JP2002003389A - Radical scavenger and cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radical scavenger having low cytotoxicity and excellent in radical scavenging effects. SOLUTION: This radical scavenger comprises a pressed and filtered substance and/or an extract of a cranberry fruit consisting essentially of an anthocyanine polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD [0001] The present invention provides low cytotoxicity,
The present invention relates to a radical scavenger excellent in radical scavenging effect and a cosmetic excellent in safety. More specifically, a radical scavenger containing a pressed and filtered extract and / or an extract of cranberry, which is a natural ingredient, has low cytotoxicity, and has an excellent radical scavenging effect, and the safety of blending this radical scavenger Regarding excellent cosmetics.

[0002]

2. Description of the Related Art Cranberries (Vaccinium m.)
(acrocarpon) is a red-fruited plant often produced in the United States, and is a member of the Japanese name "Tsuruko-kemo". The extract of cranberry has an effect as a therapeutic agent for urinary tract infection, and its application as a whitening agent containing caffeic acid glycoside derived from cranberry or the like as disclosed in JP-A-5-201846. The utility in various fields such as a method for obtaining proanthocyanidins from cranberries as disclosed in JP-A-222484 is known. However, cranberry extract containing no caffeic acid glycoside or proanthocyanidin also has a radical scavenging effect, and it has not been found that it is effective for cosmetics.

[0003]

In addition, caffeic acid glycosides and proanthocyanidins may have a problem in safety to the skin, and a component with higher safety is required.

[0004]

Means for Solving the Problems The present inventors have studied a highly safe ingredient which is a radical scavenger containing cranberry squeezed filtrate and extract. As a result, they have found that the pressed and filtered extract and / or extract of cranberry fruits mainly composed of an anthocyanin polymer have low cytotoxicity, excellent skin safety, and a radical scavenging effect. Furthermore, they have found that a cosmetic excellent in radical scavenging effect can be obtained by adding this radical scavenger to cosmetics. Further, they have found that radicals generated on the skin can be more effectively eliminated by combining with an existing ultraviolet ray protective agent or a physiologically active ingredient having antioxidant activity.

[0005] That is, a first aspect of the present invention is a radical scavenger mainly comprising a press-filtered product and / or an extract of cranberry fruit containing an anthocyanin polymer.

A second aspect of the present invention is the above radical scavenger comprising a purified product obtained by further purifying a cranberry fruit press-filtered product and / or extract by a gel filtration method or an ultrafiltration method.

A third aspect of the present invention is the above radical scavenger wherein the molecular weight of the anthocyanin polymer is 5,000 or more.

A fourth aspect of the present invention is a cosmetic containing any one of the above radical scavengers and an ultraviolet protective agent.

A fifth aspect of the present invention is the above-mentioned cosmetic wherein the ultraviolet ray protective agent is at least one selected from the group consisting of titanium oxide fine particles, zinc oxide fine particles and cerium oxide.

A sixth aspect of the present invention is a cosmetic containing any of the above radical scavengers and an antioxidant.

A seventh aspect of the present invention is that the antioxidant comprises tocopherol and a derivative thereof, nordihydroguaiaretic acid,
Butylhydroxyanisole, dibutylhydroxytoluene, propyl gallate, sodium bisulfite, erythorbic acid, sodium erysorbate, dilauryl thiodipropionate, tolylguanide, p-hydroxyanisole, octyl gallate, anhydrous sodium sulfite, apple extract, dehydrodi Creosol, apple polyphenol, lycopene, rosemary extract, mothra extract, clove extract, spinach extract, hamamelis extract, fennel extract, superoxide dismutase, deoxyribonucleic acid, carotenoid, flavonoid, tannin, lignan, saponin, phytic acid One or two or more selected cosmetics as described above.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a pressed cranberry fruit filter consisting mainly of an anthocyanin polymer and / or
Or a radical scavenger containing an extract. Cranberry (Vaccinium macroc) used in the present invention
(arpon) is the Japanese name of the azalea family, Tsurukokemo.
Is a companion. In the present invention, a cranberry fruit press filtered product is used.The pressed filter product is a juice obtained by crushing and pressing cranberry fruit, or a concentrate thereof. In order to reduce the viscosity of pectin, it is preferable to perform a pectin inactivation treatment. Also,
As an extract of cranberry fruit, cranberry fruit can be prepared by using water, polyhydric alcohols such as 1,3-butylene glycol, propylene glycol, glycerin and diglycerin, lower alcohols such as ethanol, isopropyl alcohol and propyl alcohol, acetone and the like. , A mixed solvent thereof, preferably water, polyhydric alcohol, lower alcohol, a mixed solvent thereof, more preferably an extract obtained by extraction with water such as hot water or hot water, and a concentrate thereof. As a form of the extract, an extract containing a solvent,
Solvent removal products and the like. In the present invention, it is preferable to use a press-filtrate because the production of the raw material is easy and economical.

The pressed cranberry fruit extract or extract used in the present invention may cause a problem of fading due to light depending on the production conditions. Further, it is preferably purified by a gel filtration method or an ultrafiltration method. As the degree of purification, the content of anthocyanidins in the purified product is reduced to less than 0.5% by mass, preferably less than 0.1% by mass, based on the mass of the purified product having properties to be incorporated into the cosmetic. Preferably. The purified cranberry contains mainly an anthocyanin polymer, and the molecular weight of the polymer is preferably 5,000 or more, more preferably 30,000 or more. Since anthocyanin polymer is a polymer, it has high safety to skin and low cytotoxicity. In addition, the radical scavenger of the present invention only needs to contain an anthocyanin polymer derived from cranberry.

