JPH1087469A - Ultraviolet light protecting agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject agent capable of excellently screening ultraviolet light, being safe to a human body even by long-term repetition and chronic use and exhibiting usefulness, by making the agent contain a metal compound as an ultraviolet scattering agent and a phenolic compound. SOLUTION: This agent contains (A) one or more selected from among titanium dioxide, titanium dioxide-coated mica and zinc oxide and (B) a phenolic compound, preferably tannin. The blending ratio of each component is >=0.025 pt.wt., preferably >=0.05 pt.wt. based on 1 pt.wt. of the component A. Consequently, an ultraviolet light protecting agent excellent in ultraviolet scattering effect and not emitting active oxygen by itself when receives ultraviolet rays can be expected.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to an ultraviolet ray protective agent comprising one or more selected from titanium dioxide, titanium dioxide-coated mica, and zinc oxide, and a phenolic compound, preferably tannin.

[0002]

TECHNICAL FIELD The present invention provides an ultraviolet ray protective agent applied to skin to protect the skin from light, particularly ultraviolet rays. Specifically, sunscreen cosmetics (such as sun cream), foundations, and the like are listed. In addition, even in cosmetics and external preparations for purposes other than UV protection, if the formulation contains titanium dioxide or zinc oxide and is particularly applicable when going out, use it as the UV protection agent of the present invention. be able to.

[0003]

2. Description of the Related Art Ultraviolet rays are applied to skin by erythema reaction (sunburn), pigmentation (santan), photosensitive dermatitis, DN
It is widely recognized that it causes various injuries such as A-damage, accelerated aging, abnormal pigmentation, and skin cancer, and measures against ultraviolet rays are extremely important in maintaining skin health and beauty.

In order to protect the skin from ultraviolet rays, external preparations such as cosmetics are generally used. These include those that block ultraviolet rays (scatter and absorb) and those whose main purpose is aftercare after irradiation, and are classified as sunscreen agents and aftersuncare cosmetics.

[0005] Sunscreen agents block ultraviolet rays (UVA and UVB) on the skin surface.
Ultraviolet scattering agents such as titanium dioxide and zinc oxide, and ultraviolet absorbers such as p-aminobenzoic acid (PABA) are used as main agents.

[0006] On the other hand, after-sun care cosmetics are used to care for sun-burned skin, and include anti-inflammatory agents for alleviating and suppressing inflammation such as erythema, agents for preventing or improving pigmentation, and water content. Moisturizers and the like are used to supplement moisture in the reduced skin.

[0007]

In order to protect the skin from the harm of ultraviolet rays, it is of course important to protect the ultraviolet rays first. Therefore, it is a prerequisite to take measures to block ultraviolet rays such as sunscreen agents rather than after sun care cosmetics.

By the way, fine particles of titanium dioxide, zinc oxide and the like conventionally used in sunscreen agents and the like have a high refractive index, are excellent in optical properties such as whiteness, hiding power and coloring power, and Has a very high scattering effect.
In addition, since the light resistance, weather resistance and heat resistance are all large, it is suitable for application to external preparations.

However, these metal compounds such as titanium dioxide and zinc oxide, when exposed to ultraviolet rays, cause a slight amount of superoxide radical (.
O ₂ ⁻ ), hydroxy radical (.OH), hydrogen peroxide (H ₂ O ₂ ), or the like may express very reactive active oxygen. (Ruxiong Cai et al., Induction of Cytotoxic
ityby Photoexcited TiO ₂ Particles, CANCER RESEARCH
52, 2346-2348 (1992))

[0010] Even in vivo, in various physiological reactions corresponding to self-defense, active oxygen is expressed, but surplus active oxygen attacks lipids, proteins, nucleic acids, etc. of cellular tissues, causing a variety of injuries. This has been clarified by numerous studies so far. (Reactive Oxygen and Diseases, Chemical Dojin Co., Ltd. (1989). SOD and Reactive Oxygen Regulators-Their Pharmacological Actions and Clinical Applications, Nippon Medical Center Co., Ltd. (198
9)) This phenomenon can also occur in skin tissue, in which case it is known to cause skin disorders such as, for example, rough skin, inflammation, pigmentation, aging of the skin, wrinkles, and reduced elasticity. . However, since the active oxygen as described above is generated between ultraviolet rays and a metal compound, that is, under an environment that is not controlled by a living body, there is a concern that the active oxygen may affect skin tissues.

[0011] Therefore, although the conventional ultraviolet protective agents containing titanium dioxide and zinc oxide are extremely useful from the viewpoint of blocking ultraviolet rays, when they are repeatedly and continuously applied to the skin surface for a long period of time, they are not safe. The uneasy element was left.

The present invention has been made by paying attention to such problems of the conventional UV protection agents. That is, (1) the presence of titanium dioxide and / or zinc oxide,
(2) Exposure to ultraviolet light, (3) Effective effect under the three requirements of an external preparation to be applied to the skin, and is a safe and useful ultraviolet protection agent for the human body even in repeated use over a long period of time. Is provided.

[0013]

Means for Solving the Problems Any one or two selected from titanium dioxide, titanium dioxide-coated mica, and zinc oxide
This is achieved by providing a UV protection agent containing at least one species and a phenolic compound, preferably tannin.

[0014] The present inventors also found that the phenomenon in which active oxygen is manifested by irradiating a system containing fine particles of titanium dioxide or zinc oxide useful as an ultraviolet scattering agent with ultraviolet rays is NB.
It was confirmed by the T (nitro blue tetrazolium) method. However, it was found that when a phenolic compound, preferably tannin, was present, no active oxygen was observed even when irradiated with ultraviolet rays.

