JP3340878B2 - Tyrosinase inhibitors, whitening cosmetics and anti-tarnish agents - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[Industrial applications]

The present invention provides a tyrosinase inhibitor effective for preventing the production of melanin pigment, a cosmetic product having a whitening effect, and
The present invention relates to a discoloration inhibitor for foods and the like that are easily discolored by tyrosinase.

[0002]

[Prior art]

Tyrosine, a type of amino acid, produces a dark brown or reddish brown pigment or melanin by the action of tyrosinase, causing spots and freckles on the skin, mushrooms, crustaceans,
It may cause foods such as fruits and vegetables to turn brown. Therefore, in order to prevent the production of melanin by the above mechanism, various substances capable of inhibiting the action of tyrosinase have been conventionally used or proposed in the fields of cosmetics and foods. Typical ones are ascorbic acid, sulfurs, hydroquinone, kojic acid, natural plant extracts and the like.

[0003] However, ascorbic acid has a problem in terms of stability when moisture is present, and sulfur has a problem in terms of odor. Hydroquinone has the drawback of being highly effective but highly toxic. Kojic acid and natural plant extracts have high safety but weak tyrosinase inhibitory activity, and many plant extracts have problems in taste, smell, color and the like.

[0004]

[Problems to be solved by the invention]

In recent years, with the growing public interest in the safety of foods and cosmetics that have a major impact on health maintenance, tyrosinase inhibitors used to prevent the production of melanin have
There has been a strong demand for highly safe natural products which do not adversely affect the quality of the additives in terms of taste and smell, and which can be widely used in cosmetics and foods. An object of the present invention is to provide a novel tyrosinase inhibitor that can meet such a demand.

[0005]

[Means for Solving the Problems]

The present invention provides a tyrosinase inhibitor comprising, as an active ingredient, an extract obtained by subjecting a tamarind husk to an extraction treatment with water, a hydrophilic organic solvent, or a mixture thereof.

The present invention also provides a whitening cosmetic and a food discoloration inhibitor containing the tyrosinase inhibitor according to the present invention.

[0007] It has been found that the tamarind husk extract using the above-mentioned extraction solvent contains condensed tannins in which catechin is condensed, which exhibits an excellent tyrosinase inhibitory action.

[0008] Tamarindus (Tamarindus indica L.) is a legume that has a height of 25 m or more. The polysaccharide obtained from the endosperm portion of the seed is called tamarind gum and is widely used as a thickener in food production. The tamarind husk is a part of a hard seed coat discarded when producing this tamarind gum, and a part thereof is conventionally used as a raw material for producing tannin.

In order to obtain an extract having a tyrosinase inhibitory action from a tamarind husk, the tamarind husk is appropriately pulverized and then subjected to an extraction treatment using water, a hydrophilic organic solvent or a mixture thereof. As the hydrophilic organic solvent for extraction, lower alcohols such as methanol and ethanol, polyhydric alcohols such as glycerin and 1,3-butylene glycol, and acetone are particularly suitable. The extraction method is not particularly limited, and the active ingredient can be easily extracted by immersion in a solvent maintained at a normal temperature or a temperature near the boiling point.

[0010] The extract obtained by distilling off the solvent from the extract can be used as it is as a tyrosinase inhibitor. However, a purification treatment for deodorization, decolorization, etc. is performed within a range that does not adversely affect the tyrosinase inhibitory action. May be applied. Furthermore, it can be used as a more active tyrosinase inhibitor by subjecting it to separation and purification treatment such as liquid-liquid partition extraction, various types of chromatography, ion exchange, and membrane separation.

[0011] The tyrosinase inhibitor of the present invention is highly safe from a part of a plant used in the production of food additives, and is therefore used in cosmetics, food, feed for fish and shellfish, etc. It can be blended or used for food processing. That is, it can be used to form cosmetics having a whitening effect when incorporated into cosmetics, and can also be incorporated into feeds for cultivating fish and shellfish to prevent sunburn of fish and shellfish. In addition, in order to prevent discoloration of food which is liable to be discolored due to the production of melanin, it can be added to the food or used for surface treatment.