As a method of measuring the anthocyanidin content, the following methods can be used. 2g sample
Is taken accurately, 60 mL of 2% methanolic hydrochloric acid is added, and the mixture is heated under reflux on a water bath for 30 minutes, and then cooled. This is 2
% Hydrochloric acid methanol is added to make exactly 100 mL, and the mixture is filtered with filter paper to obtain a test solution. The absorbance at the maximum absorption portion at a wavelength of about 530 nm to 550 nm is measured using 2% hydrochloric acid methanol as a control, and is determined by the following equation. Anthocyanidin content (% by mass) = {absorbance x dilution ratio (100) / sampled amount (g)} x {1/76000}
× 100

Hereinafter, a method for purifying a pressed filtered cranberry fruit or an extract used in the present invention will be described. A method for purifying cranberry fruit squeezed filtrate, or extract, is as follows:
Preferably, an ultrafiltration method and a gel filtration method are used. As the membrane used in the ultrafiltration method, a membrane having a cut-off molecular weight of 5,000 to 500,000 is useful, but a membrane having a cut-off molecular weight of 10,000 to 100,000 can obtain good results. In particular, 30,000 to 100,000 films are preferred. Examples of the material of the membrane include polyether sulfone and regenerated cellulose, and polyether sulfone is preferable. As a filtration method, there are a pressure filtration method using a pump or a centrifuge, a suction filtration method, and the like, but any method may be used.

Gels used in the gel filtration method include Sephadex, Sepharose (above, manufactured by Amersham Pharmacia), Toyopearl (manufactured by Tosoh Corporation), and Biogel (manufactured by Biorat). In addition, various buffers, aqueous organic solvents (methanol, ethanol,
Acetone, acetonitrile, etc.) can be used.

The amount of the radical scavenger in the cosmetic of the present invention (in terms of pure content excluding the solvent) is preferably 0.0001 to 99.9% by mass, more preferably 0.0001 to 99.9% by mass of the cosmetic. Is 0.1 to 30% by mass.

In the cosmetic of the present invention, when an ultraviolet protective agent is added together with the radical scavenger, the effect of the radical scavenger can be further exhibited. Examples of the UV protection component include an organic UV absorber (which may correspond to any of UV-A and B), an inorganic pigment, and a metal powder. Examples of organic UV absorbers include:
For example, 2-ethylhexyl paramethoxycinnamate, 2-
Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate, 2,
2'-dihydroxy-4-methoxybenzophenone, p
-Methoxyhydrocinnamic acid diethanolamine salt, para-aminobenzoic acid (hereinafter abbreviated as PABA), ethyldihydroxypropyl PABA, glyceryl PABA, homomenthyl salicylate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano-3,3- Diphenyl acrylate, octyl dimethyl PABA, octyl salicylate, 2-phenyl-benzimidazole-5
-Sulfuric acid, triethanolamine salicylate, 3- (4-
Methylbenzylidene) camphor, 2,4-dihydroxybenzophenine, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4 ′
-Dimethoxybenzophenone, 2-hydroxy-4-N
-Octoxybenzophenone, 4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane,
4- (3,4-dimethoxyphenylmethylene) -2,5
And 2-ethylhexyl-dioxo-1-imidazolidine propionate, and their polymer derivatives and silane derivatives. When the organic UV absorber is used, the amount is 1 to 20% by mass based on the total amount of the cosmetic.
Is more preferable, and more preferably 3 to 10% by mass.
Further, among these organic ultraviolet absorbers, 2-ethylhexyl paramethoxycinnamate, 4-tert-butyl-
4'-methoxydibenzoylmethane is particularly preferably used.

Further, it is also possible to use an organic ultraviolet absorber which is sealed in a polymer powder. The polymer powder may or may not be hollow, and the average primary particle size may be in the range of 0.1 to 50 μm, and the particle size distribution may be broad or sharp.
Examples of the type of polymer include acrylic resin, methacrylic resin, styrene resin, urethane resin, polyethylene, polypropylene, polyethylene terephthalate, silicone resin, nylon, and acrylamide resin.
Powders obtained by incorporating an organic ultraviolet absorbent in the range of 0.1 to 30% by weight of the polymer powder in these polymer powders are preferable, and in particular, 4-tert-butyl-4'-methoxydiphenyl which is a UVA absorbent. It is preferable to incorporate benzoylmethane.

Examples of the inorganic pigments and ultraviolet protective agents of metal powder include fine metal oxides, aluminum flakes and stainless steel flakes, and fine metal oxides are particularly preferable. The particulate metal oxide refers to those having an average primary particle diameter in the range of 5 to 100 nm and having an ultraviolet protection effect, and examples thereof include particulate titanium oxide, particulate zinc oxide, particulate cerium oxide, and particulate iron oxide. Fine particle titanium oxide, fine particle zinc oxide and fine particle cerium oxide are preferred. It is preferable to use one or more, preferably two or more of these fine metal oxides in combination. For example, a combination of fine particle titanium oxide and fine particle zinc oxide can be mentioned. The particle size distribution of the particulate metal oxide does not need to be particularly sharp,
It can be sharp or broad. Further, the shape of the fine particle metal oxide is not particularly limited, such as a sphere, a needle, a rod, a spindle, an irregular shape, and a plate, and the crystal shape is not particularly limited, such as an amorphous, rutile, or anatase type. Further, yellow fine particle titanium oxide obtained by doping iron into fine particle titanium oxide can also be used. It is preferable to use those components in which the contents of lead, arsenic and the like have been reduced by purification.

