JPH0745421B2 - Method for preventing discoloration of polyphenol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is caused by the passage of time in a system in which a polyphenol having three or more phenolic hydroxyl groups in the molecule (hereinafter referred to as polyphenol for convenience) is dissolved. The present invention relates to a method for preventing easy discoloration of polyphenol.

(Prior Art) The above-mentioned polyphenols have astringent action, skin conditioning action, protective action, antimutagenic action, hemostatic action, detoxification action, antioxidant action,
Although it is excellent in suppressing sebum secretion, it is very unstable and easily discolors due to heat and oxygen.

It is well known that the discoloration is particularly likely to occur in a system in which polyphenol (tannin) is dissolved, and the discoloration occurs when, for example, green tea or apple juice is left to stand.

(Problems to be Solved by the Invention) As a result of intensive studies for improving the instability of the polyphenol, the present inventor made the copper complex and the organic reducing agent coexist in a system in which the polyphenol is dissolved. In this case, the inventors have found that the polyphenol can be stabilized to prevent the above-mentioned coloring and discoloration without inhibiting the above-mentioned properties (actions and effects) of the polyphenol.

An object of the present invention is to provide a method for preventing coloration or discoloration of a system (composition) in which a polyphenol is dissolved due to aging, without inhibiting the above-mentioned properties (effects) of the polyphenol.

Another object of the present invention is to provide a method for stabilizing polyphenols.

It is still another object of the present invention to provide a polyphenol stabilizer composition (discoloration inhibitor composition).

(Means for Solving the Problems) That is, in order to achieve the above object, the present invention comprises at least one of the above polyphenols dissolved in water, a water-ethanol mixture (water-ethanol mixture system) or an oily substance. In this system, a copper complex and an organic reducing agent are mixed (coexist).

Examples of the polyphenol in the present invention include gallic acid, gallic acid esters (propyl ester, isoamyl ester, octyl ester, dodecyl ester, etc.), pyrogallol, phloroglysin, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin. Catechin gallate, epigallocatechin gallate, epigallocatechin, glucogarin, proanthocyanidins and polymers thereof, flavones (for example, rutin, quercetin, quercetagine, quercetagetin, gosipetin, etc.), ellagic acid, penta-O-galloyl glucose, tannic acid, Gallotannin (tannin of peony extract), ellagitannin (each tannin extracted from Genoshoko, Akamegasiwa, pomegranate skin, Sanshuyu, etc.), Tannin (persimmon, cinnamon,
Tannins extracted from Asenyaku, chimpanzee, etc.), tannins extracted from veiled oak peels, oak peels, nuts and the like.

Further, the copper complex is, for example, a copper complex of chlorophyllin, sulfonated phthalocyanine and their alkali metal salts (sodium salt, potassium salt). These copper complexes are used alone or in combination of two or more.

Further, as the organic reducing agent, for example, ascorbic acid, sodium ascorbate, potassium ascorbate, erythorbic acid, sodium erythorbate, erythorbic acid, dibutylhydroxytoluene, butylhydroxyanisole, phytic acid, tocopherol, tocopherol orotate, Examples thereof include tocopherol nicotinic acid ester, hydroquinone, nordihydroguaiaretic acid, higher ascorbic acid fatty acid ester (lauric acid ester, stearic acid ester, isostearic acid ester, palmitic acid ester, etc.), guaiac fat and the like. These organic reducing agents are used alone or in combination of two or more.

As a system in which the above polyphenol is dissolved in water,
For example, it is a composition in which other substances (components) described later are dissolved and / or dispersed in a polyphenol aqueous solution or water in which polyphenol is dissolved. Examples of the composition include lotions (eg, transparent lotions,
Milky lotion, after shave lotion, suntan lotion, multi-layer lotion, shaking lotion, hair set lotion, external lotion for skin, etc.), creams (eg skin cream, face cream, hand cream, hair cream, foundation cream, etc.), Packing agents, shampoos (hair shampoo, body shampoo, etc.), rinses (hair rinse, etc.), hair treatment agents (eg, hair conditioners, hair treatments, hairnics, etc.), makeup agents (eg, liquid makeup agents, etc.)
Makeup base, eyeliner, mascara, etc.), bath salts, hair nourishing agents, rubbing agents (eliment), external preparations for skin, aerosol compositions, cosmetics such as dentifrice, pharmaceuticals, etc. , Oil-in-water emulsion,
It is in the form of multi-layer liquid, gel, paste, oil-in-polyhydric alcohol emulsion, etc. However, it is not limited to the above.