Representative examples of the use as a discoloration inhibitor for foods include crabs,
It is a method for preventing browning of crustaceans such as shrimps and mushrooms such as mushrooms and shiitake mushrooms. A remarkable discoloration preventing effect can be achieved only by attaching a dilute solution to the surface by a method such as immersion or spraying. When used as a discoloration inhibitor for foods, the tyrosinase inhibitor of the present invention may be diluted with an arbitrary medium to prepare a liquid preparation or a powdery preparation.

The preferred amount of the tyrosinase inhibitor of the present invention varies depending on the type of the substance to be added, but is preferably about 0.1 when an unpurified tamarind husk extract having an average tyrosinase inhibitory activity is used. 005 to 10.0% by weight, preferably 0.01 to 1.0% by weight.

[0014] The tyrosinase inhibitor of the present invention can be used alone for the above-mentioned applications, or can be appropriately used in combination with any food processing agent or additive, a constituent material for cosmetics, and the like.

For example, when used in the food field, the tyrosinase inhibitor of the present invention can be used in combination with any discoloration inhibitor, antibacterial / preservative, etc. May bring. Specific examples of the cases where the combined use produces a preferable result are as follows.

Discoloration inhibitor: polyphosphoric acid or its salts, metaphosphoric acid or its salts, pyrophosphoric acid or its salts, citric acid or its salts, aluminum potassium sulfate, erythorbic acid or its salts, phytic acid, kojic acid, oil-soluble liquorice extract.

Antibacterial and preservatives: benzoic acid or salts thereof, orthophenylphenol or salts thereof, diphenyl, sorbic acid or salts thereof, thiabendazole, dehydroacetic acid or salts thereof, alkyl paraoxybenzoates,
Propionic acid or its salts, bleaching powder, hypochlorous acid or its salts, fumaric acid, ε-polylysine, glycine,
Lysozyme, Anise Extract, Shirako Protein (Protamine), Hinoki Extract (Hinokitiol), Clove Extract, Sage Extract, Propolis Extract, Pepper Extract, Fig Leaf Extract, Oregano Extract, Cardamom Extract, Caraway Extract, Citrus Seed Extract, Cumin Extract, Mulberry Extract, Caffeine Extract, Sasa Extract, Saffron Extract, Sansho Extract, Perilla Extract, Cinnamon Extract, Ginger Extract, (willow) Polygonum Extract, Thyme Extract, Turmeric Extract, Soybean Extract (Lecithin), Pepper Extract, Nutmeg Extract, Garlic Extract, Basil Extract, peppermint extract, vanilla extract, paprika extract, grape peel extract, Benijakoji decomposition product,
Peppermint extract, hop extract, marjoram extract, mace extract, moso bamboo extract, firgar extract, eucalyptus extract, yucca extract, wasabi extract and the like.

Antioxidants: d-α-tocopherol, ascorbic acid, B
HA, BHT, gallic acid, ryocha extract (catechin, tannin), rosemary extract, rice bran enzyme decomposition product and the like.

When a whitening effect is used in cosmetics, the tyrosinase inhibitor of the present invention is more astringent, bactericidal / antibacterial, whitening, and ultraviolet absorber than when it is used alone in a cosmetic base to form a cosmetic. , Moisturizer, cell activator, anti-inflammatory / antiallergic agent, antioxidant / active oxygen scavenger, etc. It can be used as a cosmetic. In such a case, the synergistic action between the active ingredient and the other active ingredient used in combination may bring about an excellent use effect more than expected.

