JP2003300859A - Skin care preparation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a skin care preparation having excellent skin beautifying effects, especially bleaching effects and/or aging preventing effects. <P>SOLUTION: This skin care preparation comprises a compound represented by formula (1) [wherein, R<SP>1</SP>denotes CH<SB>2</SB>OH or a COOR<SP>6</SP>; R<SP>6</SP>denotes hydrogen, a 1-3C lower alkyl group or a cation forming a salt with COO<SP>-</SP>; R<SP>2</SP>to R<SP>5</SP>denote each independently hydrogen atom or methyl group; and A denotes C(CH<SB>3</SB>), C(CH<SB>3</SB>), C(=CH<SB>2</SB>, CH(CH<SB>3</SB>) or C(OH)(CH<SB>3</SB>)] and a specific ingredient. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a skin external preparation having a whitening effect and an antiaging effect, which contains a physiologically active ingredient containing a specific compound and a specific medicinal agent.

[0002]

2. Description of the Related Art Conventionally, for external skin preparations such as emulsions, creams, lotions, packs, detergents, dispersions, ointments, solutions, aerosols, patches, poultices, liniments, etc., they have a predetermined medicinal effect. Various medicinal components are added for the purpose of giving. For example, ascorbic acid, a placenta extract, in order to prevent or improve skin darkening caused by sunburn, stains caused by pigmentation, freckles, etc.
Whitening agents such as glutathione and hydroquinone have been added. On the other hand, a cell activating agent such as vitamin A, soybean extract, or seaweed extract is added in order to prevent or improve wrinkles and sagging of the skin caused by aging, exposure to ultraviolet rays, firmness and deterioration of elasticity. ing.

[0003] In addition, Cistu belonging to the family Asteraceae
s ladaniferus L .; , Cistus c
Reticus L. , Cistus monooper
iens L. , Cistus salvifol
Hot water extracts such as stems, branches and leaves of ius and extracts such as ethanol and hexane have strong melanin production inhibitory effect, cell activating effect and antibacterial effect, and they are activities based on labdenic acids. , And an extract thereof or crude labdene acids obtained by molecular distillation, which is obtained by labd-7-en-15-oic acid (labd-7).
-En-15-oic acid), loved-8 (1
7) -En-15-Oic Acid (labd-8)
(17) -en-15-oic acid), loved-
8-En-15-Oic Acid (labd-8-e
It has been found that (n-15-oic acid) has a strong melanin production inhibitory action, cell activating action, and antibacterial action. Further, it has been found that salts thereof, methyl and ethyl ester forms thereof, and further reduced forms thereof have similar activity (see Patent Document 1).

[0004]

[Patent Document 1] Japanese Patent Laid-Open No. 11-302219

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an external preparation for the skin which is excellent in the skin beautifying effect, particularly in the whitening effect and / or the antiaging effect.

[0006]

Means for Solving the Problems As a result of intensive studies on components that can be used as a medicinal component of a skin external preparation, the present inventors have found that a compound having a specific structure,
It was found that a synergistic effect, which cannot be obtained when each of them is used alone, can be obtained by combining with a specific component, and the present invention has been completed based on this finding.

According to the present invention, (A) the following general formula (1):

[Chemical 2] (In the general formula (1), R ¹ represents —CH ₂ OH or COOR ⁶ , R ⁶ represents hydrogen, a lower alkyl group having 1 to 3 carbon atoms, or a cation capable of forming a salt with COO ⁻ , ² ~ R ⁵
Each independently represent a hydrogen atom or a methyl group, ... A ...
Is _{= C (CH 3) -,} - C (CH 3) =, - C (= C
_{H 2) -, - CH (} CH 3) - or -C (OH) (C
H ₃₎ - represents a. ) One or more compounds represented by the formula (B), and (B) asparagus extract, adzuki bean extract, sow extract, senkyu extract, age extract, rubus extract, kujin extract, gokahi extract. , Coffee extract, rice bran extract, wheat germ extract, cabbage extract, hawthorn extract, white lily extract, peony extract, tea extract (extracts of green tea, black tea, oolong tea, etc.), molasses extract, grape Extract, hop extract, mica extract, mocca extract, sardine extract, seaweed extract, dibutylhydroxytoluene, butylhydroxyanisole, mannitol, β-carotene, quercetin, quercitrin, rutin, vitamin E and its derivatives, Genoshoko extract, Yukinoshita extract, Sampens extract, Melissa extract, glycyl Tinctic acid and its derivatives, Glycyrrhetinic acid and its derivatives, Vitamin B and its derivatives, Gentiana extract, Dokudami extract, Botan extract, Aloe extract, Arnica extract, Hypericum extract, Oat extract, King ginkgo extract, Salvia extract, birch extract, perilla extract, mugwort extract, chamomile extract, comfrey extract, juniper extract, watercress extract, quince extract, elder extract, sycamore extract, mukuroji extract, Eucalyptus extract, Astragalus extract, Vitamin A and its derivatives, Tartaric acid, Malic acid, Glycolic acid, Succinic acid, Serine, Glutamic acid, Hydroxyproline, Theanine, Pyrrolidonecarboxylic acid, Astragalus extract, Soybean extract, Carrot extract, Barley extract, beech sprout extract,
Ginkgo biloba extract, Centella asiatica extract, yeast extract, lactic acid bacterium extract, bifidobacteria extract, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4
-Sodium methoxybenzophenone-5-sulfonate, 2-ethylhexyl paramethoxycinnamate, 4-
tert-butyl-4′-methoxydibenzoylmethane, Altea extract, gall extract, dio extract,
Horse chestnut extract, mallow extract (Astragalus oleracea) extract, apricot extract, lime extract, raspberry extract, almond extract, tomato extract, phospholipids and their derivatives, armature extract, coltsfoot extract and quince seed extract There is provided an external skin preparation containing one or more selected from the group consisting of the following:

As one aspect of the present invention, (A) one or more compounds represented by the general formula (1), and (C)
Touki extract, sowaku extract, senkyu extract,
Asparagus extract, Agets extract, Raspberry extract, Kujin extract, Gokahi extract, Coffee extract, Rice bran extract, Wheat germ extract, Saishin extract, Hawthorn extract, White lily extract, Peony extract, Tea extract (extracts of green tea, black tea, oolong tea, etc.), molasses extract, grape extract, hop extract, mica extract,
There is provided a skin external preparation containing one or two or more selected from the group of medicinal agents consisting of a mocca extract, an augon extract and a seaweed extract.

As another aspect of the present invention, (A) one or more compounds represented by the general formula (1) and (D) dibutylhydroxytoluene, butylhydroxyanisole, mannitol, β -Skin containing one or more selected from the group of medicinal agents consisting of carotene, quercetin, quercitrin, rutin, vitamin E and its derivatives, gem ginger extract, Yukinoshita extract, sunpens extract and melissa extract. An external preparation is provided.

As another aspect of the present invention, (A) one or more compounds represented by the general formula (1), and (E) glycyrrhizinic acid and its derivatives, glycyrrhetinic acid and its derivatives. , Vitamin B and its derivatives,
Gentiana extract, Dokudami extract, Botan extract, Aloe extract, Arnica extract, Hypericum extract, Oat extract, Goldfish extract, Salvia extract, Birch extract, Perilla extract, Artemisia extract, Chamomile extract Or a comfrey extract, a water lily extract, a watercress extract, a quince extract, an elderberry extract, a syringa extract, a sucrose extract, a eucalyptus extract and an astragalus extract. An external preparation for skin containing two or more kinds is provided.

As another embodiment of the present invention, (A) one or more compounds represented by the general formula (1), and (F) vitamin A and its derivatives, tartaric acid, malic acid, Glycolic acid, succinic acid, serine, glutamic acid,
Hydroxyproline, theanine, pyrrolidonecarboxylic acid, Astragalus extract, soybean extract, carrot extract, barley extract, beech sprout extract, ginkgo extract,
1 or 2 selected from the group of medicinal agents consisting of Centella asiatica extract, yeast extract, lactic acid bacterium extract and bifidobacteria extract
An external preparation for skin containing at least one kind is provided.

In another aspect of the present invention, (A) one or more compounds represented by the general formula (1), and (G) 2-hydroxy-4-methoxybenzophenone, 2- Hydroxy-4-methoxybenzophenone-5
-Sulfonic acid, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 2-ethylhexyl paramethoxycinnamate, and 4-tert-butyl-4'-methoxydibenzoylmethane There is provided an external skin preparation containing one or more of the following.

In another aspect of the present invention, (A) one or more compounds represented by the general formula (1), and (H) an altea extract, a shovel extract, a diorhea extract. , Horse chestnut extract, mallow extract, apricot extract, lime extract, raspberry extract, almond extract, tomato extract, phospholipids and their derivatives, armature extract, coltsfoot extract and quince seed There is provided a skin external preparation containing one or more selected from the group of medicinal agents consisting of extracts.

The external preparation for skin of the present invention is excellent as an external preparation for beautiful skin, particularly as an external preparation for whitening skin and / or an external preparation for preventing aging. In the present specification, the term "beautiful skin" means, for example, suppression of pigmentation, dull skin,
It should be interpreted in the broadest sense, including the prevention and improvement of skin darkening due to sunburn, spots and freckles, and the prevention and improvement of wrinkles, etc., and "whitening" and "aging prevention" should be included in the scope. Should be understood.

