JP7026375B2 - External skin preparation - Google Patents

Description

The present invention relates to an external skin preparation for moisturizing and firming, particularly an external skin preparation for the eyes, which makes the skin thin and easily wrinkled and gives a strong impression to others.

In order to suppress the formation of wrinkles, in cosmetics, antioxidants (Patent Document 1), plant extracts (Patent Document 2), lipoic acid, vitamin A, carotenoids, riboflavin, vitamin B6, cobalamine, etc. A skin external preparation containing one or more selected from the group consisting of vitamin C, vitamin E, vitamin K, adenosine, flavonoids, and tannins (Patent Document 3), egg yolk oil, placenta extract, vitamin C, It has been proposed to use a cosmetic having an anti-wrinkle formation effect containing two or more kinds of vitamin E (Patent Document 4) and δ-tocopheryl retinoate (Patent Document 5), but the effect is sufficient. I'm not satisfied with it.
Needless to say, it takes time to develop the effects of such drugs.

Japanese Unexamined Patent Publication No. 62-19511 Japanese Unexamined Patent Publication No. 8-175955 Japanese Unexamined Patent Publication No. 10-7541 Japanese Unexamined Patent Publication No. 11-228381 Japanese Unexamined Patent Publication No. 2004-339101 Japanese Unexamined Patent Publication No. 2012-041318

An object of the present invention is to first make wrinkles inconspicuous by an immediate method, and then to obtain a composition that enhances the absorbability and persistence of a drug effective for wrinkles and moisturizes the wrinkles.

As a result of diligent studies, the present inventors have conducted diligent studies.
An O / W emulsion containing polyvinyl alcohol and hydroxyalkyl cellulose in the range of 1: 1 to 3: 1 (weight ratio), an oily component containing an oil-soluble vitamin, a sugar ceramide, and a fine O / D containing a polyhydric alcohol. It was found that the skin external preparation in which the emulsion was dispersed is the most suitable as an external preparation that moisturizes and firms the skin.

More specifically, polyvinyl alcohol and hydroxyalkyl cellulose will be described.
The polyvinyl alcohol is not particularly limited as long as it is usually used for cosmetics, and any polyvinyl alcohol can be used.
For example, as commercial products, "PVA-205", "PVA-217", "Kuraray Poval PVA124" (all manufactured by Kuraray), "PVA-EG25", "PVA-EG40", "PVA-GL05S", Examples thereof include "PVA-EG05" (all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
The hydroxyalkyl cellulose is preferably a lower alkyl (C1-C8) hydroxyalkyl cellulose such as hydroxymethyl cellulose, hydroxyethyl cellulose, or hydroxypropyl cellulose.
The above polyvinyl alcohol and hydroxyalkyl cellulose are blended in a ratio of 1: 1 to 3: 1 (weight ratio). The blending amount varies depending on the type of polyvinyl alcohol or hydroxyalkyl cellulose, other blending raw materials, etc., but is preferably 0.05 to 3.0% by weight, preferably 0.2 to 1.0% by weight of the skin external preparation.

In addition to this, an aqueous phase containing water, a polyhydric alcohol, a water-soluble agent, etc. and an oil phase are prepared as an O / W emulsion by a conventional method.
Examples of water-soluble components include the following raw materials.
1,2 pentanediol, diethylene glycol, propylene glycol, 1,3-butylene glycol, ethylene glycol, triethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, polyethylene glycol, polypropylene glycol , Pentyl glycol, glycerin, diglycerin, pentaerythritol, tretol, arabitol, xylitol, galactitol, sorbitol, lactitol, multitoll and other polyhydric alcohols.
Lower alcohols such as ethanol and isopyropanol.
Caraginan, alginic acid or its salt, hyaluronic acid or its salt, chondroitin sulfate or its salt, β-1,3-glucan, β-1,4-glucan, β-1,6-glucan, heparin, polyvinyl alcohol, polyvinylmethyl Water-soluble polymers such as ether, polyvinylpyrrolidone, polyvinyl methacrylate, polyacrylate, polyalkylene oxide such as polyethylene oxide and polypropylene oxide or crosslinked polymers thereof, carboxyvinyl polymer, polyethyleneimine, dermatane sulfate, and keratane sulfate.
Valin, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, glycine, alanine, asparagine, glutamine, serine, cysteine, cystine, tyrosine, proline, hydroxyproline, aspartic acid, glutamic acid, hydroxylysine, ornithine, histidine, etc. , Their sulfates, phosphates, nitrates, citrates, or various amino acids such as amino acid derivatives such as pyrrolidone carboxylic acids.