Specific examples of the cosmetic component that can be used in combination with the tyrosinase inhibitor of the present invention are as follows. Astringents: citric acid or its salts, tartaric acid or its salts, lactic acid or its salts, aluminum chloride, aluminum potassium potassium sulfate, allantochlorohydroxyaluminum, allantoindihydroxyaluminum,
Zinc paraphenolsulfonate, zinc sulfate, japonicus extract, age extract, hamamelis extract, gennoshoko extract, chacatechins, gypsophila extract, sycamore extract, hypericum extract, rhubarb extract, cornflower extract, horsetail extract, kizuta extract, cucumber extract, malonier extract, salvia extract,
Melissa extract and the like.

Bactericidal and antibacterial agents: benzoic acid, sodium benzoate, paraoxybenzoate, distearylmethylammonium chloride, benzethonium chloride, alkyldiaminoethylglycine chloride solution, chlorhexidine hydrochloride, orthophenylphenol, photosensitive element 101, photosensitive element No. 201, salicylic acid, sodium salicylate, sorbic acid, halocarban, resorcin, parachlorophenol, phenoxyethanol, bisabolol, hinokitiol, menthol, chitosan, chitosan hydrolyzate, zhuyu extract, kujin extract, enmeiso extract, loquat extract, uwaurushi extract, hop extract, Yucca extract, aloe extract, cinnamon extract, zedoary extract, etc.

Whitening agent: ascorbic acid and its derivatives, sulfur, placenta extract, kojic acid and its derivatives, glucosamine and its derivatives, azelain and its derivatives, arbutin and its derivatives, hydroxycinnamic acid and its derivatives, glutathione and arnica extract , Scutellaria extract, Sengoku extract, Sohakuhi extract, Psychoextract, Boufu extract, Hamabofu extract, Mannaketake mycelium culture or extract thereof, Gymnema extract, Shinanoki extract, Peach leaf extract, Aegitsu extract, Kujin extract, Jiyu extract, Touki extract, Yokuinin Extract, oyster leaf extract, rhubarb extract, peanut extract,
Hamamelis extract, Marronnier extract, Hypericum perforatum extract, Limeflower extract, oil-soluble licorice extract (hydrophobic flavone, glabridine, grabrene, lycochalcone A).

UV absorbers: β-isopropylfuranone derivative, urocanic acid, ethyl urocanate, oxybenzone, oxybenzonesulfonic acid, tetrahydroxybenzophenone, dihydroxydimethoxybenzophenone, dihydroxybenzophenone, sinoxate, methyl diisopropylcinnamate, octyl methoxycinnamate, paraamino Glyceryl benzoate, amyl paradimethylaminobenzoate, octyl paradimethylbenzoate, paraaminobenzoic acid, ethyl paraaminobenzoate, butylmethoxydibenzoylmethane, titanium oxide, β-carotene, γ-oryzanol, rice bran extract, aloe extract, birch extract , Birch extract, chamomile extract, black beetle extract, hawthorn extract, henna extract, butterfly Mi extract, horse chestnut extract, ginkgo leaf extract,
Chamomile extract, hawthorn extract, oil-soluble liquorice extract and the like.

Humectants: serine, glycine, threonine, alanine, collagen, hydrolyzed collagen, hydronectin, fibronectin, keratin, elastin, royal jelly, chondroitin heparin, glycerophospholipid, glyceroglycolipid, sphingolipid, sphingolipid,
Linoleic acid or its esters, eicosapentaenoic acid or its esters, pectin, alge colloid,
Bifidobacterium fermented product, lactic acid fermented product, yeast extract, litchi mycelium culture or extract thereof, wheat germ oil, avocado oil, rice germ oil, jojoba oil, soybean phospholipid, γ-oryzanol, below-oil oyster extract, yoquinin extract , Jiaogu extract, Tissou extract, Kaisou extract, Kidachi aloe extract, Burdock extract, Maronie extract, Mannen wax extract, Arnica extract, Wheat bran, Rice bran extract and the like.