[0015] Such an action is caused by enzymes such as catalase and SOD which are involved in the removal of active oxygen in vivo.
Or vitamin C or vitamin E, known as antioxidants
It was confirmed that the color tone and odor of the system did not change over time.

The phenolic compounds used in the present invention include catechol, pyrogallol, gallic acid, caffeic acid, laccol, bilobal, personol, ginkyoic acid and derivatives thereof, phloroglucinol derivatives, stilbene derivatives, rutin, quercetin, Kaempferol, catechin, epicatechin, gallocatechin,
There is a phenolic compound having a flavonoid skeleton represented by epigallocatechin, genistein, soyzein, apigenin, ougonin, baicalein or the like or a derivative thereof, catechol tannin (condensed tannin), and tannin such as pyrogallol tannin (hydrolyzable tannin). . In addition, Asenyaku, Asuka, Vladimir, Carmaeko, Carabe grass, Obayashishabushi fruit, Yamashiko, Onishi-kusa, Kakidai, Kawara-yomogi, Sengakurusa, Gallicia, Kunugi, Chestnut or its astringent skin, Buckthorn, Crotch, Dingka, Gennoshoko, Tea , Green tea, koshibachi, bonbon, coffee beans, sasanqua, peony, linden, camellia, ten medicine, five times child, hamamelis, loquat leaf, peony skin, myrrh, myrobaran, yawagi,
It is also possible to use tannin herbs such as Yamaharu, Tiger Eargrass, and extracts from plants containing a large amount of tannins such as Jiyu or tannins, or tannins purified therefrom.
It is better to use 80% or more purified tannins, and even higher purity tannins. For example, when a plant extract having a low content as a phenolic compound is used, the intended effect cannot be maintained for a long time, or a large amount is required to obtain an effective amount, and as a result, the color tone is reduced. This is because there is a fear that the value as a product may be degraded due to a shift or a change over time.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The phenolic compound used in the present invention includes not only commercially available chemicals but also extracts from natural products. In the case of extraction,
This is carried out by a conventional method using one or an arbitrary mixture of polar solvents such as water, ethanol, propylene glycol and butylene glycol. For further purification, methods such as recrystallization from a poor solvent, column fractionation, and ultrafiltration are used.

Further, among the metal compounds exhibiting the ultraviolet scattering effect, for example, titanium dioxide may be any of rutile type, anatase type and ultrafine particle type.
Titanium dioxide-coated mica is obtained by forming mica into smooth flaky particles and forming a uniform layer of titanium dioxide on the surface of the particles as nuclei. Further, the zinc oxide is not particularly limited, and, similarly to the other zinc oxides, all those usually used for external preparations can be used.

The mixing ratio of the metal compound and the phenolic compound is not particularly specified, but in consideration of the test results described below, the phenolic compound is preferably 0.025 parts by weight or more, more preferably 0.025 parts by weight, based on 1 part by weight of the metal compound.
It is preferred to add 0.05 parts by weight or more.

In addition to the above essential components, the ultraviolet protective agent of the present invention may be selected from the following various components and additives usually used in skin external preparations such as cosmetics, which are suitable for use. They can be arbitrarily selected and used in combination.

[1] Various fats and oils Avocado oil, almond oil, fennel oil, perilla oil,
Olive oil, orange oil, orange luffer oil, sesame oil,
Cocoa butter, chamomile oil, carrot oil, cucumber oil, tallow, tallow fatty acid, kukuinut oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, persic oil, castor oil, cottonseed oil, peanut oil, turtle oil, Mink oil, egg yolk oil, cocoa butter, palm oil, palm kernel oil, mocro, coconut oil, tallow, lard, milk fat, or hydrogenated products of these oils (hardened oil, etc.).

[2] Waxes Beeswax, carnauba wax, whale wax, lanolin, liquid lanolin, reduced lanolin, hard lanolin, candelilla wax,
Montan wax, shellac wax, etc.

[3] Mineral oil Liquid paraffin, vaseline, paraffin, ozokeride, ceresin, microcrystalline wax, squalene, squalane, pristane, and the like.

[4] Fatty acids Natural fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, tall oil, lanolin fatty acid, isononanoic acid, caproic acid , 2-ethylbutanoic acid, isopentanoic acid, 2-methylpentanoic acid, 2
-Synthetic fatty acids such as ethylhexanoic acid and isopentanoic acid.

[5] Alcohols Ethanol, isopyropanol, lauryl alcohol,
Natural alcohols such as cetanol, stearyl alcohol, oleyl alcohol, lanolin alcohol, cholesterol, and phytosterol; and synthetic alcohols such as 2-hexyldecanol, isostearyl alcohol, and 2-octyldodecanol.

[6] Polyhydric alcohols Ethylene oxide, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, polyethylene glycol, propylene oxide, propylene glycol , Polypropylene glycol, 1,3-butylene glycol, glycerin, pentaerythritol, sorbitol, mannitol and the like.

[7] Esters Isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyl dodecyl myristate, hexyl decyl dimethyloctanoate, cetyl lactate, Myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, and the like.

[8] Metal soaps Aluminum stearate, magnesium stearate, zinc stearate, calcium stearate, zinc palmitate, magnesium myristate, zinc laurate, zinc undecylenate and the like.