Further, these fine particle metal oxides may be subjected to conventionally known surface treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil treatment, -Acylated lysine treatment, polyacrylic acid treatment,
It may or may not have been surface-treated in advance by metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, etc., but when performing surface treatment, silicone, silane, fluorine compounds, amino acid-based It is preferable that water-repellent treatment is performed by one or more surface treatments selected from compounds and metal soaps. Examples of the silicone treatment include coating and heating treatment of methyl hydrogen polysiloxane, and the silane includes an alkylsilane treatment. The fluorine compound includes a perfluoroalkyl phosphate, a perfluoropolyether, and a perfluoroalkyl. Silicone, perfluoroalkyl / polyether co-modified silicone, perfluoroalkylsilane, and the like can be mentioned. Amino acid compounds include N-lauroyl-L-lysine, and metal soaps include aluminum stearate. . Further, the fine particle metal oxide used in the present invention, in order to suppress the photocatalytic activity, silica on the particle surface,
It is preferable that a metal oxide layer selected from alumina is provided, and it is particularly preferable that the fine particle metal oxide is silica,
After coating with alumina, it is preferable that the water-repellent surface treatment is performed.

The compounding amount of the inorganic pigment and the ultraviolet protection agent of the metal powder is 0.1 to 35 with respect to the total amount of the cosmetic.
% By mass, more preferably 3 to 30% by mass. Within this range, an effective ultraviolet protection effect can be obtained. In the present invention, it is preferable to use inorganic and organic ultraviolet protection components in combination, and it is also preferable to use components corresponding to the UVA region and the UVB region in combination.

In the cosmetic of the present invention, when used in combination with an inorganic ultraviolet protective agent such as fine particle titanium oxide, fine particle zinc oxide and cerium oxide, which are known to generate radicals when exposed to ultraviolet light. Active oxygen generated from the inorganic ultraviolet protective agent can be effectively eliminated.

In the cosmetic of the present invention, when various antioxidants which are conventionally known to have antioxidant activity are used in addition to the radical scavenger, the radical scavenging action and the antioxidant action are improved. It is preferable to use them in combination. Examples of antioxidants include tocopherol (vitamin E)
, Nordihydroguaiaretinic acid, butylhydroxyanisole, dibutylhydroxytoluene, propyl gallate, sodium bisulfite, erythorbic acid, sodium erysorbate, dilauryl thiodipropionate,
Tolylbiguanide, p-hydroxyanisole, octyl gallate, anhydrous sodium sulfite, apple extract,
Dehydrodicresol, apple polyphenol, lycopene, rosemary extract, mothra extract, clove extract, spinach extract, hamamelis extract, fennel extract, superoxide dismutase, deoxyribonucleic acid, carotenoid, flavonoid, tannin, lignan, saponin, phytic acid, etc. No.

The amounts of these antioxidants in cosmetics (in the case of extracts, in terms of dry residue) differ depending on the effective concentration of each component, but are generally 0% based on the mass of the cosmetic. It is preferably in the range of 0.0001 to 5% by mass.

The method for evaluating the radical scavenger in the present invention includes, for example, the following method. Fine particle zinc oxide is dispersed in a 90% by weight aqueous ethanol solution using ultrasonic waves to prepare a 0.05% by mass sample solution. A radical trapping agent and a fixed amount of a sample are added thereto, and mixed using ultrasonic waves. Xenon lamp, D as UV irradiation source
Using a two-lamp, high-pressure mercury lamp, etc., use a filter to cut off visible light, infrared light, and UVC
A and A are adjusted so that only ultraviolet rays in the UVB region can be irradiated. Ultraviolet light is applied to the sample container installed in the ESR using an optical fiber. Using a superoxide anion radical as a target, the amount of generated radicals is measured by ESR in a time range from irradiation to 0 to 750 seconds. The comparison of the measured values for each sample is made by comparing the value of manganese measured at the same time with 1
The error between samples is corrected by using the relative value set to 00.

In order to evaluate the activity, any one of the following two methods is used because there is no clear theory at present, but in this case, the evaluation was made using the radical generation intensity (max) of (B). . (A) The rising angle (radical generation intensity angle) of the peak from 0 second irradiation is compared. (B) The maximum value of the amount of generated radicals is compared in the time range from irradiation to 0 to 750 seconds.

Thus, how the radical generation intensity (max) changes when the sample is added to the radical generation intensity (max) when the sample is not added is measured. Fine particle zinc oxide emits a certain amount of radicals by ultraviolet rays, and if this is suppressed by the addition of a sample, the radical generation intensity (max) takes a smaller value.

In the cosmetic of the present invention, in addition to the above-mentioned components, oils, pigments, surfactants and the like usually used in cosmetics are used.
Various components such as a thickener, a preservative, a fragrance, a humectant, a salt, a solvent, a whitening agent, a chelating agent, a neutralizing agent, a pH adjuster, an insect repellent, and a physiologically active component can be used.