Examples of the system in which the polyphenol is dissolved in a water-ethanol mixture (mixing ratio of water to ethanol (weight ratio) = 99: 1 to 1:99) include, for example, a polyphenol water-ethanol solution and polyphenol. Is a composition in which other substances (components) described later are dissolved and / or dispersed in a water-alcohol mixture (water-alcohol mixed system) in which is dissolved.

Examples of the composition include lotions (for example, transparent lotions, milky lotions, aftershave lotions, multi-layer lotions, shaking lotions, suntan lotions, hair set lotions, skin lotions, etc.), packs, shampoos (hair Shampoo, body shampoo, etc., rinses (hair rinse, etc.), hair treatment agents (eg, hair conditioner, hair treatment, etc.), makeup agents (eg, liquid makeup agents, makeup base, eyeliner, mascara, etc.), Examples include bath agents, hair nourishing agents, external skin agents, rubbing agents (liniment), cosmetics such as aerosol compositions, pharmaceuticals, etc., usually in the form of solutions, dispersions, water-oil-in-oil emulsions, gels, pastes, Multilayer type To have. However, it is not limited to the above.

Further, as a system in which the above-mentioned polyphenol is dissolved in an oily substance (for example, vegetable oil, animal oil, higher aliphatic hydrocarbons, higher fatty acid, higher alcohol, ester oils, fats and oils, waxes), for example, polyphenol Oily substance in which is dissolved (liquid, solid solution, etc.), other substances (components) described later in the oily substance in which polyphenol is dissolved
Are dissolved and / or dispersed. Examples of the composition include creams (for example, skin cream, face cream, hand cream, foundation cream, emollient cream, etc.), makeup agents (makeup base, etc.), hair cosmetics (for example,
Hair cream, pomade, tic, etc.), lip cosmetics (eg lipstick, lip balm, etc.), ointments, cosmetics such as external preparations for skin, pharmaceuticals, etc., usually in solid form,
It is in the form of paste, solution, gel, dispersion liquid, solid solution, water-in-oil emulsion, etc. However, it is not limited to the above.

The other substances (components) dissolved and / or dispersed in water, a water-ethanol mixture, or an oily substance in which the polyphenol is dissolved include copper complexes, organic reducing agents, and the like. In addition, for example, water, ethanol, polyhydric alcohol (eg glycerin, etc.), oily substance, fragrance,
Dyes, pigments, surface-active substances, pH regulators, viscosity regulators, preservatives, sequestering agents, antioxidants, UV absorbers,
It is a skin nutrition agent, a film-forming agent, an anti-dandruff agent, a moisturizer, an ointment base, a bactericide, an aerosol propellant, or a combination of two or more thereof.

The amount of the polyphenol used in the present invention (blending amount), that is, the amount dissolved in water, water-ethanol or an oily substance is the above-mentioned characteristics of the polyphenol, from the minimum necessary amount capable of exhibiting the effect, the solvent ( It is in a wide range up to the maximum solubility (saturated solubility) in water, water-ethanol mixture or oily substance) and is not particularly limited. 0.001 to 20 relative to the total amount (total weight of prescription ingredients)
It is within the range of weight%.

The amount of copper complex used (blending amount) is based on the total amount of the composition.
Normally 0.001 to 0.1% by weight, based on the weight of polyphenol
0.001 to 100% by weight is preferable.

The amount of the organic reducing agent used (blending amount) is preferably 0.01 to 10% by weight based on the weight of the composition, and 1/20 to 100 times the amount based on the weight of polyphenol.

(Effect) (1) In the present invention, a copper complex and an organic reducing agent are allowed to coexist (blend) in a system in which polyphenol is dissolved, so that the characteristics and effects of polyphenol are not impaired, and Stabilizes polyphenols,
The above coloring and discoloration can be prevented in advance.

(2) By applying the method of the present invention, coloring or discoloration due to polyphenol is unlikely to occur even after long-term storage.
Moreover, astringent effect on skin, skin conditioning effect, rough skin prevention and treatment effect, hemostatic effect, sebum secretion suppression effect, protective effect, antimutagenic effect, hair protection and repair effect, lip rash, crack prevention effect, inflammation (sunburn , Skin burns, eczema, etc.) can be obtained, and cosmetics and pharmaceuticals with good effects for normalizing and treating the skin can be obtained.

(Example) Hereinafter, an example will be described. The parts shown in the examples mean parts by weight. ΔE shown in the examples indicates a color difference. It was measured using a color difference meter (1001 DP type manufactured by Nippon Denshoku Industries Co., Ltd.) using a quartz cell (cell length 10 mm), and from L, a, b values (1) Calculated from the formula. The NBS unit is used as the unit of color difference, and this corresponds well to the sensory color difference, and is highly practical.