In a preferred embodiment of the present invention, the compound represented by the general formula (1) is C
istus ladaniferus L. , Cist
uscreticus L. , Cistus mono
perience L. And Cistus salv
A compound extracted from one or more plants selected from the group of plants consisting of ifolius, or the above-mentioned external preparation for skin which is a compound prepared from the compound; a compound represented by the general formula (1) Containing Cistus ladaniferus L. , Ci
stus creticus L. , Cistus m
onoperiensis L .; And Cistus s
1 selected from the group of plants consisting of alvifolius
The above-mentioned external preparation for skin, which comprises one or more extracts.

[0016] From another point of view, one or more compounds represented by the general formula (1), and a white lily extract,
A whitening skin external preparation containing one or more selected from Sohaku extract, natural vitamin E, dipotassium glycyrrhizinate, yeast extract, hydrogenated soybean phospholipid and 2-ethylhexyl paramethoxycinnamate; One or more of the compounds represented by the general formula (1), butylhydroxytoluene, carrot extract, ginseng extract,
1 selected from 2-ethylhexyl paramethoxycinnamate, retinol palmitate and coltsfoot extract
And an external anti-aging skin preparation containing two or more species.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The external preparation for skin of the present invention contains, as the component (A), one or more physiologically active components of the compounds represented by the following general formula (1).

[0018]

[Chemical 3]

In the general formula (1), R ¹ represents —CH ₂ OH or COOR ⁶ , and R ⁶ represents hydrogen, a lower alkyl group having 1 to 3 carbon atoms, or a cation capable of forming a salt with COO ^−. Represent The lower alkyl group having 1 to 3 carbon atoms may be linear or branched. As the alkyl group,
Examples thereof include a methyl group, an ethyl group, an n-propyl group and an iso-propyl group. Examples of the cation capable of forming a salt with —COO ⁻ include cations such as Na ⁺ , K ⁺ and NH ₄ ⁺ .

In the general formula (1), R ^{2 to} R ⁵ each independently represent a hydrogen atom or a methyl group, and ... A ... Is = C (C
_{H 3) -, - C (} CH 3) =, - C (= CH 2) -, - C
H (CH ₃₎ - or _{-C (OH) (CH 3)} - represents a.

The compound represented by the general formula (1) can be extracted from plants. In addition, extracts from plants are commercially available (Labdanum Absolute, manufactured by Givaudan, etc.), and commercially available products can be used in the present invention.
Further, as an extract, after obtaining an acid in which R ¹ is —COOH, it can be used as the component (A) after forming an ester form such as methyl or ethyl, a reduced form or a salt.

The type of plant from which the compound represented by the general formula (1) is extracted is not particularly limited as long as it is a plant containing the compound, but in particular Cistu
sladaniferus L .; , Cistus cr
eticus L. , Cistus monoperi
ensis L. , Cistus salvifolia
It is advantageous to use a plant of us (Helianthaceae). These may be used alone or in combination of two or more.

The extraction site of the plant is not particularly limited, and it can be extracted from leaves, branches, bark and the like.
In addition, the extraction operation may be performed immediately after collecting each site,
Alternatively, the extraction operation can be performed after each site is collected and dried. The extraction method is preferably performed using one or more solvents selected from water, lower alcohols, petroleum ethers and hydrocarbons. Here, the lower alcohol means an alcohol having 1 to 4 carbon atoms, and methyl alcohol, ethyl alcohol and the like are particularly preferable. Known petroleum ethers can be used, and commercially available ones can also be used. Examples of the hydrocarbon solvent include aliphatic hydrocarbons that are liquid at room temperature, alicyclic hydrocarbons, and aromatic hydrocarbons, but aliphatic hydrocarbons that are liquid at room temperature and aromatic hydrocarbons are particularly preferable, and among others, Hydrocarbons such as hexane and toluene are preferred.

The extraction operation varies depending on the type of the above plant and the solvent used, but usually it can be carried out by immersing the cut plant in the above solvent at a temperature of room temperature to 50 ° C. The solvent may be gently agitated during the immersion. Further, a device such as a well-known Soxhlet extractor may be used. The time required for extraction is usually about 3 hours to 48 hours. Alternatively, the leaves, branches or trunks of the above plant may be crushed and then extracted by steam distillation or boiling in hot water. In this case, it can be obtained by scooping off the gum content floating on water by steam distillation or hot water extraction, and separating it from the insoluble matter with the solvent used for the above extraction. The extract thus obtained has 2
5 to 35% by mass (hereinafter simply referred to as “%”) of labdenic acid is contained.

The crude extract from the plant or the commercially available extract can be used as it is as the component (A). The compound can be purified and used as the component (A). Below, Loved-7-En-15-
Oic Acid, Loved-8 (17) -En-15-
A typical example of a method for purifying each component from a crude extract or a commercially available product containing a mixture of euic acid and labed-8-en-15-oic acid will be described, but the present invention is limited to the following methods. It is not something that will be done. The crude extract or commercially available extract was subjected to molecular distillation under a reduced pressure of 0.1 to 0.5 mmHg, and the fractions up to 160 ° C to 230 ° C were collected. -15-Oic Acid, Rubbed-8 (17) -en-15-Oic Acid, Rubbed-8-en-15-Oic Acid. As the component (A), these acid mixtures may be used as they are, or if necessary, after preparing an ester form such as methyl or ethyl, a salt or a reduced form, the mixture may be used.

Furthermore, three acids can be separated from this acid mixture. Specifically, this acid mixture is dissolved in ethanol, reacted in the presence of a catalytic amount of sulfuric acid to give an ethyl ester, and then subjected to silica gel chromatography using silver nitrate-treated silica gel.
The column is washed with hexane and then eluted with 1% ethyl acetate-hexane. Introduction Loved-8-En-15-
Oic acid ethyl ester is eluted, and then rhabdo-7-ene-15-oic acid ethyl ester and rhabdo-8 (17) -en-15-oic acid ethyl ester are eluted in this order. The solvent is distilled off to obtain pure ethyl ester products. A free acid can be obtained by hydrolysis from the obtained ethyl ester form. Furthermore, a methyl ester can be obtained by reacting a free acid with diazomethane.

[0028] The thus obtained Cistus ladaniferus L. , C
istus creticus L. , Cistus
monoperensis L .; , Cistus s
Extracts of stems, branches, leaves, etc., such as alvifolius,
And the acid, methyl ester, ethyl ester obtained from the extract, or a mixture of two or more thereof can be used as the component (A) of the present invention. That is, as an embodiment of the present invention, (A) component is (i) Cistus ladaniferus belonging to the family Asteraceae.
L. , Cistus creticus L .; , Cis
tus monoperiensis L. , Cistu
s salvifolius stems, branches, leaves, etc. hot water extracts or organic solvents (ethanol, hexane, etc.)
Extract; (ii) Labd-7-en-15-oic acid (labd-7-en-15-oic) obtained by molecular distillation of the extract of (i) above or crude labdene acids.
acid), loved-8 (17) -en-15-oic acid (labd-8 (17) -en-15-oi
c acid) and labed-8-en-15-oic acid (labd-8-en-15-oic acid).
one or more selected from d); (iii) above (i)
The skin external preparation is a salt of an acid of i) or a methyl or ethyl ester form thereof; or (iv) a reduced form of (iii) above.

The content of the compound represented by the general formula (1) in the external preparation for skin of the present invention is preferably 0.00001 to 5% as a dry solid content, more preferably 0.0001 to 2%. Is. Within this range, the plant extract can be blended in a stable manner, and an excellent skin beautifying effect (in particular, whitening and anti-aging effect) can be exhibited. Further, when the extract is used, the concentration of the extract is not limited as long as the content of the dry solid matter as the solute is within the above range.

In the present invention, the component (B) to be combined with the component (A) is one or two selected from the agents shown below.
More than a seed. In the following specific examples, the “derivative” includes an ester and a salt. Asparagus extract, Touki extract, Sophoraceae extract, Senkyu extract, Agetsu extract, Rubus extract, Kujin extract, Gokahi extract, Coffee extract, Rice bran extract, Wheat germ extract, Saishin extract, Hawthorn extract, white lily extract, peony extract, tea extract, molasses extract, grape extract, hop extract, mica extract, mocca extract, sardine extract, seaweed extract, dibutylhydroxytoluene, butylhydroxy Anisole, mannitol, β-carotene, quercetin, quercitrin, rutin, vitamin E and its derivatives, ginger extract, Yukinoshita extract, sunpens extract, melissa extract, glycyrrhizic acid and its derivatives, glycyrrhetinic acid and its derivatives, vitamins B and its derivatives, Antiana extract, Dokudami extract, Botan extract, Aloe extract, Arnica extract, Hypericum extract, Oat extract, Goldfish extract, Salvia extract, Birch extract, Perilla extract, Artemisia extract, Chamomile extract Thing, comfrey extract, jiuyu extract, watercress extract,
Calendula officinalis extract, elderberry extract, syringa extract, mukurodi extract, eucalyptus extract, astragalus extract, vitamin A and its derivatives, tartaric acid, malic acid, glycolic acid, succinic acid, serine, glutamic acid, hydroxyproline, theanine , Pyrrolidone carboxylic acid, Eucommia ulmoides extract, soybean extract, carrot extract, barley extract, beech bud extract, ginkgo extract, Centella asiatica extract, yeast extract, lactic acid bacterium extract, bifidobacteria extract, 2- Hydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid sodium salt, paramethoxycinnamic acid-
2-Ethylhexyl, 4-tert-butyl-4'-methoxydibenzoylmethane, Altea extract, ginseng extract, dioea extract, horse chestnut extract, mallow extract, apricot extract, lime extract , Raspberry extract, almond extract, tomato extract, phospholipids and their derivatives, armature extract, coltsfoot extract and quince seed extract.