Red bud Kashiwa, Jihuang, Kidori, Jibo, Ichiyakuso, Ginkgo, Woolong tea, Uikyo, Ukon, Summer dead grass, Chen bark, Magnolia obovata, Sekimeiko, Ouren, White ginseng, Panax japonicus, Panax japonicus, Panax japonicus, Panax japonicus, Panax japonicus, Panax japonicus , Orange, chamomile or roma chamomile, camcam, galana, koboku, gyoryu, goose berry, clara, cranberry, grapefruit, clove, kobushi, mokuren, ginseng, cherry, masan, sanshichininjin, magnolia obovata, sansho, sandscon, Shikunshi, Shiso Shiso, Shiso, Shakuyaku, Watermelon, Magnolia obovata, Celoli, Senkyu, Senburi, Daiou, Tachijakousou, Panax japonicus, Tengusa, Sweet tea, Tendaiuyaku, Tokusa, Dokudami, Tochu, Toneriko , Novara, Hatomugi, Rose, Ryomi, Biwa, Blackberry, Prune, Magnolia obovata, Bowfu (windproof), Magnolia obovata, Bodaiju, Button, Hop, Hohoba, Maou, Maca, Macademia nuts, Mulberry bark, Panax japonicus, Mannentake, Panax japonicus , Mirobaran, Mukuroji, Murasaki, Ginseng, Mematsuyoigusa, Melissa, Merirot, Mokko, Yacon, Eucalyptus, Yukinoshita, Yukka, Yuzu, Yuri, Yoroigusa, Yomogi, Lavender, Lemon, Lemongrass, Rosemary, Jiyoku, Chlorella, Chlorella, Various water-soluble extracts of plants such as konbu, wakame, giant kelp, hijiki, hibamata, ginseng, asakusanori, susabinori, spirulina, ishige, iroro, and magnolia obovata, seaweeds, and algae.

Horse or pig placenta extract, silk protein and its degradation products or their derivatives, milk, casein and its degradation products or their derivatives, skim milk powder and its degradation products or their derivatives, lactoferrin or its degradation products, chicken egg components , Fish meat decomposition products, nucleic acid-related substances (ribonucleic acid, deoxyribonucleic acid) and other animal-based raw material-derived substances.
Marine components Marine products such as deep water, sea salt, dried sea water, dead sea or inorganic salts obtained from the Atlantic or Pacific Ocean, and sea mud.
Yeast bacterium extract, bacterial metabolite, bacterial extract, mold or lactic acid bacterium metabolite, mold or lactic acid bacterium extract, natto bacterium metabolite, natto extract, rice fermented extract, rice bran (red bran, white bran) fermented extract, Bacterial-derived substances such as lactic acid fermented products of raw milk or defatted powdered milk, lactic acid bacteria fermented products of legumes, and lactic acid bacteria fermented products of coconut palm plants.
Α-Hydroxy acids such as glycolic acid, citric acid, malic acid, tartaric acid and lactic acid.
Of course, water such as purified water, seawater, hot spring water, and tap water is mixed.