[9] Gum, sugars and water-soluble polymer compounds Arabic gum, benzoin gum, dammar gum, guaiac oil, Irish moss, karaya gum, tragacanth gum,
Carob gum, quinseed, agar, casein, lactose,
Fructose, sucrose and its esters, trehalose and its derivatives, dextrin, gelatin, pectin, starch, carrageenan, carboxymethyl chitin or hydroxyalkyl (C2-C4) to which alkylene (C2-C4) oxide such as ethylene oxide is added. ) Chitin or chitosan, low molecular weight chitin or chitosan, chitosan salt, sulfated chitin or chitosan, phosphorylated chitin or chitosan, alginic acid and its salts, hyaluronic acid and its salts, chondroitin sulfate and its salts, heparin, ethyl cellulose, methyl cellulose, carboxy Methylcellulose, carboxyethylcellulose, sodium carboxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, nitrocellulose, crystalline cellulose, poly Alkenyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, polyvinyl methacrylate, polyacrylic acid salts, polyalkylene oxide or crosslinked polymer thereof such as polyethylene oxide or polypropylene oxide, carboxyvinyl polymers, such as polyethyleneimine.

[10] Surfactants Anionic surfactants (carboxylates, sulfonates, sulfates, phosphates), cationic surfactants (amines, quaternary ammonium salts), amphoteric surfactants : Carboxylic acid type amphoteric surfactant (amino type, betaine type), sulfate ester type amphoteric surfactant, sulfonic acid type amphoteric surfactant, phosphate ester type amphoteric surfactant, nonionic surfactant (ether type non-amphoteric surfactant) Ionic surfactant, ether ester type nonionic surfactant, ester type nonionic surfactant, block polymer type nonionic surfactant, nitrogen-containing nonionic surfactant), other surfactants (natural surfactant) Agent, protein hydrolyzate derivative,
Polymer surfactant, surfactant containing titanium and silicon,
Fluorocarbon surfactants).

[11] Various vitamins Vitamin A group: retinol, retinal (vitamin A
1), dehydroretinal (vitamin A2), carotene,
Lycopene (provitamin A), vitamin B group: thiamine hydrochloride, thiamine sulfate (vitamin B1), riboflavin (vitamin B2), pyridoxine (vitamin B6), cyanocobalamin (vitamin B12), folate, nicotinic acid, pantothenic acid, Biotins, choline, inositols, vitamin C group: ascorbic acid and its derivatives,
Vitamin D group: Ergocalciferol (Vitamin D
2), cholecalciferol (vitamin D3), dihydrotaxerol, vitamin E group: tocopherol and its derivatives, ubiquinones, vitamin K group: phytonadione (vitamin K1), menaquinone (vitamin K2), menadione (vitamin K3), menadiol (Vitamin K4)
Such.

[12] Various amino acids Valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, glycine, alanine, asparagine, glutamine, serine, cysteine, cystine, tyrosine, proline, hydroxyproline, aspartic acid, glutamic acid , Hydroxylysine, arginine, ornithine, histidine, and the like, and their sulfates, phosphates, nitrates, citrates, and amino acid derivatives such as pyrrolidone carboxylic acid.

[13] Various additives derived from plant or animal raw materials These are processed in a conventional manner according to the type and form of the product to be added (for example, grinding, milling, washing, hydrolysis, Fermentation, purification, squeezing, extraction, fractionation, filtration, drying, pulverization, granulation, dissolution, sterilization, pH adjustment, deodorization, decolorization, etc. You can choose to serve. As for the solvent used for extraction, the usage of the product to be provided (edible, external use, bath),
It should be selected in consideration of the processing to be performed later, etc.
Usually, water and water-soluble organic solvents (eg, ethanol,
It is desirable to use one or a mixture of two or more selected from propylene glycol and 1,3-butylene glycol. However, when the content of the organic solvent is not preferable depending on the use, only water may be used, or ethanol which is easily removed after extraction may be used, and may be used alone or in an arbitrary mixture with water.

In addition, additives derived from plant or animal raw materials are
When applied to external preparations and bath preparations such as skin care and hair care, it protects the skin and hair, moisturizes, improves touch and texture, imparts flexibility, relieves irritation, relieves stress by fragrance, rejuvenates cells (cell aging) Prevention), suppression of inflammation, improvement of skin and hair quality, prevention and improvement of rough skin, hair growth, hair growth,
In addition to hair loss prevention, gloss imparting, cleansing effect, relief of fatigue, blood flow promotion, warm bath effect and other cosmetic effects, fragrance, thickening,
Antiseptic, buffer, etc. can be expected.

Further, in addition to the above, various cosmetic and pharmaceutical effects of the raw materials known so far are expected, and by combining them, the intended effect can be enhanced or various effects can be obtained. It is also possible to make products that expect functional effects.