In the component (B), asparagus extract,
Touki extract, sowaku extract, senkyu extract,
Agetsu extract, raspberry extract, kujin extract, gokahi extract, coffee extract, rice bran extract, wheat germ extract, saishin extract, hawthorn extract, white lily extract, peony extract, tea extract (green tea , Black tea, oolong tea and the like), molasses extract, grape extract, hop extract, mica extract, mocca extract, sardine extract and seaweed extract (these are components (C)),
Alone, it mainly shows efficacy as a whitening agent, but the above (A)
When used in combination with the components, they exhibit excellent whitening and / or antiaging effects that cannot be obtained when used alone.
More preferable ones include wheat germ extract, white lily extract, sowaku extract, tea extract (extracts of green tea, black tea, oolong tea, etc.), grape extract, sorghum extract, and seaweed extract.

Among the components (B), dibutylhydroxytoluene, butylhydroxyanisole, mannitol,
β-carotene, quercetin, quercitrin, rutin, vitamin E and its derivatives (dl-α (β, γ) -tocopherol acetate dl-α-tocopherol acetate, dl-α-tocopherol nicotinate, linoleic acid dl-α-
(Tocopherol, etc.), ginkgo biloba extract, Yukinoshita extract, sampens extract and melissa extract (these are referred to as component (D)) mainly show efficacy as an antioxidant alone, When used in combination, they have excellent whitening and / or antiaging effects that cannot be obtained when used alone. More preferred are vitamin E and its derivatives, dibutylhydroxytoluene, β-carotene, rutin, and Yukinoshita extract.

Of the above-mentioned component (B), glycyrrhizic acid and its derivative, glycyrrhetinic acid and its derivative, vitamin B and its derivative, gentian extract, dokudami extract, peony extract, aloe extract, arnica extract, and Hypericum perforatum extract. Substance, psyllium extract, goldfish extract, salvia extract, birch extract, perilla extract, mugwort extract, chamomile extract, comfrey extract, juyu extract, watercress extract, quince extract, elderberry extract , The extract of Phytophthora radix, the extract of Mukuroji, the extract of Eucalyptus and the extract of Forsythia (these are referred to as the component (E)) are mainly effective as an anti-inflammatory agent, but should be used in combination with the component (A). Thus, it has an excellent whitening and / or antiaging effect that cannot be obtained when used alone. More preferred are glycyrrhizic acid and its derivatives, glycyrrhetinic acid and its derivatives,
Examples thereof include aloe extract, psyllium extract, goldfish extract, perilla extract, chamomile extract, comfrey extract, and jujube extract.

In the component (B), vitamin A and its derivatives (retinol palmitate, retinol acetate, etc.),
Tartaric acid, malic acid, glycolic acid, succinic acid, serine,
Glutamic acid, hydroxyproline, theanine, pyrrolidone carboxylic acid, Eucommia ulmoides extract, soybean extract, carrot extract, barley extract, beech sprout extract, ginkgo extract, Centella asiatica extract, yeast extract, lactic acid bacterium extract and bifidus Bacterial extracts (these are referred to as (F) components), when used alone, mainly show efficacy as a cell activating agent, but when used in combination with the (A) component, they are not obtained when used alone, and are excellent. It has a whitening and / or anti-aging effect. More preferred are vitamin A and its derivatives, hydroxyproline, carrot extract,
Examples include barley extract, beech bud extract, ginkgo extract, Centella asiatica extract and yeast extract.

In the component (B), 2-hydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-
Sodium 4-methoxybenzophenone-5-sulfonate, 2-ethylhexyl paramethoxycinnamate and 4
-Tert-Butyl-4'-methoxydibenzoylmethane (these are referred to as the component (G)) mainly exhibits a medicinal effect as an ultraviolet ray inhibitor alone, but when used in combination with the component (A), It has an excellent whitening and / or anti-aging effect that cannot be obtained when used in. More preferred are 2-hydroxy-4-methoxybenzophenone, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 2-ethylhexyl paramethoxycinnamate, 4-tert-butyl-4′-.
Methoxydibenzoylmethane may be mentioned.

Among the above-mentioned components (B), Altea extract, gall extract, dio extract, horse chestnut extract, mallow extract, apricot extract, lime extract, raspberry extract, almond extract , Tomato extract, phospholipids and derivatives thereof (eg, soybean phospholipids, hydrogenated soybean phospholipids, hydrogenated soybean lysophospholipids, hydrogenated egg yolk lecithin, egg yolk lecithin, egg yolk lysophosphatidylcholine, etc.), armature extract, coltsfoot extract Also, Quinceseed extract (these are referred to as (H) component) shows the efficacy mainly as a moisturizer alone, but when used in combination with the (A) component, it cannot be obtained when used alone, Excellent whitening and / or anti-aging effect. More preferable ones include phospholipids and derivatives thereof, armilla extract, mallow extract, coltsfoot extract and quince seed extract.

The external preparation for skin of the present invention has an excellent skin beautifying effect,
In particular, it has an excellent whitening and / or antiaging effect. Among them, for external use on the skin containing one or more selected from white lily extract, sour apricot extract, natural vitamin E, dipotassium glycyrrhizinate, yeast extract, hydrogenated soybean phospholipid and 2-ethylhexyl paramethoxycinnamate The agent is excellent as an external preparation for whitening skin. In addition, a skin external preparation containing one or more selected from butylhydroxytoluene, carrot extract, green tea extract, jujube extract, 2-ethylhexyl paramethoxycinnamate, retinol palmitate and coltsfoot extract. Is excellent as an anti-aging external skin preparation.

The blending amount of the above-mentioned component (B) in the external preparation for skin of the present invention varies depending on the type (component (C) to component (H)), but it is preferably within the following range. Within this range, when combined with the component (A), it does not affect the stability of the preparation and the component (A) in the preparation over time, and has a higher skin beautifying effect (in particular, a whitening and / or antiaging effect). ) Can be demonstrated.

The blending amount of the component (C) in the external preparation for skin of the present invention is preferably 0.00001 to 10%, more preferably 0.0001 to 5%. When the extract is used as it is, the dry solid content may be within this range. Within this range, a skin external preparation having a superior whitening effect and a good feeling in use can be obtained.

The content of the component (D) in the external preparation for skin of the present invention is preferably 0.00001 to 5%, more preferably 0.0001 to 3%. When the extract is used as it is, the dry solid content may be within this range. Within this range, a superior antioxidative effect is exhibited, an excellent whitening and / or antiaging effect is exhibited, and a skin external preparation having a good feeling in use is obtained.

The content of the component (E) in the external preparation for skin of the present invention is preferably 0.00001 to 5%, more preferably 0.0001 to 3%. When the plant extract is used as it is, the dry solid content may be within this range. Within this range, an excellent anti-inflammatory effect is observed, an excellent whitening and / or antiaging effect is exhibited, and a skin external preparation having a good feeling in use is obtained.

The amount of the component (F) in the external preparation for skin of the present invention is preferably 0.00001 to 5%, more preferably 0.0001 to 3%. When the extract is used as it is, the dry solid content may be within this range. If it is in this range, a better effect of improving rough skin is exhibited, and an excellent effect of whitening and / or aging is exhibited,
In addition, a skin external preparation having a good feeling in use can be obtained.

The content of the component (G) in the external preparation for skin of the present invention is preferably 0.001 to 30%, more preferably 0.01 to 25%. Within this range, a superior external UV-preventing effect is exhibited, an excellent whitening and / or anti-aging effect is exhibited, and a skin external preparation having a good feeling in use can be obtained.

The compounding amount of the drug (H) in the external preparation for skin of the present invention is preferably 0.001 to 25%, more preferably 0.01 to 20%. When the extract is used as it is, the dry solid content may be within this range. Within this range, a superior external moisturizing effect is exhibited, an excellent whitening and / or antiaging effect is exhibited, and a skin external preparation having a good feeling in use is obtained.

In the external preparation for skin of the present invention, the above-mentioned components (A) and (B), which are essential components, are blended in various forms of bases known as ordinary external preparations for skin according to a conventional method. It can be prepared.

The form of the external preparation for skin is not particularly limited, and examples thereof include emulsions, creams, lotions, packs, detergents, makeup cosmetics, dispersions, ointments, liquids, aerosols, patches, and patches. The cosmetic may be in any form such as an agent, a liniment, etc., or may be an external drug.