An oily component is blended in the oil phase, and it is particularly in line with the gist of the present invention to blend lauroyl glutamic acid ester and pentaerythritol fatty acid ester.
Examples of lauroyl glutamic acid esters are lauroyl glutamic acid di (cholesteryl / behenyl / octyldodecyl), lauroyl glutamic acid di (cholesteryl / octyldodecyl), lauroyl glutamate di (phytosteryl / octyldodecyl), lauroyl glutamate di (octyl glutamateyl). ), Etc., as pentaerythritol fatty acid esters, hexahydroxystearic acid dipentaerythrityl, (hydroxystearic acid / isostearic acid) dipentaerythrityl, (hydroxystearic acid / stearic acid / loginic acid) dipentaerythrityl, hexa (hydroxystearic acid / stearic acid / rosin). Acid) dipentaerythrityl, hexa (bechenic acid / benzoic acid / ethylhexanoic acid) dipentaerythrityl and the like can be mentioned.

Of course, oily components other than the above can also be blended. For example below
Avocado oil, almond oil, uikyo oil, egoma oil, olive oil, orange oil, orange raffer oil, sesame oil, cacao butter, chamomile oil, carrot oil, cucumber oil, beef fat fatty acid, kukui nut oil, safflower oil, shea butter, liquid shea Fat, soybean oil, camellia oil, corn oil, rapeseed oil, persic oil, castor oil, cottonseed oil, peanut oil, turtle oil, mink oil, egg yolk oil, palm oil, palm kernel oil, mokurou, palm oil, beef fat, pork fat , Squalene, Squalane, Pristan or various oils and fats such as hydrogenated additives (hardened oils, etc.) of these oils and fats.
Rows such as beeswax, carnauba wax, whale wax, lanolin, liquid lanolin, reduced lanolin, hard lanolin, candelilla wax, monttan wax, celac wax, and rice wax.
Mineral oils such as liquid paraffin, petrolatum, paraffin, ozokelide, selecin, and microkristang wax.

Fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, docosahexaenoic acid, eikosapentaenoic acid, 12-hydroxystearic acid, undecylenic acid, tall oil, and lanolin fatty acids.
Alcohols such as ethanol, isopyropanol, lauryl alcohol, cetanol, stearyl alcohol, oleyl alcohol, lanolin alcohol, cholesterol, phytosterol, phenoxyethanol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol.
Isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, diethyl phthalate, phthalate Esters such as dibutyl acid acid, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, and propylene glycol dioleate.
Higher alcohols such as lauryl alcohol, cetanol, stearyl alcohol, oleyl alcohol, lanolin alcohol, cholesterol, phytosterol, phenoxyethanol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol.
Examples include ceramide and other oil-soluble animal and plant extracts.

If necessary, these aqueous and oil phases are heated and dissolved, and mixed with stirring to obtain an O / W emulsion.
An oily component containing an oil-soluble vitamin, a sugar ceramide, and a fine O / D emulsion containing a polyhydric alcohol are dispersed in this O / W emulsion.
Oil-soluble vitamins are selected from vitamin A and its derivatives, carotenoids and their derivatives, vitamin Es and their derivatives.
Examples of vitamin A and derivatives thereof include retinoic acid, retinol, retinal, retinol acetate, retinol palmitate, retinyl acetate, retinyl palmitate, and tocopheryl retinoate.
Examples of carotenoids are actinioerythrol, astaxanthin, bixin, canthaxanthin, capsanthin, capsorbin, apocarotenal, β-12'-apo-carotene, α-carotene, β-carotene, γ-carotene, β-cryptoxanthin. , Lutein, lycopene, biorelitrin, zeaxanthin, and esters of those containing hydroxyl or carboxyl.
Examples of vitamin Es and derivatives thereof include α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, tocotrienol, and tocophersolan.