Cell activator: riboflavin or a derivative thereof, pyridoxine or a derivative thereof, nicotinic acid or a derivative thereof,
Pantothenic acid or a derivative thereof, α-tocopherol or a derivative thereof, arnica extract, carrot extract, rape ginseng extract, eleuthero extract, loofah extract (saponin), sicon extract, birch extract, psyllium extract, peanut extract, peony extract, mukuroji extract, safflower extract , Ashitaba extract, Loquat leaf extract, Hikikoshi extract, Sakinoshita extract, Huangyi extract, Salvia extract, Garlic extract, Mannen wax extract and the like.

Anti-inflammatory and anti-allergic agents: azulene, allantoin, aminocaproic acid, indomethacin, lysozyme chloride, epsilon aminocaproic acid, oxybenzone, glycyrrhizic acid or its derivatives, glycyrrhetinic acid or its derivatives, photosensitive element 301, photosensitive element 401, hydrochloric acid Diphenhydramine, tranexamic acid or a derivative thereof, adenosine phosphate, estradiol, esulone, ethinyl estradiol, cortisone, hydrocortisone, prednisone, progesterone, corticosterone, arnica extract, cinchin extract, sanshishi extract, juya extract, horse chestnut extract, licorice extract , Touki extract, Artemisia extract, Warmoko extract, Gentian extract, Psycho extract, Senkyu extract, Bow Fuyu extract, Yarrow extract, Spinach extract, Perilla extract, etc.

Antioxidant / active oxygen scavenger: dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate,
Baicalin, baicalein, superoxide dismutase, catalase, rosemary extract, melissa extract, pentagon extract, age extract, loquat leaf extract, hop extract, hamamelis extract, peony extract, sage extract, kina extract, chamomile extract, perilla extract, ginkgo leaf extract, Eucalyptus extract, thyme extract, cardamom extract, caraway extract, nutmeg extract, mace extract, laurel extract, clove extract, turmeric extract, willow extract, etc.

[0028] Cosmetics having a whitening effect include oils, surfactants, humectants, preservatives, fragrances, water, alcohol, thickeners, coloring agents, and the like.
Emulsions, lotions, creams, jellies, packs, etc. are processed by the usual methods used for general raw materials used in cosmetics production.
In producing various cosmetics, the cosmetics can be produced by adding the tyrosinase inhibitor of the present invention at any stage of the production process. By blending the tyrosinase inhibitor of the present invention, selection of other raw materials for producing cosmetics is hardly restricted, and any of the general cosmetic base materials and auxiliaries as exemplified below can be used.

Oils and fats: soybean oil, linseed oil, tung oil, sesame oil, nuka oil,
Cottonseed oil, rapeseed oil, safflower oil, corn oil, olive oil, camellia oil, almond oil, castor oil, peanut oil, cocoa oil, mocro, palm oil, palm kernel oil, tallow, mink oil, egg yolk oil, jojoba oil

Waxes: carnauba wax, candelilla wax, beeswax,
Salami beeswax, whale wax, celax, lanolins

Hydrocarbons: liquid paraffin, petrolatum, microcrystalline wax, ceresin, squalane, polyethylene powder

Fatty acids: stearic acid, linoleic acid, lauric acid, myristic acid, palmitic acid, hevenic acid, lanolinic acid,
Oleic acid, undecylenic acid, isostearic acid

Alcohols: lauryl alcohol, cetyl alcohol, stearyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, oleyl alcohol, hexadecyl alcohol, 2-octyldodecanol, glycerin,
Sorbitol, propylene glycol, 1,3-butylene glycol, ethylene glycol and its polymers, glucose, sucrose, cholesterol, phytosterol, cetostearyl alcohol

Esters: decyl oleate, butyl stearate,
Myristyl myristate, hexyl laurate, isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyldecyl dimethyloctanoate, propylene glycol dioleate, diethyl phthalate, propylene glycol monostearate,
Ethylene glycol monostearate, glyceryl monostearate, glyceryl trimyristate, lanolin acetate, cetyl lactate

Surfactants: anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant Fragrance: menthol, carvone, eugenol, anethole, peppermint oil, spearmint oil, Peppermint oil, eucalyptus oil, anise oil

[0036]

【Example】

Hereinafter, the present invention will be described with reference to examples. Incidentally, IC ₅₀ was used to indicate the tyrosinase inhibitory activity in Example 1 is a numerical value determined by the following method, as this number is less strong tyrosinase inhibitory activity.