In addition to the above essential components, the external preparation for skin of the present invention also contains various components commonly used in cosmetics, quasi drugs, external medicines, such as water, alcohols, oils, and surface active agents. Agents, thickeners, powders, chelating agents, pH adjusting agents, various medicinal agents, extracts derived from animals and plants / microorganisms, fragrances and the like can be appropriately added within a range that does not impair the effects of the present invention. Of these, specific examples are shown below.

As alcohols, monohydric alcohols such as ethyl alcohol and polyhydric alcohols such as glycerin and 1,3-butylene glycol are used for the purpose of dissolving, cooling, antiseptic, moisturizing, etc., as long as they do not overlap with the essential components. Can be used.

The oil agent can be used regardless of its origin and properties as it improves usability and usability.
For example, liquid paraffin, squalane, triglyceride oil, ester oil, waxes, fatty acids, higher alcohols, silicone oil, fluorinated oil, various waxes and the like.

The surfactant is used for emulsification and solubilization of oils and the like, and anionic, cationic, nonionic and amphoteric surfactants can be used.

As the thickener, it is possible to use carboxyvinyl polymer, carrageenan, agar, xanthan gum, dextrin fatty acid ester, organically modified clay mineral, etc. regardless of whether they are chemically synthesized products or natural products. or,
These components can be used not only for adjusting the viscosity of the system, but also for gelling, moisturizing, film formation and the like.

The powder may be compounded or surface-treated in order to improve usability and usability regardless of shape, particle size, presence or absence of porosity, crystal structure and the like.
Inorganic powders such as talc, mica, sericite, silicic acid anhydride, organic powders such as nylon powder, fish scale foil, pearl pigments such as bismuth oxychloride, iron oxide, carbon black, inorganic pigments such as ultramarine, tar pigments and The lake, natural pigment, titanium oxide, fine particle titanium oxide, zinc oxide, fine particle zinc oxide and the like are used depending on the application. In particular, it is preferable to contain fine particle titanium oxide or fine particle zinc oxide because the effect of the present invention can be further enhanced.

In order to prevent the quality deterioration of the components in the system, EDT
A chelating agent such as A and a pH adjusting agent with a buffer such as lactic acid-sodium lactate can also be used.

Examples of the medicinal agent include various substances including vitamins, hormones, extracts derived from animals and plants, and microorganisms. For example, antibacterial agents are used for the purpose of preventing and improving acne, benzoic acid, Examples thereof include sodium benzoate, paraoxybenzoic acid ester, parachlorometacresol, benzalkonium chloride, phenoxyethanol and isopropylmethylphenol. By blending these, pigmentation due to inflammation of bacterial skin such as acne can be suppressed and a higher whitening and / or skin beautifying effect and antiaging effect can be exhibited.

The active oxygen scavenger is used for the purpose of suppressing the production of lipid peroxide due to ultraviolet rays, and it includes superoxide dismutase, catechin and its derivatives, thiamines (thiamine hydrochloride, thiamine sulfate), riboflavins (riboflavin). , Riboflavin acetate), pyridoxines (pyridoxine hydrochloride, pyridoxine dioctanoate, etc.), nicotinic acids (nicotinamide, benzyl nicotinate, etc.), and other vitamin Bs. By blending these active oxygen removing agents, dullness can be suppressed, and higher whitening and / or skin beautifying effect and antiaging effect can be exhibited.

In addition, as a combination of the compounds, the effects of the present invention can be further enhanced by using proteins or their derivatives or hydrolysates and their salts (collagen, elastin, keratin, etc.), mucopolysaccharides and their derivatives (hyaluronic acid, Chondroitin sulfate, etc.), amino acids and their derivatives (histidine, serine, glycine,
Theanine, aspartic acid, arginine, pyrrolidonecarboxylic acid, etc.), sugars (sorbitol, erythritol,
Trehalose, inositol, glucose, xylitol, sucrose and its derivatives, dextrin and its derivatives, honey, etc.), D-panthenol and its derivatives,
Glycolipid, ceramide, ashitaba extract, avocado extract,
Hot spring water, Scutellaria barbata extract, Odorikosou extract,
Ononis extract, oat extract, gardenia extract,
Kumazasa extract, Burdock extract, Wheat extract, Sophoraceae extract, Spirea extract, Ginger extract, Peppermint (Peppermint) extract, Pleurotus cornucopia (Thyme) extract, Camellia extract, Tormentilla extract, Parsley extract Thing, peppermint extract, hamamelis extract,
Rose extract, cypress extract, sunflower extract, butchers bloom extract, prune extract, loofah extract,
Examples thereof include Bodaiju extract, pine extract, quince extract, mucin, cornflower extract, lavender extract, apple extract, and gentian (ryutan) extract.
Furthermore, as agents having a sealing effect on the skin surface, jojoba oil, macadamia nut oil, olive oil, apricot kernel oil, persic oil, safflower oil, sunflower oil, avocado oil, medhome oil, camellia oil, almond oil, perilla oil, sesame oil. By blending borage (borage) oil, cacao butter, shea butter, etc., higher whitening and / or skin beautifying effects can be achieved, and it is expected that a transparent skin can be realized (in the parentheses, Other names of plants, crude drug names, etc. are listed).

The blood circulation promoting agent is used for the purpose of promoting excretion of melanin by promoting blood flow in the skin, and examples include capsicum tincture and γ-oryzanol, and examples of the enzyme include lipase and papain. By blending these, higher whitening and / or skin beautifying effect can be exhibited.

[0057]

EXAMPLES The present invention will be described in more detail with reference to Reference Examples, Test Examples and Examples, but the present invention is not limited thereto.

[Example 1] Cistus ladanif
erus L. Preparation of Extracts Hannicaceae; Cistus ladanife
rus L. Oil was removed from 20 Kg of crushed leaves and twigs by steam distillation. Then, n-hexane 2
The extract obtained by performing extraction at 00 Kg was distilled under reduced pressure to remove low-boiling-point substances to obtain 150 g of a solid-paste extract.

[Example 2] Preparation of labdene acids and their methyl and ethyl esters Commercially available Labdanum Absolute (manufactured by Givaudan) 10
g under molecular pressure distillation under reduced pressure (0.1 mmHg), 180 ° C
Fractions up to 220 ° C (4.3 g) were collected. Compound 1 (labd-8-ene-15-oic acid) and compound 4 (labd-7-ene-15) shown below were contained in this fraction.
-Oic acid), Compound 7 (Labd-8 (17)
-En-15-Oic acid) was contained (this mixture is hereinafter referred to as an acid mixture). 1 g of this acid mixture
Was dissolved in 2 mL of ether, and a diazomethane ether solution was added dropwise to obtain 0.96 g of a methyl ester compound (this methyl ester compound is hereinafter referred to as a methyl ester mixture).
Similarly, 10 g of this acid mixture was dissolved in 100 mL of ethanol, and esterification was performed in the presence of a sulfuric acid catalyst to obtain 9.5 g of an ethyl ester body (this ethyl ester body is hereinafter referred to as an ethyl ester mixture).

The ethyl ester mixture was then chromatographed on silica gel to separate the three acids. Specifically, 10 g of the ethyl ester mixture was dissolved in 100 mL of hexane and injected into a column of silica gel treated with silver nitrate, and then a solvent was injected and eluted. The injected solvent was hexane first, and then a mixed solvent in which 1 vol% of ethyl acetate was added to hexane. First, compound 3 (labd-8-ene-15-oic acid ethyl ester) was eluted, and then compound 6 (labd-
7-ene-15-oic acid ethyl ester and compound 9 (labd-8 (17) -en-15-oic acid ethyl ester) were eluted in this order. The solvent was distilled off from each eluate to obtain pure ethyl esters (0.83 g, 0.16 g and 0.63 g in the order of elution). The obtained ethyl ester form was hydrolyzed by a conventional method to obtain a free acid. Furthermore, a diazomethane ether solution was added dropwise to the free acid, and the solvent was distilled off to give a methyl ester form.

[0061]

[Chemical 4]

[0062]

[Chemical 5]

[0063]

[Chemical 6]

3. Ethyl ester mixture obtained in Example 2.
3. Dissolve 3 g in 10 mL of ethanol, add 0.2 g of 5% palladium carbon catalyst, and carry out hydrogenation reaction.
1 g of compound 11 was obtained. Furthermore, it hydrolyzed and obtained the compound 10.

[0065]

[Chemical 7]

Example 3 Suppression of Melanin Production by Cell Culture and Cell Viability Test B16 melanoma cultured cells derived from mice were used. Two
An appropriate amount of 10% FBS-containing MEM medium was placed on a single 6-well plate, B16 melanoma cells were seeded, and left standing at 37 ° C. in a carbon dioxide concentration of 5 vol%. The next day, the Cistus ladaniferus L. The extract and labdene acids obtained in Example 2 and their methyl and ethyl esters were added to a final concentration of 0 (control), 5, 10 μ.
g / mL, or a whitening agent Shirayuri extract (manufactured by Maruzen Pharmaceutical Co., Ltd.) was added and mixed with the sample preparation solution so as to be 0 or 100 μg / mL. On the 5th day of culture, the medium was exchanged and the sample preparation solution was added again. On the next day, the medium was removed and one plate was washed with phosphate buffer (pH 7) and then collected, and the whiteness of the B16 melanoma cultured cells was evaluated according to the following criteria.