Specific plants (crude drugs) as raw materials include
For example, Ai (Aiba), Aokazura (Seifu Fuji), Aotsu-Juraji (Kibo), Acacia, Akasugi fruit, Akagrape, Akamegashiwa (Akabu Kashiwa), Akane (Akane grass root), Akayajiou (Jihuang), Agi (Awei), Akinire (Roasted skin), akebi
(Kidori), Asa (Jin Asako), Asagao (Toshiko), Ashitaba
(Tomorrow's leaf), Adzuki (red azuki bean), Asenyaku (Asenyaku), Acerola, Anise fruit, Abemaki fruit, Avocado, Ama, Amacha (Amacha), Amadokoro (Tamatake), Amigasa lily (Shellfish), Almond, Altea, Arnica , Aloe (log), aloe vera, apricot (almond jelly), ansokkou (benzuka), Igakozolina (biliary head), knotweed (tiger cane root), strawberry, fig (non-flower fruit) or its leaves, strawberry (winter aoiko),
Itohimehagi (Enshi), carob, rice seed or seed coat,
Inondo seeds, nettle, ylang-ylang, ginkgo (gingko leaves, ginkgo), Ibuki-yakosou, fennel (fenka), ukiyagara (sanryou), turmeric fruit, turmeric
(Utsubane), Usbania Oyster, Usbenita Oyster, Usubasaishin (spicy), Utsubogusa (summer hay), Udo or Shishiudo (Qang activity, independence, Tang Dynasty activity), Ume (Umebai) or its pulp, Vladigashi, Uwaurushi, Unshurikan ( Chen), Estragon, Eleuthero (Ezo Goka), Enoki, Ebisugusa (Keiko), Elderberry fruit, Elemi, Enju
(Gossip, Gossip rice), ogre (Astragalus radiata), Ouren (Orchid), Ookarasuri (Karonin), Ootsu-la-Fuji (self-defense), Psyllium (Carmae, Carmaegrass), Toucan (Haruko), Obananaokera ( White ajutsu), fruit beetle fruit, hawthorn
(Yamako), barley (barley), ogurma (turning over), okra fruit, okera (white jujube), panax ginseng (carrot), hypericum (brother's cut grass), odorikosou (intermittent), onamimi (blue ears),
Origurumi, Oninoyagara (Tianma), Oniyuri (Yuri), Oninos, Halibut (Hihayu), Ominaeshi (defeated), Dutch strawberry, Dutch garashi, Dutch parsley, Dutch honeyspot, olive, oregano, orange fruit or peel,
Kaikei (ripe yellow), seaweed [green algae, brown algae, red algae],
Cacao seeds, oysters or their leaves or their leaves (persimmon), kagikazura (crop), cassia, kasinaki fruit (mushrooms), gajutsu (shadowatsu), kasiwa (shadow tree), cascarilla, kanikusa
(Kin Sato), valerian (Kisokone), pumpkin, kapok-no-ki seed, kahoku sansho (shopper), cattail (kamo yellow), chamomile, kamiyatsude (tsukusa), karasuri (roasted gourd), rasuggi, rasabisaku (midsummer), Guarana seeds, Karaya, Karin (Gourd melon), Kawayanagi, Kawaratake, Kawarayomogi (Inchinko), Kansui (Enzyme), Licorice (Licorice), Candelilla, Kanto, Canna, Raspberry, Kiwi fruit, Kikarasuuri (Ururone) , Kikyo (Kikyo, Kikyo root), Chrysanthemum (Chrysanthemum flower), Catalpa (Azumizumi), Rigid grass (Yotei root), Kizuta, Kidachi aloe, Kidachiha, Kinoki, Yellowfin (yellow),
Kibana Ogi (Garden Radix), Gymnema Sylvesta, Kiraja Saponaria, Kiraya, Cabbage, Cabbage Unripe Fruit, Cucumber, Kumquat Fruit, Kinma, Kinmizuki (Senraku grass), Guayule, Quercus infectria's Insect Gall, Cucuinuts, Wolfberry, lycium, lycium leaves, ground bone bark, cedar crab (tenmon winter), cypress (kuzukone), camphor tree, gooseberry fruit, gardenia (herb gardenia), kunugi (bokusou), kumazasa, kuromatsuzura (horsepoda) , Clara (Bitterfruit), Cranberry fruit, Chestnut or its astringent skin, Curculigo-Latifolia fruit, Grapefruit fruit, Buckthorn, Black squirrel (rescue rescue), Kurobana Hikioko (Enhanced grass), Chlorella, Mulberry (Mulberry leaf, Mulberry bark), Guava fruit, kaygai
(Cow flower, rooster), Keirinsaishin (spicy), laurel,
Gentian, Gennoshoco (Old treasured grass), Cilantro fruit, Koushinbara (Monthly flower), Kosui mint, Kozo fruit, Black tea, Kouhone (Raw bone), Kouhon (Straw and Kara straw),
Koulyang, Cowberry (Koshibachi), Koganebana (Yellow Gon), Kogomebaotogirisou, Coconut fruit, Goshuyu (Gusyuyu), Goshoichigo (covered bonsai), Pepper (pepper), Copaiba balsam, Coffee beans, Kobushi (Spicy), Burdock ( Burdock, burdock), kobotdur, sesame (sesame), sesame cranberry (gensan), wheat (wheat), rice or rice bran (red bran, white bran), cola acuminata seed, cola vera seed, fenugreek fruit, colombo, conzulango , Kombu, Comfrey (Finbari grass), Konjac, Sakisima button dzuru (Wei-sen), cherry blossoms / leaves / fruits / bark (cherry bark), pomegranate, sasa, sasayuri (yuri), sasanqua, sagemodaka (sawaka) ,
Sweet potato, sugar cane, sugar beet, sun jujube (acid jujube), saffron (red safflower, western safflower), pomelo fruit, savonso, salmonberry fruit, sarashinasho (masuma), salvia, sawagkyo (soybean beetle), sakugurumi leaf, sankirai (Yamakoi), Hawthorn (Yamako), Panax ginseng (Samseng carrot), Sanshuyu (sanshuyu), Sansho (Sansho), Sandscon (Yamazone), Cyanoki fruit, Shiitake mushroom, Jio (jihuang), Shion (Shion) , Digitalis, Shikunshi (Kimiko), Shishido (Independent, Tang-do), Shiso, Aodiso, Chirimenjiso, Catamendiso (Shiyoha, Shiso), Shidare-kamba (white birch bark), Rosewood, Shinanoki, Chinese beetle
(Forsythia), Sesame olive (Chrysanthemum flower), Spiraea, Potato, Peony (Shakuyaku), Shajin (Sasan), Janohige
(Wheat gate winter), white birch seed, white walnut butterfly seed, white blossoms, white blossoms, white blossoms, white blossoms, white blossoms, ginger, ginger, ginger, ginger, birch, Cinconas sacyl bra, cinnamon, watermelon (watermelon), honeysuckle (gold and silver flowers, Shinobi winter), sorrel (acid pattern), swimberry fruit,