Measurement method of tyrosinase inhibitory activity: 0.5 ml of a 0.05% tyrosine solution to which a tyrosinase inhibitor was added, 0.7 ml of a tyrosinase solution (60 μg / ml) and a 1/15 M phosphate buffer (p
H6.8) 1.8ml was mixed well and allowed to react for 1 hour at 37 ° C., the absorbance is measured A ₁ in 475 nm. Absorbance A ₁
Is proportional to the concentration of a group of coloring components such as melanin generated from tyrosine. The same operation was performed for the case where no tyrosinase inhibitor was added, and the absorbance A ₀ at 475 nm was measured.
The tyrosinase inhibition rate is calculated from the following equation.

Tyrosinase inhibition rate (%) = (1-A ₁ / A ₀ ) × 100
The above-mentioned inhibition rate is measured by changing the sample concentration stepwise, and the sample concentration at which the inhibition rate is 50% is determined by an interpolation method, and is defined as IC ₅₀ .

Example 1 100 g of crushed tamarind husk was extracted with 1000 extraction solvents.
The solution is immersed in 50 ml and left at 50 ° C. for 24 hours to extract soluble components. Thereafter, the obtained extract is concentrated to dryness under reduced pressure. The extraction solvent was changed, and the above-mentioned 10 extraction operations (including comparative examples) were performed, and the tyrosinase inhibitory activity of the obtained dried extract was examined. Table 1 shows the results. The mixing ratio of water and the organic solvent when using a mixed solvent is a volume ratio.

[0040]

Table 1 Tyrosinase inhibitory activity of Tamarind Husk extract Extraction solvent Extraction yield (% by weight) IC ₅₀ (μg / ml) Water / methanol mixture (1/1) 19 190 Water 9 1000 Ethanol 23 160 Methanol 22 100 Water Water / ethanol mixture (1/1) 18 130 Water / ethanol mixture (1/4) 23 80 Acetone 21 100 Water / acetone mixture (1/1) 20 150 Methylene chloride Example) 0.4> 1000

Example 2 The following ingredients were uniformly emulsified by a conventional method for producing a cream to produce a vanishing cream having a whitening effect. Stearic acid 10 parts by weight Stearyl alcohol 4 Butyl stearate 8 Potassium hydroxide 0.4 Glycerin monostearate 2 Propylene glycol 10 Glycerin 8 Fragrance 0.1 Preservative / antioxidant 0.1 Tamarind husk extract 0.2 Purified water To make the total amount 100 parts by weight. (Tamarind Husk extract: ethanol extract of Example 1)

Example 3 The following ingredients were homogenized by a conventional method for producing cream,
A neutral cream having a whitening effect was produced. Stearic acid 2 parts by weight Stearyl alcohol 7 Reduced lanolin 2 Squalane 5 Octyldodecanol 6 Polyexethylene cetyl ether 3 New oil type glyceryl monostearate 2 Fragrance 0.1 Preservative / antioxidant 0.1 Propylene glycol 5 Tamarind husk extraction Product 1 Make the total amount 100 parts by weight with purified water. (Tamarind Husk extract: methanol extract of Example 1)