As a comparative example, Yokuinin extract (100
The same test was performed for (μg / mL). Yokuinin extract is 70vol in 10g of Yokuinin (JP).
Add 100 mL of 100% hydrous ethyl alcohol and stir at room temperature for 3
After extraction for a day, it was obtained by filtration. At this time, the dry solid content of Yokuinin extract was 0.8%.

(Judgment criteria) ++: Very white with respect to the control. +: Clearly white with respect to the control. ±: slightly whiter than the control. -: The same black color as the control.

For the remaining one plate, cells were fixed with formalin and then stained with 1% crystal violet solution. The cell viability for each sample concentration was measured with a monoserator (Olympus). The above results are shown in Table 1.

(Result)

[Table 1]

As is clear from the results of Table 1, Cistu
s ladaniferus L .; It was confirmed that the extract, labdene acids and their methyl esters and ethyl esters have the ability to suppress melanin production alone and have low toxicity to B16 melanoma cultured cells. Furthermore, when used in combination with the whitening agent Shirayuri extract, a synergistic whitening effect was obtained compared to the case of single treatment. Therefore, Cistus ladaniferus L. By applying a combination of extract and labdenic acid and its methyl ester and ethyl ester and white lily extract to the skin, it exerts an extremely excellent melanin production inhibitory effect, blackening of the skin due to sunburn, spots, freckles, etc. Can be effectively suppressed, and whitening and beautiful skin effects can be expected.

[Example 4: Cream] Each cream having the composition shown in Table 2 was prepared. First, the components (1) to (6) and (1
2) was mixed, and the component (16) heated and kept at 70 ° C. was added to the mixture heated and kept at 70 ° C. further,
The components (7) to (11) and (13) to (15) were mixed and then cooled to obtain a cream. With respect to each of the obtained creams, whitening and skin beautifying effects were examined by the following test methods.

(Test method) 27 per cream product tested
~ 15-year-old women a panel of 12 people every day for 12 weeks,
After washing the face twice in the morning and at night, an appropriate amount of the test cream was applied to the face, and the whitening and skin-beautifying effects of the application were evaluated according to the following criteria. The evaluation results are shown by the number of panel members corresponding to each evaluation. (Evaluation Criteria) <Evaluation><Contents> Effectiveness The dullness of the skin became inconspicuous. Somewhat effective The dullness of the skin became less noticeable. Ineffective No change from before use.

(Composition and Results)

[Table 2]

As shown in the results of Table 2, as compared with the comparative product, Cistus ladaniferus L. The cream of the product of the present invention in which the extract and various components (components (8) to (13)) which are the component (B) of the present invention are used in combination,
It was clarified that by applying these to the skin, it is possible to prevent and improve the generation of "dullness" on the skin and to make the skin beautiful.

[Example 5 Cell activation test by cell culture] Human newborn-derived fibroblasts NB1RGB were used. Two
Proper amount of culture medium in a 4-well plate, fibroblast NB1RG
B was seeded and left standing at 37 ° C. in a carbon dioxide concentration of 5 vol%. Next day, the Cistus ladan obtained in Example 1
iferusL. The extract, labdene acids obtained in Example 2 and the methyl ester and ethyl ester thereof had a final concentration of 0 (control), 5, 10 μg / mL, and a carrot extract (manufactured by Maruzen Pharmaceutical Co., Ltd.) as a cell activating agent. , 100 μg /
The sample preparation solution was added and mixed so as to be mL. Culture 4
On the day, the medium was exchanged and the sample preparation solution was added again. On the next day, the medium was removed, the cells were washed with phosphate buffer, collected, and grown in each sample preparation solution. Fibroblast NB1RG
The number of B cells was evaluated as the cell proliferation rate compared to the control.

As a comparative example, a soybean extract (100 μg / m 2) which is already known to have a cell activating effect is also used.
The same test was performed for L). The soybean extract was obtained by adding 100 ml of 70 vol% hydrous ethyl alcohol to 10 g of soybean seeds and performing extraction at room temperature for 3 days.
Obtained by filtration. At this time, the dry solid content of the soybean extract was 0.
It was 5%.

(Evaluation Criteria) The number of cells grown by adding each sample preparation solution was compared with the number of control cells, and the cell activation effect was evaluated using the cell growth rate as an index. The number of cells was counted using a hemocytometer.

(Result)

[Table 3]

As is clear from the results shown in Table 3, the plant extract was found to have a cell activating effect on human newborn-derived fibroblasts NB1RGB. It was confirmed that the combined use of these products had a superior cell activation ability. Therefore, the cell activating agent of the present invention is a Cistus ladanifer.
us L. By applying a combination of extract and labdenic acid and its methyl ester and a combination of ethyl ester and carrot extract, it exerts an extremely excellent anti-aging effect, and wrinkles on the skin caused by aging, exposure to ultraviolet rays, etc. It is expected that slackness will be effectively improved.

Example 6: Cream A cream having the composition shown in Table 4 was prepared. First, the components (1) to (6) and (10) are mixed and heated to a mixture kept at 70 ° C.,
A portion of component (15) heated and kept at 70 ° C. was added.
Components (7) to (9) and (11) to (14) were mixed with this, and then cooled to obtain a cream. The wrinkle improving effect of each of the obtained creams was examined by the following test method.

(Composition and Results)

[Table 4]

(Test method) 35 per one test cream
-A panel of 20 women aged 59 years old, 2 daily in the morning and at night
After washing the face once and for 12 weeks, an appropriate amount of the test cream was applied to the face. The effect of improving wrinkles by coating was evaluated according to the following criteria. (Evaluation Criteria) <Evaluation><Contents> Effectiveness The wrinkles on the skin became inconspicuous. Somewhat effective Wrinkles on the skin are less noticeable. Ineffective No change from before use.

As shown in the results of Table 4, as compared with the comparative product, Cistus ladaniferus L. The cream of the product of the present invention in which the extract and each component (B) are used in combination can improve "wrinkles" and the like of the skin by applying these to the skin, and give a beautiful and firm skin. It became clear to do.

[Example 7: Face wash] The following components (1) to (1)
0) was mixed by heating and maintained at 70 ° C. This was cooled to room temperature, and (11) to (16) were added and mixed to obtain a face wash. (Component) (%) (1) N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine 20.0 (2) lauryl dimethylamino acetic acid betaine 10.0 (3) coconut oil fatty acid diethanolamide 3.0 (4) Coconut oil fatty acid potassium 5.0 (5) Stearic acid 2.0 (6) Glycerin 20.0 (7) Polyethylene glycol 400 5.0 (8) Erythritol 2.0 (9) Propylene glycol 10.0 (10) Preservative Agents Appropriate amount (11) Perfume Appropriate amount (12) Cistus ladaniferus L. Extract * 1 1.0 (13) Aloe extract * 2 0.02 (14) Chamomile extract * 3 0.02 (15) Gypsophila extract * 4 0.02 (16) Purified water balance * 1 Example Manufactured in 1 * 2 Made by Maruzen Pharmaceuticals * 3 Made by Maruzen Pharmaceuticals * 4 Made by Maruzen Pharmaceuticals

The obtained face wash was excellent in stability over time, and when applied to the skin, it was a face wash which gave a transparent and beautiful skin.

[Example 8: Emulsion] The following components (1) to (8) were heated and mixed to 70 ° C. To this mixture, (9) to (13) and (22) heated and mixed at 70 ° C. were added and mixed, cooled, and further (14) and (15) to (21).
Was added and mixed to obtain an emulsion. (Component) (%) (1) Hydrogenated soybean phospholipid 3.0 (2) Cholesterol 0.2 (3) Polyoxyethylene (5) Cetyl ether 0.2 (4) Polyoxyethylene (10) Hydrogenated castor oil 1.0 (5) cetostearyl alcohol 2.0 (6) olive squalane 5.0 (7) dipropylene glycol 7.0 (8) 1,3-butylene glycol 5.0 (9) L-serine * 10 .2 (10) Sodium pyrrolidonecarboxylate * 2 0.1 (11) Trimethylglycine 2.0 (12) Hydroxypropylmethylcellulose 0.1 (13) Carboxyvinyl polymer 0.2 (14) Potassium hydroxide 0.1 ( 15) Preservative Suitable amount (16) Perfume Suitable amount (17) Cistus ladaniferus L. Extract * 3 0.1 (18) Quinceseed extract * 4 5.0 (19) Almond extract * 5 0.2 (20) Yeast extract * 6 0.2 (21) Altea extract * 70 2 (22) Remaining amount of purified water * 1 Made by Ajinomoto Co., Inc. * 2 Made by Ajinomoto Co., Inc. * 3 Manufactured in Example 1 * 4 Made by Koei Kogyo Co., Ltd. * 5 Made by LABORATORIES SEROBIOLOGIQUES * 6 Made by Maruzen Pharmaceutical Co., Ltd. * 7 Maruzen Pharmaceutical Co., Ltd. Company