Oil-based ingredients other than oil-soluble vitamins can also be blended, but the oil-based ingredients may be blended in the oil phase of the O / W emulsion, but since they are finely dispersed, oil-based active ingredients such as ceramide can be blended in the oil phase of the O / D emulsion. Needless to say, the efficacy is improved when blended.
Glycolipids are glycolipids in which sugar moieties such as galactose, glucose, and mannose are added to ceramides, and include galactosylceramide and glucosylceramide. For example, there are those present in tissues such as the brain and spinal cord of mammals such as cows and horses, those present in the cell membranes of plants such as rice bran, those present in the cell membranes of some microorganisms, and those obtained by chemical synthesis. ..
The polyhydric alcohol to be blended in the O / D emulsion is not particularly limited, but glycerin is most preferable.
The polyhydric alcohol and the oil phase are heated and dissolved as necessary and mixed with stirring to obtain an O / D emulsion.
When preparing an O / D emulsion, it is more preferable to use a disperser capable of high dispersion because the active ingredient can be used more effectively when it is as fine as possible.
The O / D emulsion prepared by the above method is added to the O / W emulsion and stirred to obtain a skin external preparation.
The blending amount of the O / D emulsion is 1.0 to 70% by weight, preferably 5 to 50% by weight of the external skin preparation, and the blending amount of sugar ceramide varies greatly depending on the type and amount of other raw materials. It is 0.0001 to 5% by weight, preferably 0.001 to 1.0% by weight of the external skin preparation, and 0.001 to 5% by weight, preferably 0.001 to 5% by weight of the external skin preparation, although the oil-soluble vitamin varies greatly depending on various conditions. 0.01-0.5% by weight is preferable.

Examples are shown below, but the present invention is not limited to this.
The numbers in Examples and Comparative Examples represent parts by weight.

Example 1 Cream A
Liquid paraffin 5.00
Octyldodecyl myristic acid 2.00
Cetyl palmitate 2.00
Bacil alcohol 3.00
Stearyl alcohol 2.00
Stearic acid 0.50
Di (phytosteryl / octyldodecyl) lauroyl glutamate 2.00
(Hydroxystearic acid / isostearic acid) Dipentaerythrityl 2.00
B
Hydrogenated lecithin Note-1 2.00
Polyvinyl alcohol Note-2 0.30
Hydroxyethyl cellulose 0.15
Glycerin 8.00
1,3-butylene glycol 6.00
Polyethylene glycol 2.00
Sodium hyaluronate 0.10
Phenoxyethanol 0.20
Methyl paraoxybenzoate 0.20
Purified water 61.55
C
Production example 1 3.00

In the manufacturing method, A and B were weighed respectively, A was gradually added to B while stirring after heating, and Production Example 1 prepared separately was added and cooled.

Production Example 1 was created as follows.

Tocopherol 5.00
Retinyl palmitate 3.00
Hydrogenated retinol 2.00
Bird (caprylic / capric acid) glyceryl 5.00
Sugar ceramide Note-3 3.00
Glycerin 67.00
1,3-butylene glycol 5.00
Dipropylene glycol 5.00
70% sorbitol 5.00
The production method was weighed, heated, and then treated with a high-pressure emulsifier Microfluidizer (M-110P) while stirring.
The notes of Example 1 and Production Example 1 are as follows.
Note-1 Made by Nisshin Oillio Griep, trade name Basis LS-60HR
Note-2 Made by Nippon Synthetic Chemical Industry Co., Ltd., trade name Gosenol EG-25
Note-3, manufactured by LABORATOIRES SEROBIOLO, trade name Bioceramide CH

The effectiveness has been confirmed below, so it is described below.
In Comparative Example 1 used in the test, purified water was blended instead of Production Example 1, and other than that, the same blending and preparation method as in Example 1 was used.
(A) Skin elasticity test The following method was used.
1. 1. After washing the face, the patient was rested in a constant temperature and humidity room (21 ° C., 45%) for 20 minutes.
2. 2. Both cheeks were marked 2 cm x 2 cm and the initial skin elasticity was measured.
3. 3. 0.1 g of Example 1 was applied to the left cheek and Comparative Example 1 was applied to the right cheek, and the mixture was left for 10 minutes and then wiped off with a tissue.
4. After 5 minutes, 15 minutes, and 30 minutes after wiping, the skin elasticity of both cheeks was measured.

The skin elasticity was measured as follows.
Using an elasticity measuring device (CUTOMETER MPA580 Courage + manufactured by Khazaka), apply a probe to the measurement site, suck at a constant negative pressure, and then suddenly release the negative pressure. The skin return rate (skin recovery rate) 0.1 seconds after the opening of suction with respect to the amount of change due to suction was measured. The measurement was performed 3 times per site, and the average value was used as data. The measured values are shown as relative values with the test start date as 1.000. The test was conducted with 8 subjects (female only, 41.4 ± 6.1 years old).
The results are shown in Table 1.