ΔL, Δa, and Δb represent the difference between the measured values at the time of preparation and at the time of storage at 45 ° C.

The relationship between ΔE and the sensational hue change with the naked eye is as shown in Table 1.

It should be noted that the larger the value of ΔE (color difference), the greater the change in color,
This indicates that the polyphenol is unstable and is colored or discolored due to heat history.

Among the characteristics of the cosmetics shown in the examples, the astringency is a professional inspector.
Sensory evaluation was performed by 10 people. Furthermore, the evaluation of the durability of the makeup effect on the face of this make-up cosmetics is made by a specialist inspector.
After washing the face of 10 people, apply the cosmetic of the present invention only to the right half face,
Then, a makeup agent was applied to all the faces, and after 2 hours, the makeup effect on the left and right faces was observed. This effect is shown by the fact that the protein aggregating action of polyphenols tightens the skin and suppresses excessive sebum secretion. Further skin conditioning
Regarding the protective effect, similarly, 10 expert inspectors examined the state of healing of rough skin before and after use.

The specialist in this case selected a person with rough skin and tested it.

Each effect was represented by the average of the following evaluation scores.

“Very good”… 5 points, “Good”… 4 points, “Normal”… 3
Points, "bad" ... 2 points, "Very bad" ... 1 point.

Reference Example 1 Fruits of astringent persimmon (Diospyros Lotus L.) were cut into small pieces, pressed to collect fruit juice, and solids were removed by excess to obtain persimmon astringent juice. Add a proper amount of ethanol to Kakishibu. 1000 kg of Kakishibu containing ethanol was adsorbed on a column filled with 1000 l of synthetic adsorbent Diaion HP20 (manufactured by Mitsubishi Kasei Co., Ltd.), and the column was washed with 2000 l of purified water, and 2000 l of hydrous ethanol was added. Elute with. Next, this eluate was concentrated under reduced pressure and then freeze-dried to obtain 30 kg of the condensed persimmon tannin (proanthocyanidin-based polymer) belonging to the above polyphenol.

The condensed persimmon tannin was used in Examples 1 and 2 described later.

Reference Example 2 1 kg of dried root powder of commercially available mud is mixed with 3 l of water-acetone (1: 1)
At room temperature, extract at room temperature and concentrate to dryness under reduced pressure. This extract
Dissolve 50 g in 200 ml of ethanol and use Sephadex LH-20
Adsorb on a column packed with (1.5 l) and absorb with ethanol.
The extract was washed with 10 l, eluted with 70% acetone, and the fraction was freeze-dried to obtain 10 g of red tannin. This ground tannin was used in Example 4 described later.

Reference Example 8 1 kg of dried ginkgo biloba powder was immersed in 5 l of an ethanol-water (1: 1) mixture for extraction, and then concentrated to dryness under reduced pressure to obtain 250 g of a crude extract. This extract is dissolved in water 1, ethyl ether 1 is added thereto, and the mixture is shaken well to remove the ethyl ether layer. After repeating this operation three times, 0.3 l of ethyl acetate is added to the remaining aqueous layer and shaken well for extraction. After repeating this operation 3 times, the extracts were combined, and then concentrated under reduced pressure to dryness at room temperature to obtain a ginkgo biloba extract.

15 g of this extract is subjected to a droplet countercurrent distribution chromatography and developed by a descending method using a chloroform-methanol-water (45:50:21) mixed solution. Fractions of 0.3l to 0.4l were collected, concentrated under reduced pressure at 40 ° C, the precipitate precipitated from water was collected, and yellow powdery geraniin (the above polyphenol) was collected.
I got 1.0g. This gelinin was used in Examples 6 and 7 described later.

Example 1 (Astringent lotion) (1) Formulation Ingredients shown in Table 2 are dissolved, and then ingredients 1 to 3 are dissolved. Finally, the dissolved ingredients were added and mixed uniformly to obtain the astringent lotion of the present invention.

Further, each astringent lotion of Comparative Examples 1 to 8 was obtained in the same manner as above except that the component or or the component and was not used.

Next, the stability (discoloration), astringency, and persistence of the makeup effect of these astringent lotions (hereinafter referred to as a makeup mochi for convenience) were investigated. As a result, (a) the astringent lotion according to the present invention had a very small color difference (ΔE) value of 1.05 after 32 days from the preparation, had substantially no discoloration sensuously, and had very good storage stability. there were.
The astringency evaluation score was 5.0, and the makeup lasting effect evaluation score was 4.8, indicating that all effects were extremely good.