Strawberry fruit, horsetail (Thorn), stevia, plum fruit, Scots pine cone, pine larch, Scots ivy, Scots walnut, Scots pear fruit, Scots pine, Scots scotch, Scots scotch I, mistletoe, mint,
Horseradish, Sekisho (Iris), Zeniaoi, Senega, Seri, Celery, Senkyu (River Kyu), Senna fruit or leaf, Senninsou (Large Tate), Sembri (Drug), Souka (grass), Buckwheat seed, Somenimo , Rhubarb (Ohio),
Radish, Soybean, Daidai (Orange, Kikomi), Thyme, Takatodai (Daihiki), Takawarabi (Inu), Dark Sweet Cherry Fruit, Tachijakosou (Hyakurika), Tachibana (Tachibana),
Twill willow, tamarind seeds, onion, tamshiba (spicy), tanuki or its root bark, tanjin (dansin), dammar, cherry fruit, tigaya or its root (chinese root), chicory,
Butterfly (cloves, cloves), ginseng (gomiko), ginseng (daisies), ginseng (buoy), ginseng (carrots), artemisia (ginseng), ginseng, ginseng, camellia, camellia, Centrum,
Tsumekusa (lacquer lacustrine), Tsuyukusa (duckling grass), Tsuruazuki (red azuki bean), Tsurudukudami (what's a crow), Tsuruna (apricot), Carrot (four-leaf ginseng), Tsuwabuki, Deiko, Teuchigulumi, Duberry fruit, Tengusa, Tendaiyaku (crow) Medicine), Pepper (winter melon), Pepper (bansho), Touki (Toki), Calendula, Maize or Maize Hair (Nanban Hair),
Scutellaria mochi (Female Sadako), Scutellaria (Ryubile), Dokudami (Juyaku), Tokon (Spot), Tochiban Ginseng (Bamboo Ginseng),
Eucommia (Tonaka, Tonaka leaf), tomato, tragacanth, triacanthus seed, tolmentilla, dronoki, toromallow, Niseria berry fruit, potato (herbal medicine), squid, naginata koju, nazuna, jujube, jujube
(Daijutsu), Naniwaibara (gold cherry), Narco lily (yellow), peanut (peanut), nanten (minamitenmi), nigaki (makinoki), bitter mugwort (bitumen), nikuzuku, nikkei (cinnamon bark),
Chinese chive (Nirako), elderberry (bone-bonded tree), carrot, garlic
(Garlic), nulde (five times), leek, thistle (daiji), wild rose (real fruit), yarrow, Japanese radish (maehu), wild rose, peach, palm, hibiscus (bussouge, fusulin bussouge, roselle), pineapple fruit, hakata lily
(Yuri), Hakamauraboshi (Bone Crushing), Hakusen (White Moss),
Huckleberry fruit, chickweed (red), hazel (haruko), hasidoro (roth root), basil, lotus (lotus, lotus root), parsley, batata, hachiku (bamboo-boiled), patchouli, mint (light-weight, light-weight leaf), adlay (Yokuinin), Hanasuge (grandmother), banana, hanamint, vanilla bins, papaya,
Stilts (rats), habusou, paprika, hamago
(Thorn vines), Hamasuge (Katsutsuki), Hamabishi (Situriko), Hamanas (My rose flower), Hamabou (Hama wind), Hamamelis, Rose (rose), Parietaria, Harunire (Yellow, Yu white bark, Yu leaf) ), Breadfruit, giant forage (sun-dried), lizard ginseng (party), pecan nut, giganbana (stone, garland), cypress (extended life grass), cypress (hishomi), pistachio, beet, hitoshiba (stone reed) , Hinata no Kozuchi (cow knees), Hiba, Castor, Sunflower, Bell pepper, Himegama (Kaba), Himematsutake, Pimenta fruit, Hiyu fruit, Belodo oyster, Hiroha okinagusa (Hakuto Okina), Hirohase nega
(Senega), loquat (loquat, loquat leaf), betel nut (large belly skin, betel loquat), carp squash (southern wisteria), butterbur, butterbur poppy (winter flower, winter leaf), fujibakama (lanca), fuji bean (flat bean),
Butcher bloom, grape skin or fruit, beech, eucommia mushroom (Cordyceps sinensis), Brazilian liquorice, black currant fruit, blackberry fruit, plum fruit, furcellaria, blueberry fruit, prune, blonde psyllium, bundou (green bean), loofah, Safflower
(Safflower), belladonna, berry fruit, boysenberry fruit, boufu (windbreak), spinach, physalis (Torone), honoki (koboku, Japanese gopaku), bokeh (gourd), hosobaokera (sojutsu), hosobabarengiku, bodaiju, button
(Peony skin), hop, jojoba, white berry fruit, Hong apricot (almond jelly), Hong shimeji, Meizurutennanshaw
(Tiannan star), Ephedra (mao), Macadamia nut, Macri
(Sea grass), magwa (mulberry leaf, mulberry bark), medake (bamboo-boiled), matabi (mokuten tate), matsukasa, matsuhodo (bukuryo), marigold, malvanojazine (alpin ginseng), mulberry fruit, quince, Marronnier, Mango, Mangosteen, Mansugurumi, Mandarin fruit, Mannentake (Lingzhi), Mannenrow, Citrus fruit (Kikomi), Mishimasaiko (Saiko), Mizokakushi (Hanbe lotus), Misohagi (Chisatsuna), Mitsugashiwa, Honey bee, honey bee maggot (vine thorns), green peppermint, mimosa, mioka, miracle fruit fruit, myrrh, mirobaran, mukuge
Murasaki (purple root), Murasaki corn, swordfish (mother grass), mebuki, melaleuca, melissa, melilot, melon fruit, sagebrush, mosouchikku, magnolia (spicy), mokoko (tree incense), maple fruit, peach fruit, seeds ) Or leaves (peach leaves), sprouts, morello cherry fruits, moroheiya, yakawamurasakiimo, yakuchi (masuti), cornflower, cornflower, cornflower,
Yashabushi (arrow wheel), yachiyanagi, yatsude (octagonal gold plate),
Mistletoe (willow parasite), willow leaf, yabugarashi, yabukouji (purple gold beef), pokeweed (commercial land), yamanoimo (yakuyaku), yamahanoki (yamaharu), yamamomo (yangbai skin), eucalyptus, yucca brevifolia, yukinoshita (Tiger eargrass), Yuzu fruit, lily, mugwort (Aiba leaf), yogurusa, lime fruit, peanut, lakanka fruit, raspberry fruit, lavender, longan (longan meat), green tea, apple fruit, rubus
Suavisimus, lettuce, red currant fruit,
Lemon fruit, lemongrass, forsythia, astragalus, wax palm, loganberry fruit, rosehip,
There are rosemary, Roman chamomile, seaweed, wasabi, waremokou (chiyu).