Examples of the physiologically active ingredient used in the present invention include substances that give some physiological activity to the skin when applied to the skin. Among these physiologically active ingredients, those having an antioxidant effect can be used in addition to the above-mentioned antioxidants. Examples of the physiologically active component include anti-inflammatory agents, anti-aging agents, tightening agents, hair growth agents, hair growth agents, humectants, blood circulation promoters, antibacterial agents, bactericides, drying agents, cooling sensation agents, warming sensation agents, Examples include vitamins, amino acids, wound healing promoters, stimulants, analgesics, cell activators, and enzyme components. Among them, natural plant extract components, seaweed extract components, and crude drug components are particularly preferable. In the present invention, it is preferred that one or more of these physiologically active components are blended in an amount of about 0.0001 to 10% by mass. For example, Ashitaba extract, Avocado extract, Amacha extract, Altea extract, Arnica extract, Aloe extract, Apricot extract, Apricot nucleus extract, Ginkgo extract, Turmeric extract, Age extract, Echinashi leaf extract, Ogon extract, Oubaku extract, Barley extract, St. John's wort extract, Spice lily extract, Dutch mustard extract, orange extract, seawater dried product, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, chamomile extract, carrot extract, kawagomugi extract, calcade extract, kiwi extract, kina extract, cucumber extract, Guanosine, Gardenia extract, Kumazasa extract, Clara extract, Walnut extract, Grapefruit extract, Clematis extract, Chlorella extract, Mulberry extract, Gentian extract Black tea extract,
Yeast extract, Burdock extract, Rice bran extract, Rice germ oil, Comfrey extract, Collagen, Cowberry extract, Psychic extract, Psychoextract, Saitai extract,
Salvia extract, Sabonsou extract, Sasa extract, Hawthorn extract, Sansho extract, Shiitake extract, Jio extract, Shikon extract, Perilla extract, Shinanoki extract, Shimotsukusou extract, Peony extract, Shobu root extract, Birch extract, Japanese horse chestnut extract, Sedum oak extract, Scotch hawthorn Extracts, Aspergillus niger extract, Achillea millefolium extract, Aesculacea mint extract, Sage extract, Zeniaoi extract, Senkyu extract, Assemble extract, Soybean extract, Tissou extract, Thyme extract, Chigaya extract, Chimpi extract, Touki extract, Tokinsenka extract, Tonin extract,
Spruce extract, dokudami extract, tomato extract, natto extract, carrot extract, garlic extract, nobara extract, bakmondou extract, lotus extract, parsley extract,
Honey, Parietaria extract, Hikikoshi extract, Bisabolol, Coltsfoot extract, Fukinotou extract, Bakuryo extract, Butcher bloom extract, Grape extract, Propolis, Loofah extract, Safflower extract, Peppermint extract, Bodaiju extract, Button extract, Hop extract, Pine extract, Mizubasho Extracts, mud mushroom extract, peach extract, cornflower extract, eucalyptus extract, saxifrage extract, yuz extract, yokuinin extract, mugwort extract, lavender extract, lettuce extract, lemon extract, vetch extract, rose extract,
Roman chamomile extract, royal jelly extract and the like can be mentioned.

Also, mucopolysaccharides such as sodium hyaluronate and sodium chondroitin sulfate, collagen, elastin, chitin, chitosan, biopolymers such as hydrolyzed eggshell membranes, glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, Amino acids such as arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, tryptophan, hormones such as estradiol and ethenylestradiol, amino acids, sodium lactate, urea, sodium pyrrolidonecarboxylate, moisturizing ingredients such as betaine, whey, sphingo Oily components such as lipids, ceramides, cholesterol, cholesterol derivatives, phospholipids,
Anti-inflammatory agents such as ε-aminocaproic acid, glycyrrhizic acid, β-glycyrrhetinic acid, lysozyme chloride, guaiazulene, hydrocortisone, allantoin, tranexamic acid, azulene, vitamins A, B2, B6, D, K, calcium pantothenate, biotin, nicotine Active ingredients such as acid amide, allantoin, diisopropylamine dichloroacetate and 4-aminomethylcyclohexanecarboxylic acid, cell activators such as α-hydroxy acid and β-hydroxy acid, blood circulation promoters such as γ-oryzanol, retinol, retinol derivatives Wound healing agents such as cepharanthin, licorice extract, pepper tincture, hinokitiol, garlic iodide extract, pyridoxine hydrochloride, nicotinic acid, nicotinic acid derivatives, calcium pantothenate, D
-Pantothenyl alcohol, acetyl pantothenyl ethyl ether, biotin, allantoin, isopropylmethylphenol, estradiol, ethinylesteradiol, capronium chloride, benzalkonium chloride,
Diphenhydramine hydrochloride, tacanal, camphor, salicylic acid, vanylyl nonylate, vanillyl nonanoate, pyroctone olamine, glyceryl pentadecanoate, 1-menthol, camphor, etc. Hair restoration agents such as mexiletine hydrochloride, auxin, female hormones, cantharis tincture, cyclosporine, zinc pyrithione, hydrocortisone, minoxidil, polyoxyethylene sorbitan monostearate, peppermint oil, and sasanishiki extract. In the present invention, α-hydroxy acids, β-hydroxy acids, retinol, vitamin A such as retinol derivatives, γ-aminobutyric acid, diisoprovylamine dichloroacetate, mucopolysaccharides and other cell activators and anti-wrinkling agents are used in combination. It is preferable to mix them because excellent anti-aging cosmetics can be obtained. The amount of these physiologically active ingredients (the extract is calculated as dry residue)
0.0001 to 10% by mass is preferred.