(B) Wrinkle immediacy effect confirmation test 1. After washing the face, the subject entered a constant temperature and humidity room (21 ° C., 45%) and rested for 20 minutes.
2. 2. After resting, I took a replica of the left corner of the eye.
3. 3. A mark of 3.5 cm × 3.5 cm was made on the outer corner of the left eye, 0.07 g of the test product was applied, and after leaving for 10 minutes, a replica of the outer corner of the left eye was taken.
4. The day was changed, and 1 to 3 operations were performed for the control product.
5. The wrinkle depth was measured using a laser microscope as follows.
-The heights of 5 points of the same site of the same wrinkle were measured in all replicas of each subject.
・ The average value of the height of wrinkles in 5 places was taken as the wrinkle depth.
・ Measuring equipment: Color 3D laser microscope VK-9700, VK-9710 (KEYENCE)
The test was conducted with 6 subjects (2 males, 4 females, 48.3 ± 7.6 years old).

The results are shown in Table 2.

As described above, in Example 1, wrinkles were immediately made inconspicuous, and then the absorption and persistence of the drug effective for wrinkles were enhanced. As a result, wrinkles were reduced and youthful skin could be obtained.

Example 2 Cream A
Squalene 5.00
Octyldodecyl myristic acid 2.00
Cetyl palmitate 2.00
Behenyl alcohol 1.00
Beeswax 0.50
Di (octyldodecyl / phytosteryl / behenyl) lauroyl glutamate
5.00
Dipentaerythrityl hexahydroxystearate 2.00
B
Hydrogenated lecithin Note-1 2.00
Polyvinyl alcohol Note-2 0.50
Hydroxyethyl cellulose 0.50
Glycerin 8.00
1,3-butylene glycol 6.00
Sodium hyaluronate 0.10
Phenoxyethanol 0.20
Methyl paraoxybenzoate 0.20
Purified water 60.00
C
Production Example 2 5.00

In the manufacturing method, A and B were weighed respectively, A was gradually added to B while stirring after heating, and Production Example 2 prepared separately was added and cooled.

Production Example 2 was created as follows.

Tocopherol 5.00
Retinyl palmitate 5.00
Tocopheryl retinoate 5.00
Sugar ceramide Note-4 5.00
Glycerin 80.00
The production method was weighed, heated, and then treated with a high-pressure emulsifier Microfluidizer (M-110P) while stirring.
The notes of Example 2 and Production Example 2 are as follows.
Note-1 Made by Nisshin Oillio Griep, trade name Basis LS-60HR
Note-2 Made by Nippon Synthetic Chemical Industry Co., Ltd., trade name Gosenol EG-25
Note-4, manufactured by Kikkoman Biochemifa, trade name Biosphingo

In Example 2, as in Example 1, wrinkles are immediately made inconspicuous, and then the absorption and persistence of the drug effective for wrinkles are enhanced. As a result, wrinkles can be reduced and youthful skin can be obtained. rice field.

Claims (3)

An O / W emulsion containing polyvinyl alcohol and hydroxyalkyl cellulose in the range of 1: 1 to 3: 1 (weight ratio), an oily component containing an oil-soluble vitamin, a sugar ceramide, and a fine O / D containing a polyhydric alcohol. Emulsion-dispersed skin external preparation (however, (1) polyalkylene glycol-diisocyanate copolymer, (2) extract of phytoplankton belonging to the genus Senedesmus with a water-containing solvent, or (3) α-hydroxy acid, Except for compositions containing one or more selected from the group consisting of salicylic acids, trichloroacetic acids and phenols, and acrylamide-based thickeners) . The skin external preparation according to claim 1, wherein the oil-soluble vitamin is one or more selected from vitamin A and its derivatives, carotenoids and their derivatives, vitamin Es and their derivatives. The external skin preparation for the eyes according to any one of claims 1 and 2.