Materials derived from animal raw materials include cockscomb extract, bovine / human placenta extract, swine / cattle stomach, duodenum or intestinal extract or its degradation product, water-soluble collagen, acylated collagen and the like. Collagen derivatives, collagen hydrolysates, elastin, elastin hydrolysates,
Water-soluble elastin derivative, keratin and its degradation products, silk protein and its degradation products, porcine and bovine hemocyte protein degradation products (globin peptide), porcine and bovine hemoglobin degradation products (hemin, hematin, heme, protohem, heme iron, etc.) ,milk,
Casein hydrolyzate, skim milk powder and its decomposition products, chicken egg, fish meat and its decomposition products, etc.

[14] Microbial culture metabolites Yeast metabolites, yeast extract, rice ferment extract, rice bran extract, euglena extract, lactic acid fermentation of skim milk powder, etc.

[15] α-hydroxy acid Glycolic acid, citric acid, malic acid, tartaric acid, lactic acid and the like.

[16] Inorganic pigments Silicic anhydride, magnesium silicate, talc, kaolin,
Bentonite, mica, titanium mica, bismuth oxychloride, zirconium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, yellow iron oxide, red iron oxide, black iron oxide, gunjou, chromium oxide, chromium hydroxide, carbon black, calamine and the like.

[17] Ultraviolet absorber p-aminobenzoic acid derivative, salicylic acid derivative, anthranilic acid derivative, coumarin derivative, amino acid compound,
Benzotriazole derivatives, tetrazole derivatives, imidazoline derivatives, pyrimidine derivatives, dioxane derivatives, camphor derivatives, furan derivatives, pyrone derivatives,
Nucleic acid derivatives, allantoin derivatives, nicotinic acid derivatives,
Vitamin B6 derivatives, oxybenzone, benzophenone, guaiazulene, shikonin, baicalin, baicalein, berberine and the like.

[18] Astringent Lactic acid, tartaric acid, succinic acid, citric acid, allantoin, zinc chloride, zinc sulfate, calamine, zinc p-phenolsulfonate, aluminum potassium sulfate, resorcinol, ferric chloride and the like.

[19] Antioxidants ascorbic acid and its salts, stearic acid ester, tocopherol and its ester derivatives, nordihydroguaseletenic acid, butylhydroxytoluene (BHT),
Butylhydroxyanisole (BHA), parahydroxyanisole, propyl gallate, sesamol, sesamolin, gossypol and the like.

[20] Anti-inflammatory agent Ictamole, indomethacin, kaolin, salicylic acid, sodium salicylate, methyl salicylate, acetylsalicylic acid, diphenhydramine hydrochloride, d or dl-
Camphor, hydrocortisone, guaiazulene, camazulene, chlorpheniramine maleate, glycyrrhizic acid and its salts, glycyrrhetinic acid and its salts and the like.

[21] Disinfectant / Disinfectant Acrinol, sulfur, benzalkonium chloride, benzethonium chloride, methylrosaniline chloride, cresol, calcium gluconate, chlorhexidine gluconate, sulfamine, mercurochrome, lactoferrin or a hydrolyzate thereof.