Examples of oils include avocado oil, linseed oil, almond oil, ibotaro wax, eno oil, olive oil, cacao butter, kapok wax, kaya oil, carnauba wax, liver oil, candelilla wax, tallow, beef tallow, beef bone Fat,
Hardened beef tallow, ginger oil, whale wax, hardened oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugar cane wax, sasanqua oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojoba wax, shellac wax, turtle Oil, soybean oil, teaseed oil, camellia oil, evening primrose oil, corn oil, lard oil, rapeseed oil, Japanese kiri oil, bran wax, germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil, hardened Castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil, macadamia nut oil, beeswax, mink oil, cottonseed oil, cotton wax, mokuro, mokuro kernel oil, montan wax,
Coconut oil, hydrogenated coconut oil, tricoconut oil fatty acid glyceride,
Sheep fat, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin Alcohol ethers, egg yolk oils and the like; hydrocarbon oils such as ozokerite, squalane, squalene, ceresin, paraffin, paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax, petrolatum, etc .;
Higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid,
Oleic acid, linoleic acid, linolenic acid, arachidonic acid,
Eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid and the like; as higher alcohols, lauryl alcohol, myristyl alcohol, palmityl alcohol,
Stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol, POE
Cholesterol ether, monostearyl glycerin ether (bacyl alcohol), monooleyl glyceryl ether (serakyl alcohol) and the like; ester oils include diisobutyl adipate, 2-hexyl decyl adipate, di-2-heptyl undecyl adipate, mono N-alkyl glycol isostearate, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, tetra-2- Pentaerythritol ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate,
Neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate Isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearylate, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, myristic acid 2-hexyldecyl, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glu Min acid-2-octyldodecyl ester, diisostearyl malate, and the like; The glyceride oil, acetoglyceryl, triisooctanoate glyceryl triisostearate, glyceryl triisopalmitate, glyceryl monostearate,
Glyceryl di-2-heptylundecanoate, glyceryl trimmyristate, diglyceryl isostearate myristate and the like can be mentioned.

As the surfactant, anionic,
There are cationic, nonionic and amphoteric activators, but there is no particular limitation, and any of them can be used as long as it is used for ordinary cosmetics.
To be specifically exemplified below, examples of anionic surfactants include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and salts thereof, carboxylate salts such as condensation of amino acids and fatty acids, and alkyl salts. Sulfonic acid, alkene sulfonate, fatty acid ester sulfonate, fatty acid amide sulfonate, alkyl sulfonate and its formalin condensate sulfonate, alkyl sulfate salt, secondary higher alcohol sulfate salt, Alkyl and allyl ether sulfates, fatty acid ester sulfates, fatty acid alkylolamide sulfates, sulfates such as funnel oils, alkyl phosphates, ether phosphates, alkyl allyl ether phosphates, amidolines Acid salt, N-acid Amino acid-based surfactants and the like; cationic surfactants include amine salts such as alkylamine salts, polyamines and amino alcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridium salts, imidazolium salts and the like; Nonionic surfactants include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, and polyoxypropylene alkyl ethers. Oxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Oxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene Cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, polyoxyalkylene / alkyl co-modified organopolysiloxane, alkanolamide, sugar ether,
Sugar amide and the like; Examples of the amphoteric surfactant include betaine, aminocarboxylate, and imidazoline derivative.
When the surfactant is used, the amount is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, based on the total amount of the cosmetic. One or more surfactants can be used.

Examples of the antibacterial and preservatives include alkyl paraoxybenzoate, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, and phenoxyethanol. Antibacterial agents include benzoic acid, salicylic acid, phenolic acid, and the like.
Sorbic acid, alkyl paraoxybenzoate, parachloromethcresol, hexachlorophen, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, triclosan, photosensitizer, phenoxyethanol and the like.

Examples of the humectant include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol,
Examples include glycerin, diglycerin, sorbitol, malbitol, trehalose, raffinose, xylitol, mannitol, hyaluronic acid and salts thereof, glycols such as polyethylene glycol and polyglycerin, polyhydric alcohols and polysaccharides. These are preferably used alone or in combination of two or more.

Examples of the powders and coloring agents used in the present invention include those used in ordinary cosmetics, such as spherical, rod-like, needle-like, plate-like, irregular, flake-like, and spindle-like. ), Particle size (fog, fine particles, pigment grade, etc.) and particle structure (porous, non-porous, etc.), any of which can be used. For example, inorganic powder, organic powder , Surfactant metal salt powders, colored pigments, pearl pigments, natural pigments, etc. Specific examples of the inorganic powders include zirconium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, and calcium carbonate. , Magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, phlogopite, biotite, lithia mica,
Silicic acid, Silicic anhydride, Aluminum silicate, Magnesium silicate, Aluminum magnesium silicate, Calcium silicate, Barium silicate, Strontium silicate, Metal tungstate, Hydroxyapatite, Vermiculite, Heidilite, Bentonite, Montmorillonite, Hector Light, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, silica, etc .; organic powders include polyamide powder, polyester powder,
Polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk powder, nylon powder, 12 nylon, 6 nylon, silicone powder, silicone rubber Powder, silicone elastomer spherical powder, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin , Microcrystalline fiber powder, starch powder, lauroyl lysine, etc .; surfactant metal salt powder (metal soap) includes stearic acid Aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, sodium zinc cetyl phosphate, and the like; as the colored pigments, inorganic red pigments of iron hydroxide and iron titanate; Inorganic black pigments such as carbon black; inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate; inorganic blue pigments such as navy blue and ultramarine blue; and tar pigments Lakes of pigments, lakes of natural pigments, and synthetic resin powders of composites of these powders; pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, oxidized Titanium-coated bismuth oxychloride Titanium oxide coated talc, fish scales, titanium oxide-coated colored mica; as tar pigments include Red No. 3, No. 104 Red, Red 10
6, Red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 227
No., Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 2
03, Yellow 204, Yellow 401, Blue 1, Blue 2, Blue 201, Blue 404, Green 3, Green 2
01, green 204, green 205, orange 201,
Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 20
No. 7, etc .; natural pigments are powders selected from carminic acid, laccaic acid, calsamine, bradyline, crocin, etc. These powders are also composites of powders as long as they do not impair the effects of the present invention. And general oils, silicone oils,
Those treated with a fluorine compound, a surfactant or the like can also be used. For example, fluorine compound treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment The surface treatment may or may not be performed in advance by plasma treatment, mechanochemical treatment, or the like, and one or more surface treatments may be used in combination as needed. In the present invention, one or more of these powders can be used in combination.