Example 4 The following ingredients were uniformly emulsified by a conventional method for producing an emulsion.
An emulsion having a whitening effect was produced. Stearic acid 2 parts by weight Cetanol 1.5 Vaseline 3 Lanolin alcohol 2 Liquid paraffin 10 Polyoxyethylene monooleate 2 Fragrance 0.1 Preservative / antioxidant 0.1 Glycerin 3 Propylene glycol 5 Triethanolamine 1 Tamarind husk extraction Product 0.01 Make up to 100 parts by weight with purified water. (Tamarind Husk extract: ethanol extract of Example 1)

The following whitening effect test was performed on the above emulsion and the comparative emulsion prepared in the same manner as above except that the tamarind husk extract was not blended. Test method: 15 women aged 20 to 45 years sun-tanned by sunbathing for 1 hour and 3 days a day as panelists, washed the above emulsion on one of the washed left and right forearm flexors and the comparative emulsion on the other. Each of them was applied at least once daily for three months, and finally the skin condition was evaluated according to the following criteria.

◎: Sunburn, spots and freckles were almost inconspicuous and remarkably improved. ：: Sunburn, spots and freckles were reduced. X: There was almost no change. Table 2 shows the test results.

[0046]

[Table 2] Whitening effect of emulsion containing Tamarind Husk extract

Example 5 The following ingredients were uniformly emulsified by a conventional method to produce a W / O emulsified cream foundation having a whitening effect. Sericite 5.4 parts by weight Kaolin 4.0 Titanium dioxide 9.3 Bengala 0.4 Yellow iron oxide 0.8 Black iron oxide 0.15 Liquid paraffin 5.0 Decamethylcyclopentanesiloxane 12.0 Polyoxyethylene-modified dimethyl Siloxane 4.0 1.3-butylene glycol 5.0 Dispersant 0.1 Stabilizer 2.0 Fragrance 0.2 Tamarind Husk extract 0.5 Make up to 100 parts by weight with purified water. (Tamarind Husk extract: acetone extract of Example 1)

Example 6 Ten live shrimp were killed in a refrigerator at 5 ° C. and immersed in a 1% aqueous solution of a water extract of tamarind husk according to Example 1 for 1 minute. After immersion, place the shrimp in the refrigerator for 5
Stored at 7 ° C for 7 days. For comparison, the shrimp were refrigerated and stored in the same manner except that the immersion treatment was performed using water instead of the aqueous solution of the tamarind husk extract.

Seven days later, the shrimp were taken out of the refrigerator and inspected for external appearance. In the tamarind husk extract-treated section, discoloration was observed in only one animal, but all the control sections were discolored.

Example 7 A 1% aqueous solution of a tamarind husk extract obtained in Example 1 using a water / ethanol mixture (1/1) was sprayed on 10 mushrooms and covered with a sheet to prevent drying. And stored in a refrigerator at 10 ° C. for 7 days. For comparison, a similar preservation test was performed on mushrooms sprayed with water instead of the aqueous solution of the tamarind husk extract.

After 7 days, the mushrooms were taken out of the refrigerator and subjected to an appearance inspection. In the tamarind husk extract-treated section, discoloration was observed in two pieces, but in the control section, all discolorations were observed.

[0052]

EFFECT OF THE INVENTION The tyrosinase inhibitor according to the present invention is a highly safe natural product, and has a whitening effect because it does not adversely affect the taste or smell of the substance to be added by standard use. Used to make up cosmetics, food,
It can be widely used to prevent discoloration and maintain quality of fish and shellfish feeds.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-8-73321 (JP, A) JP-A-7-258105 (JP, A) JP-A-7-53335 (JP, A) JP-A-61-1985 7208 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 7/00 A23L 3/3472 A61K 35/78 A61P 17/00 CA (STN) MEDLINE (STN)

Claims (3)

(57) [Claims] 1. A tyrosinase inhibitor comprising, as an active ingredient, an extract obtained by extracting a tamarind husk with water, a hydrophilic organic solvent or a mixture thereof. 2. A whitening cosmetic comprising the tyrosinase inhibitor according to claim 1. 3. A discoloration inhibitor comprising the tyrosinase inhibitor according to claim 1.