[22] Fragrance Natural animal flavors such as musk, civet, castorium, ambergris, anise essential oil, angelica essential oil, ylang-ylang essential oil, iris essential oil, fennel essential oil, orange essential oil, cananga essential oil, caraway essential oil, cardamom essential oil, Guayakwood essential oil, cumin essential oil, black letter essential oil, cinnamon essential oil, cinnamon essential oil, geranium essential oil, copaiba balsam essential oil, coriandel essential oil, perilla essential oil, cedarwood essential oil, citronella essential oil, jasmine essential oil, ginger grass essential oil, cedar essential oil, spearmint essential oil, western Mentha essential oil, Great Fengxiang essential oil, Tuberose essential oil, T-shaped essential oil, Orange flower essential oil, Winter green essential oil, Truval sam essential oil, Batturi essential oil, Rose essential oil, Palmarosa essential oil, Cypress essential oil, Hiba essential oil,
Sandalwood essential oil, Petitgren essential oil, Bay essential oil, Vetiva essential oil, Bergamot essential oil, Peruvian balsam essential oil, Boad rose essential oil, Camphor essential oil, Mandarin essential oil, Eucalyptus essential oil, Lime essential oil, Lavender essential oil, Linaloe essential oil, Lemongrass essential oil, Lemon essential oil, Rosemary Vegetable flavors such as essential oils and Japanese peppermint essential oils, and other synthetic flavors.

[23] Dyes / colorants Red cabbage dye, red rice dye, madder dye, anato dye, squid dye, turmeric dye, ende dye, krill dye, persimmon dye, caramel, gold, silver, gardenia dye, corn dye , Onion pigment, tamarind pigment, spirulina pigment, buckwheat whole plant pigment, cherry pigment, laver pigment, hibiscus pigment, grape juice pigment, marigold pigment, purple potato pigment, purple yam pigment, lac pigment, etc.

[24] Sweeteners Sugar, sweet tea, fructose, arabinose, galactose, xylose, stevia, mannose, maltose, honey, glucose, miraculin, monelin, licorice extract and the like.

[25] Nutrition fortifier Shell calcined calcium, cyanocorabamine, yeast, wheat germ, egg yolk powder, hemicellulose, etc.)

[26] Other humectants, hormones, sequestering agents, pH adjusters,
Chelating agents, preservatives / antibiotics, cooling agents, stabilizers, emulsifiers, animal / vegetable proteins and their degradation products, animal / vegetable polysaccharides and their degradation products, animal / vegetable glycoproteins and their degradation products, Blood flow enhancers, anti-inflammatory agents / anti-allergic agents, cell activators, keratolytic agents, wound treatment agents, foam enhancers, thickeners, deodorants
Deodorants, enzymes, and the like are used, and additive and synergistic effects can be expected when used in combination therewith.

[0051]

[Examples] Inhibitory effect of active oxygen expression was examined by the NBT method. (Test method) 3.4 mL of 0.05 M sodium bicarbonate buffer (pH = 10.2) in a sample tube, 0.75 mM nitro blue tetrazolium (NBT), 0.15 ^W / _V % bovine serum albumin, and a sample solution (target is purified water only) ) 0.2 mL, 1 mL of 2.5 mg / mL metal compound suspension is added, and ultraviolet rays (Toshiba FL-20
Three SE lamps and three FL-20SBL lamps are arranged in parallel,
(Irradiation at a distance of 15 cm) for 45 minutes, and it was observed that NBT reacts with active oxygen generated by ultraviolet rays to develop a blue color.

(Test Results) The results are shown in the following table (Table 1). The concentration of each sample is a value shown as the content contained in the system. The numerical value of the NBT coloring degree was 5 when the color was recognized as a blue color, and was 0 when there was no change, and the intermediate discoloring degree was divided into 1 to 4.

[Table 1]

[0053]

EXAMPLES Inhibition of lipid peroxidation It has been known that the peroxidation of lipids is promoted by ultraviolet rays. The presence of titanium dioxide or zinc oxide in such systems will alter the degree of lipid peroxide production, and will inhibit lipid peroxidation when additional phenolic compounds are added to the system. For the purpose of examining this, evaluation was made by the TBA method. (Test method) Linolenic acid was suspended in a 0.8% SDS (sodium dodecyl sulfate) solution to a concentration of 0.1%, and 3.9 mL of this solution was mixed with 0.1 mL of a sample and 1 mL of a 1% aqueous zinc oxide suspension for testing. Liquid. The test solution was irradiated with ultraviolet rays (three FL-20SE lamps and three FL-20SBL lamps manufactured by Toshiba in parallel, irradiation at a distance of 15 cm) for 2 hours, and 1 mL of this solution was added to 4.5% BHT (butylhydroxytoluene). ) Transfer to a centrifuge tube containing 0.02 mL, and add 0.67% TBA
(Thiobarbituric acid) / 15% acetic acid aqueous solution (pH = 3.5) 1
mL was added and heated at 95 ° C. for 1 hour. After cooling, 4 mL of a 15% methanol-containing n-butanol solution was added, and the mixture was shaken well, centrifuged, and the absorbance at 532 nm of the n-butanol layer was measured to determine the amount of lipid peroxide. Similarly, the amount of lipid peroxide was measured without UV irradiation, and the difference from the irradiated amount was defined as the amount of lipid peroxide produced.

(Test Results) The results are as shown in the following figure (FIG. 1).

FIG.

[0055]

EXAMPLES Preparation of various external preparations Various UV protection agents according to the present invention were prepared. The formulation examples are shown below, but the UV protective agent according to the present invention is not limited to these.