The specific use of the cosmetic of the present invention is not particularly limited, but preferred examples thereof include skin care products, hair products, antiperspirant products, make-up products, and ultraviolet protection products. For example, emulsions, creams, lotions, calamine lotions, sunscreens, suntans, aftershave lotions, preshave lotions, packs, cleansing agents, face wash, anti-acne cosmetics, basic cosmetics such as essences, foundations, white powder, eyes Makeup cosmetics such as shadow, eyeliner, eyebrow, teak, nail color, lipstick, shampoo, rinse, conditioner, hair color, hair tonic, set agent, body powder, hair restorer, deodorant, depilatory, soap, body shampoo Bath salts, hand soaps, perfumes and the like. In particular, a sunscreen, a foundation, or an antioxidant effect containing an inorganic ultraviolet protective agent such as fine particle titanium oxide, fine particle zinc oxide, and cerium oxide, which are known to generate radicals when exposed to ultraviolet light, is required. Anti-aging cosmetics are preferred. Although there is no particular limitation on the form of the product, it can be applied to a liquid, an emulsion, a cream, a solid, a paste, a gel, a powder, a multilayer, a mousse, a spray, and the like.

[0038]

The present invention will be described below in more detail with reference to Examples and Comparative Examples.

Production Example 1 An undiluted juice obtained by squeezing and filtering cranberry fruit (manufactured by MILNE FRUIT PRODUCT, USA)
(Company S, 6-fold concentrated solution) is purified by ultrafiltration. That is, 10 kg of the cranberry juice stock solution was mixed with Sartorius Sartcon slice PSU-30K (fraction molecular weight 3
0000) to perform fractionation by pressurization using a pump. 400 g of the concentrated solution was washed five times with 400 g of a 10% ethanol solution to remove low molecular components. Then, ethanol was removed by a freeze-drying method to obtain a desired purified cranberry extract (42-fold concentrated solution). When the anthocyanidin content of this purified cranberry extract was tested by the method described above, it was less than 0.01% by mass. Further, as a result of analysis under the following conditions by high performance liquid chromatography, no peak of caffeic acid glycoside was detected.

[Analytical Method for Caffeic Acid Glycoside] Conditions for High Performance Liquid Chromatography Apparatus: Waters, Inc. Column: Puresil C18 4.6 × 150 mm (Waters, Inc.) Mobile phase: A (0.5%) Phosphoric acid aqueous solution) B (5 parts of phosphoric acid + 295 parts of water + 700 parts of acetonitrile) B10% → 100% (30 minutes) gradient Flow rate: 0.7 mL / min Detector: 996 photodiode array, detection wavelength 200 nm to 600 nm

In order to clarify the difference between the above purified cranberry extract and the known proanthocyanidins disclosed in Japanese Patent No. 2528087 and the like, the following confirmation experiments were conducted.

The UV-Vis spectrum (FIG. 1) of a diluted solution of the purified cranberry extract in citrate buffer (pH 3.0) confirmed that it had a maximum absorption at 510 to 520 nm. The property of having an absorption maximum around 520 nm in an acidic solution is a characteristic property of anthocyanins. Confirmation test of anthocyanin Citrate buffer of purified cranberry extract (pH 3.
0) The solution (1 + 100) exhibited a red to dark blue color. When the solution was made alkaline by adding a sodium hydroxide solution (1 + 25) to the solution, it was confirmed that the solution was anthocyanin. From the HPLC chart, it was confirmed that most of the constituents were polymers. (FIG. 2) [HPLC analysis conditions] Apparatus: Waters Co. Column: SymmetrySild RP18 5 μm, 4.6 × 150 mm (Waters Co.) Mobile phase: A Phosphoric acid 5 Acetonitrile 100 Water 895 B Phosphoric acid 5 Water 295 Acetonitrile 700 A100% → B100% (30 minutes) linear gradient Flow rate: 0.7 mL / min Detector: 996 photodiode array, detection wavelength 200 nm to 600 nm

According to Japanese Patent No. 2528087, proanthocyanidin is flavan-3-
It contains at least one member selected from the group consisting of dimers and octamers combined with all or flavan-3,4-diol as a constituent unit, such as conker shells, cranberry (cranberry) and barley. Of various plant bodies as a raw material using a solvent, and the extract is fractionated and purified by liquid chromatography or the like, or is treated with a selective adsorbent of procyanidin to concentrate the proanthocyanidin fraction. Is stipulated.