[Example 9: Emulsion] The following components (13) to (1)
7) was mixed by heating and kept at 70 ° C.
Similarly, a mixture obtained by heating (12) to (12) is added and emulsified. After cooling this, components (18) to (25) were added,
A uniform mixture was obtained to obtain an emulsion. (Component) (%) (1) sorbitan monostearate 0.3 (2) polyoxyethylene monooleate (20) sorbitan 0.1 (3) lipophilic glyceryl monostearate 0.2 (4) stearic acid 0.5 (5) Cetanol 0.5 (6) Squalane 3.0 (7) Liquid paraffin 4.0 (8) Glyceryl tri-2-ethylhexanoate 2.0 (9) Dimethylpolysiloxane 1.0 (10) ) Hydrogenated soybean phospholipid 0.1 (11) Acetic acid-dl-α-tocopherol * 1 0.05 (12) Preservative Suitable amount (13) Carboxyvinyl polymer 0.1 (14) Sodium hydroxide 0.05 (15) ) Glycerin 5.0 (16) 1,3-butylene glycol 7.0 (17) Purified water Remaining amount (18) Ethyl alcohol 5.0 (19) Cistus la aniferus L. Extract * 2 0.05 (20) Yukinoshita extract * 3 0.1 (21) Age extract * 4 0.1 (22) Kujin extract * 5 0.1 (23) Coffee extract * 60. 1 (24) Eucommia ulmoides extract * 7 0.1 (25) Perfume proper amount * 1 Made by Eisai * 2 Made by Example 1 * 3 Made by Ichimaru Falcos * 4 Made by Maruzen Pharmaceutical * 5 Made by Maruzen Pharmaceutical * 6 Made by Ichimaru Falcos * 7 Made by Maruzen Pharmaceutical

[Example 10: Gel cosmetic] The following component (1)
~ (5) and (19) were mixed by heating and cooled to room temperature. This mixture was heated and mixed at 70 ° C. (6) to
(10) was added and mixed, and further (11) to (18) were added and mixed to obtain a gel cosmetic. (Component) (%) (1) Methylcellulose 2.0 (2) Xanthan gum 1.0 (3) Sodium alginate 0.2 (4) Alkyl-modified carboxyvinyl polymer 0.2 (5) Sodium hyaluronate 1% aqueous solution 1. 0 (6) Glycerin 10.0 (7) Polyethylene glycol 20000 1.0 (8) Methyl glucose 2.0 (9) Hydrogenated egg yolk phospholipid 0.2 (10) Phytosterol 0.1 (11) Sodium hydroxide 0 1 (12) Preservative Amount (13) Perfume Amount (14) Cistus ladaniferus L. Extract * 1 0.001 (15) Oolong tea extract * 2 0.3 (16) Sunpens extract * 3 0.3 (17) Salvia extract * 4 0.3 (18) Mallow extract * 5 0. 3 (19) Remaining amount of purified water * 1 Made in Example 1 * 2 Made by Maruzen Pharmaceutical Co., Ltd. * 3 Made by Maruzen Pharmaceutical Co., Ltd. * 4 Made by Maruzen Pharmaceutical Co., Ltd. * 5 Made by Maruzen Pharmaceutical Co., Ltd.

[Example 11: Oil gel cosmetics] The following components (1) to (9) were heated and mixed at 70 ° C and cooled to room temperature. To this mixture, (10) and (21) were added and mixed, and further (11) to (20) were added and mixed to obtain an oil gel cosmetic. (Component) (%) (1) Polyoxyethylene (20) polyoxypropylene (4) cetyl ether 1. 0 (2) Polyoxyethylene (20) Glyceryl triisostearate 0.2 (3) Alkyl-modified carboxyvinyl polymer 0.2 (4) Glycerin 10.0 (5) Dipropylene glycol 2.0 (6) 1,3 -Butylene glycol 5.0 (7) Polyoxyethylene (10) methyl glucose 0.2 (8) Glyceryl tri-2-ethylhexanoate 75.0 (9) Squalane 2.0 (10) Triethanolamine 0.1 (11) Preservative Suitable amount (12) Perfume Suitable amount (13) Stearyl glycyrrhizinate * 1 0.1 (14) Cistus ladaniferus L. Extract * 2 0.005 (15) β-carotene * 3 0.002 (16) Safflower oil * 4 1.0 (17) Tomato oil * 5 1.0 (18) Nicotinic acid-dl-α-tocopherol * 6 0.1 (19) Retinol palmitate * 7 0.3 (20) Dibutylhydroxytoluene * 8 0.002 (21) Remaining amount of purified water * 1 Maruzen Pharmaceuticals * 2 Manufactured in Example 1 * 3 Sigma * 4 Ajinomoto * 5 ENNAGRAM * 6 Eisai * 7 Nippon Roche * 8 Sigma

[Example 12: Lotion] The following components (1) to
The mixture obtained by mixing and dissolving (9), (12) and (17) is added to the mixture obtained by mixing and dissolving the components (10), (11), (13) to (16) and (18) to (24), Lotion was obtained by mixing. (Component) (%) (1) Macadamian nut oil 0.01 (2) Borage oil 0.01 (3) Cetyl octanoate 0.01 (4) Glyceryl tri-2-ethylhexanoate 0.01 (5) Acetic acid-dl-α-tocopherol * 1 0.02 (6) Sorbitan sesquioleate 0.1 (7) Polyoxyethylene monooleate (20) sorbitan 0.1 (8) Polyoxyethylene (8) alkyl ether phosphorus Acid 0.2 (9) Ethanol 10.0 (10) Sorbitol (70% aqueous solution) 5.0 (11) Glycerin 1.0 (12) 2-Hydroxy-4-methoxybenzophenone * 2 0.2 (13) 2 -Hydroxy-4-methoxybenzophenone-5-sulfonate sodium * 3 0.2 (14) Lactic acid (50% aqueous solution) 0.1 (15) Lactic acid sodium Arm (50% aqueous solution) 0.3 (16) preservative suitable amount (17) Perfume Appropriate amount (18) Cistus ladaniferus L. Extract * 4 0.01 (19) Dipotassium glycyrrhizinate * 5 0.1 (20) White lily extract * 6 0.05 (21) Perilla extract * 7 0.05 (22) Raspberry extract * 8 0. 05 (23) Horse chestnut extract * 9 0.05 (24) Purified water balance * 1 Eisai * 2 Kyodo Yakuhin * 3 Shonan Chemical * 4 Manufactured in Example 1 * 5 Maruzen Pharmaceutical * 6 Made by Maruzen Pharmaceuticals * 7 Made by Maruzen Pharmaceuticals * 8 Made by Esperis * 9 Made by Maruzen Pharmaceuticals

[Example 13: Lotion] Toner lotion was obtained by adding the mixture prepared by mixing and dissolving the components (1) to (9) to the mixture prepared by mixing and dissolving (10) to (20). (Components) (%) (1) γ-lino-sucrose ester 0.05 (2) polyoxyethylene monoisostearate (50) hydrogenated castor oil 1.0 (3) L-ascorbyl isopalmitate 0. 1 (4) Polyoxyethylene (10) alkyl ether phosphate 0.1 (5) Octyl methoxycinnamate * 1 0.05 (6) Glycerin 3.0 (7) N-acetyl-L-glutamic acid * 20 1 (8) 1,3-butylene glycol 5.0 (9) ethanol 8.0 (10) sodium citrate 0.02 (11) citric acid 0.05 (12) preservative appropriate amount (13) perfume appropriate amount ( 14) Cistus ladaniferus L .; Extract * 3 0.05 (15) Centella asiatica extract * 4 0.2 (16) Ginkgo biloba extract * 5 0.2 (17) Beech sprouts extract * 6 0.05 (18) Armature extract * 7 0.05 (19) Geno ginger extract * 8 0.05 (20) Purified water balance * 1 BASF * 2 Kyowa Hakko * 3 Manufactured in Example 1 * 4 Maruzen Pharmaceutical * 5 Evergreen plant Made by Chemical Research Institute * 6 Made by Gate Jose * 7 Made by Maruzen Pharmaceutical * 8 Made by Maruzen Pharmaceutical

[Example 14: Whitening lotion] The following components (1) to
The mixture prepared by mixing and dissolving (10) was added to and mixed with the mixed and dissolved components (11) to (21) to obtain a cloudy lotion. (Component) (%) (1) polyoxyethylene (60) hydrogenated castor oil 0.7 (2) sodium polyoxyethylene alkyl ether phosphate 0.2 (3) cholesterol 0.01 (4) hydrogenated egg yolk phospholipid 0.02 (5) Dimethyl polysiloxane 0.05 (6) Acetic acid dl-α-tocopherol * 1 0.5 (7) 2-Ethylhexyl paramethoxycinnamate * 2 0.2 (8) Glycyrrhetinic acid stearyl * 3 0.1 (9) Ethanol 15.5 (10) Polyethylene glycol 6000 0.2 (11) Citric acid 0.01 (12) Disodium monohydrogen phosphate 0.2 (13) Rutin * 4 0.01 (14) ) Preservative Amount (15) Fragrance Amount (16) Cistus ladaniferus L. Extract * 5 0.002 (17) Hydroxyproline * 6 0.01 (18) Watercress extract * 7 0.1 (19) Coltsfoot extract * 8 0.1 (20) Bifidobacterium extract * 9 0. 1 (21) Remaining amount of purified water * 1 Made by Eisai * 2 Made by BASF * 3 Made by Maruzen Pharmaceutical * 4 Made by Sigma * 5 Made by Example 1 * 6 Made by Kyowa Hakko * 7 A. M. Company I * 8 Maruzen Pharmaceutical Company * 9 Kotobuki Chemical Company