1) Example of manufacturing sunscreen emulsion The sunscreen emulsion was manufactured according to the following formulation. % By weight Stearic acid 2 2. 2. Self-emulsifying glyceryl monostearate 1 Cetanol 14 Dimethylpolysiloxane 2 5. p-Aminobenzoic acid 26. Liquid paraffin 2 7. Triethanolamine 1 8.1,3-butylene glycol 2 9 Titanium dioxide 5 10. Bentonite 0.5 11. Tannin powder extracted and purified from gallic 0.5 13. Hydrolyzed silk solution (solid content 1%) 1 14. Purified water 100 residue

2) Production Example of Water-Dispersible Whitening Powder The following was prepared according to the following formulation. % By weight Zinc oxide 10 2. Magnesium carbonate 3 3. Black iron oxide appropriate amount 4. Glycerin 7 5. Tannin-containing powder extracted and purified from Gotobiko 1 6. Collagen solution 1 7 Purified water 100 residue

3) Production Example of Aqueous Suspension Type Eyeliner It was produced according to the following formulation. % By weight Acrylic resin alkanolamine salt 4 2. Bentonite 5% dispersion 40 3.1,3-butylene glycol 7 4. Polyvinyl alcohol 2.5 5. Black iron oxide 15 6. Titanium dioxide coated mica 2 7. 7. Green tea extracted flavonoid tannin-containing liquid (solid content 1%) 1 Purified water 100 residue

4) Production example of emulsified cream eyeshadow The emulsion eyeshadow was produced according to the following formulation. % By weight Stearic acid 4 2. 2. Self-emulsifying glyceryl monostearate 3 Vaseline 8 4. Isopropyl myristate 5 5. Squalane 5 6. Triethanolamine 0.5 7.1 1,3-butylene glycol 5 8. Titanium dioxide coated mica 7 9. Kaolin 2 10． Hamamelis hydroalcoholic extract (solid content 1%) 1 11. Purified water 100 residue

5) Production Example of Cream Foundation The cream foundation was produced according to the following formulation. % By weight Stearic acid 4 2. Glycerin monostearate 3 3. Cetanol 14 Isopropyl myristate 5 5. Liquid paraffin 10 6. Sarah beeswax 3 7. 7. Hydroxyethyl chitosan solution (1% solid content) Triethanolamine 1 9 Glycerin 3 10. Bentonite 1 11． Titanium dioxide 8 12. Zinc oxide 3 13. Quercetin 0.2 14. Gallic acid 0.2 15. Asen Yakuhin 10% butylene glycol extract (solid content 1%) 2 16. Shakuyaku 20% butylene glycol extract (1% solid content) Purified water 100 residue

6) Production Example of Solid Foundation The foundation was produced according to the following formulation. % By weight Serisite 40 2. Titanium dioxide 5 3. Titanium dioxide coated mica 5 4. Mica 16 3. Nylon powder 6 4. Talc 15 5. Liquid paraffin 10 6. Vaseline 1.5 7. 7. A powder containing persimmon extracted tannin 0.5 Five-fold extract purified tannin 1

7) Production Example of Sunscreen Cream The sunscreen cream was produced according to the following formulation. % By weight Liquid paraffin 30 2. Lanolin 5 3. Cetanol 5 4. Stearic acid 3 5. Self-emulsifying glyceryl monostearate 3 6. Titanium dioxide 5 7. Glycerin 3 8.1,3-butylene glycol 2 9 10. 10% butylene glycol extract of tomorrow leaves (solid content 1%) Water extract of genoshoko (1% solid content) 1 11. 1 20% butylene glycol extract of tiger ear grass (1% solid content) Gallic acid 0.1 13. Japanese Pharmacopoeia tannin 0.5 14. Purified water 100 residue

[0063]

Example: Use test of external preparations For the test, a UV-prevention cream with a simple formulation was prepared, and volunteers (7) who had not tanned had to try and use each one day. . The next day, I tried a questionnaire for volunteers. (Prescription of cream) Stearic acid (2 parts by weight), self-emulsifying glyceryl monostearate (1), liquid paraffin (20), 1,3-butylene glycol (2), titanium dioxide (2), zinc oxide (2 ), Tannin extracted and purified from Gobiko (0.5), Purified water (residual weight of 100 parts by weight) (Test environment) Sunny: Volunteers enjoying sunbathing in the pool or sea for the first time this summer (5 people) Sunny: Daytime, outdoors Volunteers wash their own car at (2 people) (Test method) All volunteers shall set the test area from shoulder to wrist, and the test area shall be exposed to sunlight. The left side of the test section is rubbed with the cream of the above-mentioned formula, and the right side of the cream is rubbed with an equal amount of tannin excluding the quintan extract tannin, and each time is spent. During the test, use of the test cream is free under the same conditions in the left and right test sections. Water can be freely entered, but when it comes out of the water, cream must be applied to both the left and right test plots.

(Questionnaire results) The results are shown in the following table (Table 2).

[Table 2]

[0065]

The ultraviolet protective agent according to the present invention comprises titanium dioxide and zinc oxide, which have an excellent ultraviolet scattering effect, similarly to the conventional ones. However, even in such a system, when it receives ultraviolet rays, it has the characteristic that the expression of active oxygen itself is not recognized, which is not present in conventional products. Active oxygen generated in an environment that is not controlled by the living body can be excessive for the living body,
In applications such as cosmetics which are used repeatedly and continuously over a long period of time, there is a concern that they may affect the skin. It exhibits the same ultraviolet protection effect as the conventional one, and can be used safely even when applied for a long time.

[Brief description of the drawings]

FIG. 1 is a graph showing the change in the amount of lipid peroxide produced due to the presence of zinc oxide and the inhibitory effect of a phenolic compound.

Claims (2)

[Claims] 1. Titanium dioxide, mica coated with titanium dioxide,
An ultraviolet ray protective agent characterized by containing one or more selected from zinc oxide and a phenolic compound. 2. The ultraviolet protective agent according to claim 1, wherein the phenolic compound is tannin.