[0044]

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Considering the chemical structure of flavan-3,4-diol, the molecular weight of flavan-3,4-diol is 306, and proanthocyanidin is a 2- to 10-mer of flavan-3,4-diol. As a result, the molecular weight was found to be less than 5000. From these points, it is considered that the purified cranberry extract is a compound mainly composed of an anthocyanin polymer having a molecular weight of 30,000 or more, while proanthocyanidin contains flavan-3,4-diol or flavan-3-ol having a molecular weight of less than 5000. Since it was found that the extract was a condensed tannin as a constituent unit, it was found that the extract of the present invention was an anthocyanin polymer, not a known proanthocyanidin, and did not contain proanthocyanidin.

Next, evaluation methods for various properties of the cosmetics of the examples and comparative examples are shown below.

[Evaluation of Cytotoxicity] B16 melanoma cells were seeded on a 12-well plate at 2 × 10 4 cells / well, and
After 4 hours, the medium was replaced with the theophylline-containing medium containing each sample. After culturing for 72 hours, the cells were treated with 10% TCA, 1: 1 ethanol: dimethyl ether, and then changed to a 1N NaOH solution containing 10% dimethyl sulfoxide. After lysis, an appropriate amount was diluted and the amount of protein was measured to determine the number of cells. The cytotoxicity was evaluated from the change in cell number.

[Evaluation of Radical] Based on the above evaluation method, JEF-FE2XG manufactured by JEOL Ltd. was used as ESR, and 5,5-dimethyl-1-
Pyroline-1-oxide (DMPO) at a concentration of 1.5 wt.
%, And the evaluation was performed focusing on the superoxide anion radical as the measured radical species. Also, as an ultraviolet ray source, SPOT CURE-U manufactured by Ushio Inc.
Ultraviolet irradiation was performed at an irradiation energy of 20 mW / cm ^-2 using IS25102. In addition, the measurement of the amount of ultraviolet rays
cells Band Po from EllsGriot
The measurement was performed using a lower / Energy Meter 13PE001 type. The evaluation was performed using the above-described radical generation intensity (max). Further, the amount of radicals generated when the product was directly charged instead of the zinc oxide used as the reference system was also measured.

[Evaluation of Skin Irritation] Ten expert panelists were prepared and evaluated according to the evaluation criteria shown in Table 1, and the evaluation results were obtained based on the total score of all panelists. Therefore,
The higher the score, the higher the skin irritation (full score: 50)
point).

[0050]

[Results of Evaluation of Cytotoxicity of Purified Cranberry Extract] When the cytotoxicity of the purified cranberry extract was evaluated in the range of 0.1 to 1% by mass, it was confirmed that the cell number was not reduced and the safety was high. Was. In addition, as a comparative control, a cranberry extract fraction containing proanthocyanidin and caffeic acid glycoside was tested and found to show cytotoxicity.

[Results of Evaluation of Radical Scavenging Activity of Purified Cranberry Extract] Radical generation intensity (ma)
When x) was examined, the results shown in Table 2 were obtained. The radical generation intensity (max) used a manganese relative value.

[Table 2] Sample radical generation intensity (max) ------------------------------------ ------------------------------- No additive (zinc oxide standard system) 23 Purified cranberry extract (Production Example 1) 12 Cranberry Extract (including proanthocyanidins and caffeic acid glycosides) Fractions with molecular weight less than 5000 13

Example 1 A foundation was obtained using the above purified cranberry extract according to the formulation shown in Table 3. The unit of the compounding amount is mass% (the same applies hereinafter).

[Table 3] Component A Talc 20 Fine particle titanium oxide 3 Fine particle zinc oxide 3 Methyl hydrogen polysiloxane heating surface treatment Pigment grade titanium oxide 12 Sericite Remaining amount N-lauroyl-L-lysine treated pigment grade iron oxide 5 (mixture of red iron oxide, yellow iron oxide, iron black) spherical polyurethane powder 1 aluminum myristate treated spherical acrylic resin powder 1 silicone elastomer spherical powder 1 component B perfluoropolyether 0.3 tocopherol 0.2 retinol palmitate 0. Reference Signs List 1 glycerin 0.2 petrolatum 1 vegetable squalane 6 perfluoroalkyl-modified dimethiconol 3 component C purified cranberry extract 2 preservative appropriate amount

Component A was mixed using a mixer. Next, the component B that had been heated and mixed in advance was added to the component A, followed by stirring. Further, the component C was added, mixed, pulverized, passed through a sieve, and then pressed into a metal plate using a metal mold to obtain a product.

Comparative Example 1 A product was obtained in the same manner as in Example 1 except that purified water was used instead of the purified cranberry extract of Example 1.