[Example 15: Serum] Components (1) to (4),
The mixture of (6) and (7) mixed and dissolved at 50 ° C. and the components (8) to (13) and (25) are heated and mixed at 50 ° C.,
The mixture cooled to room temperature and the components (5) and (14)-
And (24) were added and mixed to obtain a viscous serum. (Component) (%) (1) Polyoxyethylene isostearate (50) Hydrogenated castor oil 0.2 (2) Hydrogenated soybean phospholipid 0.5 (3) Glycerin 7.0 (4) dl-α-tocopherol * 1 0.3 (5) Touki extract * 2 0.2 (6) Cholesterol 0.1 (7) Ethanol 6.0 (8) 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid sodium salt * 3 0. 2 (9) Magnesium L-ascorbyl phosphate 0.5 (10) Citric acid 0.01 (11) Sodium citrate 0.1 (12) Xanthan gum 0.1 (13) Methylcellulose 0.1 (14) Seaweed extraction Product * 4 0.1 (15) Gokahi extract * 5 0.1 (16) Wheat germ extract * 6 0.1 (17) Peony extract * 7 0.1 (18) Ami nicotinate * 8 0.05 (19) Oat extract * 9 0.1 (20) Tomato extract * 10 0.1 (21) Sophoraceae extract * 11 0.1 (22) Preservative Amount (23) Perfume Amount ( 24) Cistus ladaniferus L .; Extract * 12 1.0 (25) Purified water balance * 1 Eisai * 2 Nippon Powder Chemicals * 3 Shonan Chemical Co., Ltd. * 4 Maruzen Pharmaceuticals * 5 Maruzen Pharmaceuticals * 6 Seiwa Kasei Company * 7 Inabata Koryo * 8 Wako Pure Chemicals * 9 Maruzen Pharmaceuticals * 10 Esperis * 11 Maruzen Pharmaceuticals * 12 Example 1

[Example 16: Sunscreen emulsion] Components (1) to
(10) was heated and mixed at 70 ° C., and dispersed in a slurry state. In addition, the components (11) to (13) and (15) to
The mixture of (22) dissolved and mixed at 50 ° C. was mixed and the component (14) was added to obtain a sunscreen emulsion. (Component) (%) (1) Neopentyl glycol dicaprate 10.0 (2) 2-Ethylhexyl paramethoxycinnamate * 1 5.0 (3) Octamethylcyclotetrasiloxane 10.0 (4) Decamethyl Cyclopentasiloxane 10.0 (5) Dimethylpolysiloxane 5.0 (6) Fine particle titanium oxide 10.0 (7) Fine particle zinc oxide 5.0 (8) Polyalkylene-modified organopolysiloxane 5.0 (9) Nylon powder 2.0 (10) Polyethylene powder 1.0 (11) Glycerin 5.0 (12) Ethanol 5.0 (13) Preservative Suitable amount (14) Perfume Suitable amount (15) Cistus ladaniferus L. Extract * 2 0.2 (16) Dipotassium glycyrrhizinate * 3 0.1 (17) Sophoraceae extract * 4 0.1 (18) Maika extract * 5 0.01 (19) Green tea extract * 6 0. 01 (20) Melissa extract * 7 0.01 (21) Gentian extract * 8 0.01 (22) Purified water Remainder * 1 Made by BASF * 2 Made by Example 1 * 3 Made by Maruzen Pharmaceutical * 4 Maruzen Pharmaceuticals * 5 Maruzen Pharmaceuticals * 6 Maruzen Pharmaceuticals * 7 Maruzen Pharmaceuticals * 8 Maruzen Pharmaceuticals

[Example 17: Water-in-oil type sunscreen cream]
The components (1) to (9) were heated and mixed at 70 ° C. to this,
The components (10) to (13) and (15) to (20) heated and mixed at 50 ° C. were added and mixed, and the component (14) was added to obtain a water-in-oil type sunscreen cream. (Component) (%) (1) Polyoxyalkylene-modified organopolysiloxane 2.0 (2) Octyl palmitate 15.0 (3) Decamethylcyclopentasiloxane 20.0 (4) Glyceryl tribehenate 1.0 (5 ) Fine particle zinc oxide 12.0 (6) Fine particle titanium oxide 3.0 (7) 2-Ethylhexyl paramethoxycinnamate * 1 7.0 (8) 4-tert-butyl-4′-methoxydibenzoylmethane * 2 1.0 (9) Perilla oil * 3 0.05 (10) Dipropylene glycol 5.0 (11) Ethanol 5.0 (12) Polyethylene powder 3.0 (13) Preservative Amount (14) Perfume Amount (15) ) Cistus ladaniferus L. Extract * 4 0.2 (16) Birch extract * 5 0.2 (17) Artemisia extract * 6 0.2 (18) Mannitol * 7 0.05 (19) Lime extract * 8 0.2 ( 20) Remaining amount of purified water * 1 Made by BASF * 2 Made by Givaudan * 3 Made by Example 1 * 4 Made by Maruzen Pharmaceutical * 5 Made by Maruzen Pharmaceutical * 6 Made by Wako Pure Chemical Industries * 7 Made by Wako Pure Chemical Industries * 8 Made by Maruzen Pharmaceutical Co., Ltd.

[Example 18: Water-in-oil type cream] Component (1)
-(8) were mixed by heating to 70 ° C, and the components (9)-(16) and (18)-(2) were mixed by heating at 50 ° C.
5) was added and mixed, and the component (17) was added to obtain a water-in-oil cream. (Component) (%) (1) Hydrogenated soybean phospholipid 0.05 (2) Polyoxyalkylene-modified organopolysiloxane 2.0 (3) Cholesterol hydroxystearate 2.0 (4) Cholesterol 0.2 (5) Squalane 2.0 (6) Decamethylcyclopentasiloxane 7.0 (7) Ethylene glycol diisooctanoate 15.0 (8) 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid * 1 1.0 (9) L-ascorbate magnesium phosphate 3.0 (10) sodium citrate 0.5 (11) edetate disodium 0.05 (12) ethanol 2.0 (13) 1,3-butylene glycol 5.0 (14) ) Crystalline cellulose 2.0 (15) Spherical nylon powder 1.0 (16) Preservative appropriate amount (17) Perfume appropriate amount (18 ) Cistus ladaniferus L. Extract * 2 0.3 (19) Molasses extract * 3 0.1 (20) Hop extract * 4 0.1 (21) Arnica extract * 5 0.1 (22) Barley extract * 6 0. 1 (23) Apricot extract * 7 0.1 (24) Shobu extract * 8 0.1 (25) Purified water Remaining amount * 1 Badesh * 2 Made in Example 1 * 3 Taiyo Kagaku * 4 Made by Maruzen Pharmaceuticals * 5 Made by Maruzen Pharmaceuticals * 6 Made by Sansho Pharmaceuticals * 7 Made by Esperis * 8 Made by Maruzen

[Example 19: Cream] The following components (1) to
(10) is heated to 70 ° C and mixed, and this mixture is mixed with 70 ° C.
Ingredients (11) to (13), (24) and (27) which have been heated and mixed in step (3) are added and mixed, and further components (14) to (2).
3), (25) and (26) were added and mixed, and cooled to room temperature to obtain a cream. (Component) (%) (1) cetostearyl alcohol 3.0 (2) glycerin fatty acid ester 2.0 (3) polyoxyethylene (20) sorbitan monooleate 1.0 (4) sorbitan monostearate 1.0 (5) N-stearoyl-N-methyltaurine sodium 0.5 (6) Vaseline 5.0 (7) Dimethyl polysiloxane 3.0 (8) Glyceryl tri-2-ethylhexanoate 20.0 (9) dl- α-tocopherol * 1 1.0 (10) Titanium oxide 1.0 (11) Dipropylene glycol 10.0 (12) L-ascorbate magnesium phosphate 3.0 (13) Sodium citrate 0.5 (14) Dipotassium glycyrrhizinate * 2 0.1 (15) Lactic acid (50% aqueous solution) 0.1 (16) Carrot extract * 3 0.1 ( 7) Saishin extract * 4 0.3 (18) Hawthorn extract * 5 0.02 (19) King ginkgo extract * 6 0.02 (20) Houou extract * 7 0.02 (21) Soybean extract * 8 0.02 (22) Touki extract * 9 0.02 (23) Disodium edetate 0.03 (24) Preservative Suitable amount (25) Perfume Suitable amount (26) Cistus ladaniferus L. Extract * 10 0.5 (27) Purified water balance * 1 Eisai * 2 Maruzen Pharmaceuticals * 3 Ichimaru Falcos * 4 Maruzen Pharmaceuticals * 5 Maruzen Pharmaceuticals * 6 Nagaoka Fragrance * 7 Maruzen Pharmaceutical Co., Ltd. * 8 Koei Kogyo Co., Ltd. * 9 Nippon Powder Chemicals Co., Ltd. * 10 Manufactured in Example 1