(B) The astringent lotion of Comparative Example 1 had a color difference (ΔE) value of 32.5 after 32 days from the preparation, which was very large and had a great sensory discoloration (remarkably), and the copper complex chlorophyllin sodium alone was added. No discoloration preventing effect was observed. The astringency evaluation score was 4.2 points, and the makeup lasting effect evaluation score was 4.0 points.

(C) The astringent lotion of Comparative Example 2 has a large color difference (ΔE) value of 6.35 after 32 days from the preparation, and has a considerable color change sensuously, and is due to the addition of erythorbic acid (organic reducing agent). The effect of preventing discoloration is extremely low and not practical. The astringency evaluation score was 4.8, and the makeup lasting effect evaluation score was 4.2.

(D) The astringent lotion of Comparative Example 3 had a color difference (ΔE) value of 32.4 after 32 days from the preparation, which was extremely large, and was significantly discolored sensuously. Condensed persimmon tannin contained was a solution. It is clear that the system is also very susceptible to discoloration.
The astringency evaluation score was 4.3, and the makeup lasting effect evaluation score was 4.0.

(E) As is clear from these results, erythorbic acid (organic reducing agent) and copper chlorophyllin sodium were
The combined use (coexistence) makes it possible to prevent the discoloration of the condensed persimmon tannin (polyphenol). Moreover, the properties and effects of condensed persimmon tannin tend to be improved rather than impaired.

Example 2 (External Skin Lotion) Skin external lotion of the present invention was carried out in the same manner as in Example 1 above except that ethanol and disodium edetate were not used and 99.48 parts of purified water was used. The agent was prepared. After 40 days from the preparation of this lotion, the color difference (Δ
The E) value was 1.07, which was very small, there was no discoloration even with feeling, and the storage stability was also very good. Thus, even in an aqueous system, the effect of preventing discoloration by combining erythorbic acid and sodium copper chlorophyllin is extremely high.

Comparative Example 4 (External lotion for skin) Comparative skin was prepared in the same manner as in the invention of Example 1 except that ethanol, disodium edetate and erythorbic acid were not used, and 99.68 parts of purified water was used. An external lotion was prepared. The color difference (ΔE) value of this lotion after 40 days from the preparation was 35.5, which was very large, and the color changed sensuously. Thus, the discoloration-preventing effect of sodium copper chlorophin was not observed even in the water system.

Comparative Example 5 (External lotion for skin) Ethanol, sodium edetate, and copper chlorophyllin sodium were not used, but 99.68 parts of purified water was used,
A comparative external lotion for skin was prepared in the same manner as in the present invention of Example 1. From the preparation of this lotion
The color difference (ΔE) value after 40 days was as large as 7.12, and the color changed sensuously considerably, and the effect of preventing discoloration by erythorbic acid was extremely low.

Comparative Example 6 (lotion for external application to skin) Ethanol, disodium edetate, erythorbic acid and sodium copper chlorophyllin were not used, and 99.78 parts of water was used, and the same procedure as in Example 1 of the present invention was carried out. A lotion for external use on the skin was prepared. The color difference (ΔE) value of this lotion after 40 days from preparation was 35.2, which was extremely large, and the color changed sensuously. As described above, the condensed persimmon tannin is apt to change its color remarkably even in water.

Example 8 (Cream) (1) Formulation (part) Squalane 25.0 Cetyl alcohol 3.0 Glycerin tri-2-ethylhexanoate 5.0 Glycerin monostearate 2.0 Lithium stearate 0.5 Xanthan gum 0.1 Sodium N-stearyl-L-glutamate 0.7 Paraoxy Methyl benzoate 0.2 Disodium edetate 0.1 Sodium citrate 0.1 Sodium copper chlorophyllin 0.005 L-Ascorbic acid 0.1 Catechin (reagent) 0.1 Perfume 0.1 Purified water 63.0 (2) Manufacturing method Dissolve the above components uniformly at about 80 ° C. (Solution 1). About some of the above water-soluble ingredients
Dissolve uniformly at 80 ° C (solution 2). To the above ingredients
Are uniformly dissolved at room temperature (solution 3). Next, while stirring Solution 1 with a homomixer, Solution 2 was added to emulsify and then cooled. In the cooling process, the components were added at 70 ° C., the temperature was lowered to 30 ° C., Solution 3 was added, and stirring was stopped.

The obtained cream of the present invention is filled in a glass container and stored at 40 ° C.
Even when it was stored for 30 days, it had good stability with substantially no sensory hue change.

Further, a continuous test was conducted by 10 professional inspectors for rough skin for 2 weeks, and the evaluation score (average score) of skin conditioning / protecting effect was 4.6, which was a good result.