Production Example 2 and Example 2 A hot water extract of cranberries was concentrated under reduced pressure using a rotary evaporator to obtain a 5-fold conch product. To 50 g of this cranberry concentrate, the same amount of 60% ethanol was added and dissolved. This solution was applied to a column (bed volume φ5 × 21 cm) packed with Sephadex LH-20. Using 60% ethanol as the eluate, flow rate 10
Chromatography treatment was performed at 0 mL / hr, and 200 mL fractions were collected. Fr1 to Fr2 fractions were obtained, and Fr9 to Fraction 12 fractions eluted last were concentrated to 40 fractions.
0 g. The resulting purified cranberry extract has an anthocyanidin content of 0.004% by mass, a polyphenol content of 0.06% by mass, and a dry residue of 0.1% by mass.
It was 7% by mass. Further, as a result of analysis by high performance liquid chromatography, no peak of caffeic acid glycoside was detected. This purified cranberry extract has a molecular weight of 5
It contained over 000 anthocyanin polymers. Using the purified cranberry extract, a lotion was obtained according to the formulation in Table 4, and this was impregnated into a nonwoven fabric to obtain a lotion mask. In addition, rosemary extract and butylhydroxytoluene were blended as antioxidants.

[Table 4] Ingredient Compounding amount --------------------------------------- ------------ Refined cranberry extract 20 1.3-butylene glycol 10 Rosemary extract (dry residue 8% by mass) 0.5 Butylhydroxytoluene 0.01 Preservatives Appropriate amount Purified water balance

Comparative Example 2 Instead of the purified cranberry extract of Example 2, the cranberry fruit juice used in Production Example 1 was subjected to squeezing filtration to fractionate the components of the undiluted juice cranberry having a molecular weight of less than 5000. A product was obtained in the same manner as in Example 2 except that the same amounts of proanthocyanidin and caffeic acid glycoside were used.

The evaluation results of the cosmetics of Examples and Comparative Examples are shown below.

[Evaluation of Superoxide Anion Radical Generation Amount of Product] When the generation amount of superoxide anion radical was measured for Example 1 and Comparative Example 1, the generation amount of Example 1 was about 40% as compared with Comparative Example 1. There were few.

[Table 5] Feeling uncomfortable on skin -------------------------------------- ------------------ Example 2 15 Comparative Example 2 45

From the results shown in Table 2, it was found that the purified cranberry extract of the present invention effectively eliminated the superoxide anion radical generated by the photocatalytic activity of zinc oxide. Furthermore, it was found that the compound had the same or better radical scavenging activity as compared with those containing proanthocyanidin, caffeic acid glycoside, and the like, which have been reported in the past. From the results of evaluation of the amount of generated superoxide anion radicals in the product, it was found that the product in which the radical scavenger of the present invention was blended suppressed the generation of radicals more effectively than in the case where it was not blended.

From the results of the cytotoxicity evaluation, it was found that the radical scavenger of the present invention was more excellent in safety than the conventionally known radical scavenger comprising an active ingredient derived from cranberry. This was also confirmed from the fact that there was a difference in the presence or absence of discomfort to the skin in the product tests in Table 5. This difference is considered to be due to the property that the radical scavenger of the present invention is a polymer.

[0066]

In view of the above, the present invention provides a radical scavenger comprising a cranberry berry pressed filtrate and / or extract, which is a natural component, has low cytotoxicity, and has an excellent radical scavenging effect, It is clear that cosmetics excellent in safety containing the radical scavenger are provided.

[Brief description of the drawings]

FIG. 1: Citrate buffer of purified cranberry extract (p
H3.0) is a UV-Vis spectrum diagram of a diluted solution.

FIG. 2 is an HPLC chart of a purified cranberry extract.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) A61K 7/00 A61K 7/00 H 7/021 7/021 31/7048 31/7048 A61P 39/06 A61P 39 / 06 F-term (reference) 4C083 AA111 AA112 AB211 AB212 AB241 AB242 AB351 AB442 AC012 AC022 AC091 AC122 AC291 AC341 AC471 AC472 AC511 AC662 AC741 AC761 AC841 AC851 AD042 AD072 AD152 AD162 AD391 AD601 AD621 AD622 AD661 AD662 BB46 ABB11A21A EA08 GA17 NA06 NA14 ZC37 4C088 AB44 AC04 BA14 BA25 CA02 CA03 MA63 NA07 NA14 ZA89 ZC37

Claims (7)

[Claims] 1. A radical scavenger consisting mainly of a pressed filtrate and / or an extract of cranberry fruit containing an anthocyanin polymer. 2. The radical scavenger according to claim 1, further comprising a purified product obtained by further purifying the pressed and / or extracted cranberry fruit by gel filtration or ultrafiltration. 3. The molecular weight of the anthocyanin polymer is 500.
3. The radical scavenger according to claim 1, which is 0 or more. 4. A cosmetic comprising the radical scavenger according to claim 1 and an ultraviolet protective agent. 5. The ultraviolet protective agent is one or more selected from the group consisting of titanium oxide fine particles, zinc oxide fine particles, and cerium oxide.
The cosmetic according to claim 4, which is at least one kind. 6. A cosmetic comprising the radical scavenger according to claim 1 and an antioxidant. 7. The antioxidant is tocopherol and a derivative thereof, nordihydroguaiaretinic acid, butylhydroxyanisole, dibutylhydroxytoluene, propyl gallate, sodium bisulfite, erythorbic acid, sodium erysorbate, dilauryl thiodipropionate. , Torilbiguanide, p-hydroxyanisole,
Octyl gallate, anhydrous sodium sulfite, apple extract, dehydrodicresol, apple polyphenol,
Lycopene, rosemary extract, mothra extract, clove extract, spinach extract, hamamelis extract, fennel extract, superoxide dismutase, deoxyribonucleic acid, carotenoid, flavonoid, tannin, lignan, saponin, one selected from the group consisting of phytic acid, or The cosmetic according to claim 6, wherein the cosmetic is at least two kinds.