[Example 20: Pack cosmetic] The following component (1)
-(5) and (23) were heated and mixed at 70 ° C, and components (6) to (22) were added and mixed to the mixture cooled to room temperature to obtain a pack cosmetic. (Component) (%) (1) Polyvinyl alcohol 15.0 (2) Glycerin 10.0 (3) Polyoxyethylene (10) Methyl glucose 3.0 (4) Glyceryl trioctanoate 5.0 (5) Polyoxyethylene Sodium alkyl ether phosphate 1.0 (6) Ethanol 20.0 (7) Kaolin 2.0 (8) Titanium oxide 2.0 (9) Seaweed extract * 1 0.1 (10) Dipotassium glycyrrhizinate * 20 1 (11) Wheat germ extract * 3 0.1 (12) Mocca extract * 4 0.1 (13) Rice bran extract * 5 0.01 (14) Hypericum extract * 6 0.01 (15) Raspberry extract * 7 0.01 (16) Ginger extract * 8 0.01 (17) Ginger extract * 9 0.01 (18) Lactic acid (50% aqueous solution) 0.5 (19) Lactic acid Thorium (50% aqueous solution) 0.5 (20) preservative suitable amount (21) Perfume Appropriate amount (22) Cistus ladaniferus L. Extract * 10 0.02 (23) Purified water balance * 1 Maruzen Pharmaceutical Co., Ltd. * 2 Maruzen Pharmaceutical Co., Ltd. * 3 Seiwa Kasei Co., Ltd. * 4 Maruzen Pharmaceutical Co., Ltd. * 5 Koei Kogyo Co., Ltd. * 6 Maruzen Pharmaceutical Co., Ltd. Company * 7 Esperis * 8 Maruzen Pharmaceuticals * 9 Koei Kogyo * 10 Example 1

[Example 21: Liquid foundation] The following components (1) to (7) were heated and mixed, and the components (13) to (18) were added to the mixture and mixed and kept at 70 ° C. The components (8) to (12) are mixed and kept at 70 ° C., and the above mixture is added thereto to uniformly emulsify. After cooling, the ingredients (1
9) to (25) were added to obtain a liquid foundation. (Component) (%) (1) Dipentaerythritol fatty acid ester 2.0 (2) Liquid paraffin 5.0 (3) Stearic acid 2.0 (4) Cetanol 1.0 (5) Self-emulsifying monostearic acid Glyceryl 1.0 (6) 2-Ethylhexyl para-methoxycinnamate 8.0 (7) Preservative Appropriate amount (8) Glycerin 5.0 (9) Triethanolamine 1.0 (10) Carboxymethylcellulose 0.2 ( 11) Bentonite 0.5 (12) Purified water Remaining amount (13) Titanium oxide 6.0 (14) Fine particle titanium oxide 2.0 (15) Fine particle zinc oxide 4.0 (16) Mica 2.0 (17) Talc 4.0 (18) Coloring pigment Appropriate amount (19) Cistus ladaniferus L. Extract * 1 0.01 (20) Scutellaria extract * 2 0.1 (21) Button extract * 3 0.1 (22) Comfrey extract * 4 0.1 (23) Elderberry extract * 50 1 (24) Mukurodi extract * 6 0.1 (25) Perfume proper amount * 1 Made in Example 1 * 2 Made by Ichimaru Falcos * 3 Made by Ichimaru Falcos * 4 Made by Ichimaru Falcos * 5 Made by Sepex * 6 Made by Koei Kogyo Co., Ltd.

The various cosmetics obtained in Examples 8 to 21 are all excellent in stability over time, and when applied to the skin, dull skin due to sunburn, stains and freckles, and age-related wrinkles and sagging The cosmetics were excellent in prevention and improvement effects, and had various kinds of cosmetics to give a transparent and beautiful skin.

[0102]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to provide an external preparation for skin which is excellent in beautiful skin effect, particularly in beautiful skin and / or antiaging effect. This excellent effect is a synergistic effect obtained by using the compound represented by the general formula (1) in combination with a specific component, and the compound represented by the general formula (1) alone is used. It has a remarkably excellent whitening, beautiful skin and / or anti-aging effect that cannot be obtained when used or when a specific component is used alone.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) A61K 35/78 A61K 35/78 C A61P 17/16 A61P 17/16 (72) Inventor Masakazu Muto Tokyo North 48-18 Sakae-cho, Kouse Co., Ltd., Research Headquarters (72) Inventor Kumi Kameyama 48-term, Sakaemachi, Kita-ku, Tokyo F-Term (Reference) 4K083 AA031 AA032 AA082 AA111 AA112 AA122 AB032 AB212 AB242 AB282 AB322 AB432 AB442 AC072 AC102 AC122 AC132 AC182 AC211 AC242 AC291 AC301 AC311 AC312 AC341 AC342 AC352 AC392 AC422 AC432 AC442 AC472 AC532 AC542 AC581 AC611 AC642 AC662 AC712 AC791 AC842 AC902 AD022 AD042 AD072 AD072 AD092 AD112 AD152 AD162 AD172 AD202 AD222 AD222 AD202 AD222 AD222 AD222 AD202 AD202 AD222 AD392 AD492 AD512 AD531 AD532 AD571 AD621 AD642 AD662 CC04 CC05 CC07 CC12 CC19 CC23 DD0 2 DD23 DD32 DD41 EE12 EE16 EE17 4C088 AB12 AC05 AC06 BA08 BA09 BA10 BA32 CA05 CA06 CA09 MA02 MA03 MA07 MA08 MA63 NA14 ZA89 4C206 AA01 AA02 DA12 DB20 DB42 KA01 MA02 MA04 MA83 NA14 ZA89

Claims (5)

[Claims] 1. (A) The following general formula (1): (In the general formula (1), R ¹ represents —CH ₂ OH or COOR ⁶ , R ⁶ represents hydrogen, a lower alkyl group having 1 to 3 carbon atoms, or a cation capable of forming a salt with COO ⁻ , ² ~ R ⁵
Each independently represent a hydrogen atom or a methyl group, ... A ...
Is _{= C (CH 3) -,} - C (CH 3) =, - C (= C
_{H 2) -, - CH (} CH 3) - or -C (OH) (C
H ₃₎ - represents a. ) One or more compounds represented by the formula (B), and (B) asparagus extract, adzuki bean extract, sow extract, senkyu extract, age extract, rubus extract, kujin extract, gokahi extract. , Coffee extract, rice bran extract, wheat germ extract, cabbage extract, hawthorn extract, white lily extract, peony extract, tea extract, molasses extract, grape extract, hop extract, mica extract, Mocca extract, sardine extract, seaweed extract, dibutylhydroxytoluene, butylhydroxyanisole, mannitol, β-carotene,
Quercetin, Quercitrin, Rutin, Vitamin E and its derivatives, Genshosho extract, Yukinoshita extract, Sanpens extract, Melissa extract, Glycyrrhizic acid and its derivatives, Glycyrrhetinic acid and its derivatives, Vitamin B and its derivatives, Gentiana extract , Dokudami extract, Botanical extract, Aloe extract, Arnica extract, Hypericum extract, Oat extract, Kingfish extract, Salvia extract, Birch extract, Perilla extract, Artemisia extract, Chamomile extract, Con Free extract, Chinese cabbage extract, Watercress extract, Calendula officinalis extract, Elderberry extract, Huangzhou extract, Mukuroji extract,
Eucalyptus extract, Astragalus extract, Vitamin A and its derivatives, Tartaric acid, Malic acid, Glycolic acid, Succinic acid, Serine, Glutamic acid, Hydroxyproline, Theanine, Pyrrolidonecarboxylic acid, Astragalus extract, Soybean extract, Carrot extract, Barley extract, beech bud extract, ginkgo extract, Centella asiatica extract, yeast extract, lactic acid bacterium extract, bifidobacteria extract, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid sodium salt, 2-ethylhexyl paramethoxycinnamate, 4-tert-butyl-4'-methoxydibenzoylmethane, Altea extraction Substance, ginger extract, sorghum extract, horse chestnut extract, mallow extract, apricot extract, apricot extract, lime extract, raspberry extract, almond extract, tomato extract, phospholipids and their derivatives, armature 1 selected from the group consisting of extracts, coltsfoot extracts and quince seed extracts
A skin external preparation containing one or more kinds. 2. The external preparation for skin according to claim 1, which is an external preparation for whitening skin. 3. The skin external preparation according to claim 1, which is an antiaging skin external preparation. 4. The compound represented by the general formula (1) is
Cistus ladaniferu of the family Asteraceae
s L. , Cistus creticus L .; , C
istus monoperiensis L. And C
The compound for external use according to any one of claims 1 to 3, which is a compound extracted from one or more plants selected from the group of plants consisting of istus salvifolius, or a compound prepared from the compound. Agent. 5. A cystus ladani of the family Asteraceae containing the compound represented by the general formula (1).
ferus L .; , Cistus creticus
L. , Cistus monoperensis
L. And the external preparation for skin according to any one of claims 1 to 4, which comprises one or two or more kinds of extracts selected from the group of plants consisting of Cystus salvifolius.