In addition, as a result of applying 0.05 g of the cream of the present invention to the lips as a lip balm in winter and continuously applying it for 2 weeks, all the specialist inspectors alleviated or healed the symptoms such as peeling of the lips and cracks from the 2nd to 4th day. The protective effect on the lips was also confirmed.

Comparative Example 7 (Cream) A comparative cream was prepared in the same manner as in the invention of Example 3 except that 63.1 parts of purified water was used without using L-ascorbic acid. When this cream was stored at 40 ° C. for 30 days, it was confirmed that the sensory hue change (discoloration) was remarkable and that copper chlorophyllin sodium had no discoloration preventing effect.

Comparative Example 8 (Cream) Example 3 except that copper chlorophin sodium was not used.
Comparative creams were prepared in the same manner as the present invention. It was confirmed that when this cream was stored at 40 ° C. for 30 days, the color changed considerably, and the effect of preventing discoloration by L-ascorbic acid was extremely low.

Example 4 (Toothpaste) (1) Formulation (part) Dicalcium phosphate dihydrate 45.0 Carboxymethyl cellulose sodium 0.5 Carrageenan 0.5 Glycerin 10.0 Sorbitol 10.0 Sodium lauryl sulfate 1.5 Saccharin sodium 0.2 Copper tannin 0.5 Copper chlorophyllin sodium 0.01 L-Ascorbic acid Sodium 0.5 Purified water 31.2 (2) Manufacturing method Mix and disperse a part of the above components (1) and (2) uniformly.
Then, the rest of the components was added with a homogeneously dissolved component (1) and mixed uniformly to obtain the toothpaste of the present invention.

The obtained toothpaste of the present invention is filled in a laminated tube and is stored at 40 ° C.
Even when it was stored for 60 days, there was substantially no sensory change in hue and it had good stability.

Example 5 (hair treatment shampoo) (1) Formulation (part) Lauryl sulfate triethanolamine salt (40% aqueous solution)
25.0 Lauric acid diethanolamide 5.0 Propylene glycol 10.0 Ethanol 4.0 Dibutylhydroxytoluene 0.01 Phthalocyanine tetrasulfonic acid copper tetrasodium 0.01 Erysorbic acid 0.1 Tannic acid (Pharmacopoeia) 0.5 Sodium citrate 0.12 Purified water 55.26 (2) Manufacturing method After being mixed and dissolved in, the ingredients 1 to 3 were mixed and dissolved to obtain a hair treatment shampoo of the present invention.

The obtained hair treatment shampoo of the present invention was filled in a propylene container, and Δ even when stored at 40 ° C. for 60 days.
At E = 1.32, there was virtually no perceptible hue change and it was stable.

Example 6 (aftershave lotion) (1) Formulation (part) Ethanol 65 Gelainine 0.2 Copper chlorophyllin sodium 0.002 Sodium erythorbate 0.2 Dipropylene glycol 1.0 Perfume 0.05 Purified water 32.8 (2) Production method After the mixture was dissolved and mixed, the component and the rest of the mixture were uniformly mixed and dissolved, and the mixture was uniformly mixed to obtain an aftershave lotion of the present invention by filtration at -5 ° C.

The obtained aftershave lotion of the present invention was ΔE = 1 even when filled in a glass container and stored at 45 ° C. for 32 days.
At 20, there was virtually no perceptible hue change and it was stable.

Furthermore, as a result of using the aftershave lotion of the present invention after shaving with a razor by 5 male inspectors, all 5 inspectors recognized the skin-smoothing effect after shaving, and 4 of them The bleeding of the resulting cut stopped immediately.

Example 7 (Ointment) (1) Formulation (part) Purified lanolin 5.0 White beeswax 5.0 White petrolatum 89.8 dl-α-tocopherol 0.1 Copper chlorophyll 0.004 Geraniin 0.1 (2) Manufacturing method A part of the above components is uniformly added Dissolve (A). Then, after the rest of the ingredients and ingredients are heated and melted and mixed thoroughly, cooling is begun immediately before hardening.
Were mixed to obtain an ointment of the present invention. The obtained ointment of the present invention had good stability with almost no sensory change in hue even when stored in an ointment pot at 30 ° C. for 60 days.

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Claims (1)

[Claims] 1. At least one of copper complexes of chlorophyllin and sulfonated phthalocyanine in a system in which at least one polyphenol having three or more phenolic hydroxyl groups in the molecule is dissolved in water, a water-ethanol mixture or an oily substance. A discoloration-preventing method for polyphenols, which comprises blending a salt with an organic reducing agent.