of comparative example 4 for example 4. For the lotion and Example 5, the skin lotion of Comparative Example 5 was applied at least twice daily, and after 2 months, each comparative item was scored for each evaluation item based on the following criteria. The evaluation was based on the total score. The test subjects were divided into 3 groups of 20 people per group, and each skin lotion of Examples 3 to 5 was assigned to each group for testing. The results are shown in Table 5.

(Criteria)
+3: Examples 3-5 are much better than Comparative Examples 3-5 +2: Examples 3-5 are much better than Comparative Examples 3-5 +1: Examples over Comparative Examples 3-5 3-5 is slightly better 0: No difference -1: Comparative Examples 3-5 are slightly better than Examples 3-5 -2: Comparative Examples 3-5 are better than Examples 3-5 -3: Comparative Examples 3 to 5 are much better than Examples 3 to 5

  As is apparent from Table 5, skin lotion containing the antioxidant, active oxygen scavenger or cosmetic fragrance composition of the present invention as an active ingredient prevents rough skin, and improves skin gloss, elasticity and brightness. It is excellent in the effect of keeping and improving wrinkles, and can be used as a cosmetic for preventing skin aging.

Examples 6 to 8 and Comparative Example 6: Bathing agent Bathing agents having the following compositions were prepared according to a conventional method. In addition, this bath agent is diluted about 3000 times at the time of use.

  All 60 subjects used the bathing agent of Comparative Example 6 when bathing every day for three weeks. Thereafter, the subjects were divided into 3 groups of 20 people per group, Examples 6 to 8 were assigned to each group, and each bath agent of Examples 6 to 8 was used following Comparative Example 6. Then, using Comparative Example 6 as a reference, each evaluation item was scored according to the following criteria, and the evaluation was made based on the total value of the scores.

(Criteria)
+3: Examples 6 to 8 were improved and much better than Comparative Example 6 +2: Examples 6 to 8 were significantly improved compared to Comparative Example 6 +1: Examples 6 to 6 than Comparative Example 6 8 is slightly improved 0: No difference -1: Comparative Example 6 is slightly better than Examples 6-8 -2: Comparative Example 6 is considerably better than Examples 6-8- 3: Comparative Example 6 is much better than Examples 6-8

As is clear from Table 7, the bath containing the antioxidant, active oxygen scavenger or cosmetic fragrance composition of the present invention as an active ingredient prevents rough skin, and gives the skin gloss, elasticity and brightness. It is excellent in the effect of keeping and improving wrinkles and can be used as a bath agent for preventing skin aging. In addition, abnormalities such as redness and drying due to the skin lotion and bathing agent according to the above examples were not observed.

  The compounds of the present invention are useful as active ingredients for antioxidants and active oxygen scavengers. Further, the antioxidant and active oxygen scavenger of the present invention are isolated from plant extracts and have high safety and exhibit very excellent antioxidant effect and active oxygen scavenging effect. Therefore, it can be suitably used in all fields involving oxidation and active oxygen, such as cosmetics. In addition to the safety, antioxidant effect, active oxygen scavenging effect, etc., the perfume composition for cosmetics of the present invention is excellent in expressing a wide variety of attractive fragrances. It can be suitably used.

Claims (4)

The following chemical formula

The antioxidant or active oxygen scavenger which uses as an active ingredient the compound 2-hydroxy-3,5,5-trimethyl-2-cyclohexone represented by these.   A fragrance composition for cosmetics, wherein the antioxidant or active oxygen scavenger according to claim 1 is blended.   A cosmetic comprising the antioxidant or active oxygen scavenger according to claim 1 or the cosmetic fragrance composition according to claim 2.   A cosmetic for preventing skin aging, comprising the antioxidant or active oxygen scavenger according to claim 1 or the cosmetic fragrance composition according to claim 2.