JPS63145213A - Prevention of change of color of polyphenol - Google Patents

Abstract

PURPOSE:To prevent coloring and change in color of a system having a dissolved polyphenol containing three or more phenolic hydroxyl groups, by blending the system with a porphyrin metallic complex containing copper as a ligand metal and an organic reducing agent. CONSTITUTION:A system wherein at least one phenolic hydroxyl group of a polyphenol (e.g. tannin) containing three or more phenolic hydroxyl groups in the molecule, which has astringing action, skin dressing action, protecting action, antimutagenicity, hemostatic action, antidotal action, antioxidative action, suppressing action on sebum secretion, etc., but is extremely unstable and liable to change in color by heat and oxygen, is dissolved in water, a mixture of water and ethanol or an oily substance is blended with a porphyrin metallic complex (e.g. copper chloroporphyrin sodium) containing copper as a ligand metal and an organic reducing agent (e.g. ersorbic acid) to stabilize the polyphenol and to prevent coloring and change in color of the system without damaging the characteristics at all.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to a system in which a polyphenol having eight or more monophenolic hydroxyl groups in its molecule (hereinafter referred to as polyphenol for convenience) is dissolved over time. This invention relates to a method for preventing the discoloration of polyphenols that tends to occur.

(Conventional technology) The polyphenols mentioned above have astringent and skin conditioning effects.

Protective, antimutagenic, hemostatic, and detoxifying effects.

The paternal side, which has excellent antioxidant effects and sebum secretion suppressing effects,
The drawback is that it is extremely unstable and easily discolors when exposed to heat or oxygen.

This discoloration is particularly likely to occur in systems in which polyphenols (tannins) are dissolved, and it is well known that, for example, green tea or apple juice discolors when left standing.

(Problems to be Solved by the Invention) As a result of intensive research to improve the instability of polyphenols, the present inventor discovered that the porphyrin-copper complex described below and an organic reducing agent were added to a system in which polyphenols were dissolved. When coexisting with polyphenols, the above-mentioned properties (actions,
The present invention has been completed based on the discovery that it is possible to stabilize polyphenols and prevent the above-mentioned coloring and discoloration without impeding the effects of the present invention in any way.

An object of the present invention is to provide a method for preventing discoloration and discoloration of a system (composition) in which polyphenols are dissolved over time, without impairing the above-mentioned properties (actions and effects) of polyphenols.

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

Still another object of the present invention is 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 uses a small amount of the above-mentioned polyphenols (one of which is water, a water-ethanol mixture (water-ethanol mixture system), or an oily substance). A porphyrin metal complex having copper as a coordinating metal in the dissolved system (hereinafter referred to as a porphyrin-copper complex for convenience)
The composition is such that the organic reducing agent and the organic reducing agent are blended (coexisting).

Examples of the polyphenol in the present invention include gallic acid, gallic acid esters (propyl ester, isoamyl ester, and octyl ester).

dodecyl ester, etc.), pyrogallol, phloroglycin, catechin, shrimp catechin, and gallocatechin.

Catechin gallate, galoka chicken gallate, shrimp chicken gallate, epigallocatechin gallate.

Epigallocatechin, glucogallin, proanthocyanidins and their polymers, flavones (e.g. rutin, quercetin, quercetagin, quercetagetin, gossypetin, etc.), ellagic acid, penta-0-galloylglucose, tannic acid, gallotannin (tannin of peony extract) , ellagitannins (tannins extracted from gennoshirouko, akamegashiwa, pomegranate peel, cornscheil, tone, etc.), condensed tannins (various tannins extracted from persimmon juice, cinnamon bark, asenyaku, jiyue, etc.), and white oak peel.

Various tannins extracted from Quercus bark, Quercus nuts, etc. can be mentioned.

Further, the above-mentioned porphyrin-#I complex is a copper complex in which copper is coordinated at the center of a porphyrin skeleton, such as protoporphyrin and hematoporphyrin.

Preferred are copper complexes of sulfonated tetraphenylporphyrin, chlorophyrin, sulfonated phthalocyanine and their alkali metal salts (sodium salt, potassium salt), copper complexes of tetraphenylporphyrin, octaethylporphyrin, and the like. These porphyrin-copper complexes are
They may be used singly or in combination.

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

As a system in which the above-mentioned polyphenols are dissolved in water,
For example, it is a polyphenol aqueous solution, a composition in which other substances (components) described later are dissolved and/or dispersed in water in which polyphenols are dissolved. Examples of the composition include, for example, transparent resins (for example, transparent resins),
milky lotion, aftershave lotion, suntan lotion, multi-layered lotion, shaking lotion, AS set lotion, skin external lotion, etc.)
, creams (e.g. skin creams).

face cream, hand cream, hair cream,
foundation cream, etc.), pack agents.

Shampoos (hair shampoo, body shampoo, etc.), conditioners (hair rinse, etc.), hair treatment agents (for example, hair conditioner, hair treatment, etc.)
hair tonics, etc.), make-up products (e.g., liquid make-up products, make-up pastes, eyeliners, mascara, etc.), bath salts, hair nourishing products, rubbing agents (elements), and external skin preparations.

Examples include aerosol compositions, cosmetics such as dentifrices, pharmaceuticals, etc., and are usually in the form of solutions, monodispersed liquids, oil-in-water emulsions, multilayer liquids, gels, and pastes.

It is in the form of oil-in-polyhydric alcohol emulsion. However, it is not limited to the above.

In addition, the polyphenol described above can be added to a water-ethanol mixture (
Mixing ratio of water to ethanol (heavy ratio) = 99:1 to 1:9
Examples of systems dissolved in 9) include water-ethanol solutions of polyphenols.

A water-alcohol mixture in which polyphenols are dissolved (
Other substances (components) listed below in water-alcohol mixed system)
are dissolved and/or dispersed therein.

Examples of the composition include, for example, rosyrons (eg, transparent rosy wrappers, milky rosy wrappers).

Aftershave lotion, multi-layered lotion.

Shaking lotion, suntan lotion, hair set lotion, external skin lotion, etc.), pack agents, shampoos (hair shampoo, body shampoo, etc.),
Conditioners (hair rinse, etc.).

Hair treatment agents (e.g. hair conditioners).

hair treatments, etc.), make-up products (e.g. liquid make-up products, make-up pastes).

eyeliner, mascara, etc.), bath additives, hair nourishing products.

Cosmetics such as external skin preparations, liniments, aerosol compositions, pharmaceuticals, etc.N1 Normally, solution form9 dispersion liquid form, oil-in-water-ethanol emulsion, W-n, gel form, paste form, multilayer type It is in the form of a liquid note. However, it is not limited to the above.

Furthermore, the polyphenol may be an oily substance (e.g., vegetable oil, animal oil, higher aliphatic hydrocarbon, lower grade fatty acid, higher alcohol, ester oil, oil or fat, wax) IC.
Examples of dissolved systems include oily substances (liquid, solid solution, etc.) in which polyphenols are dissolved, and other substances (components) described later dissolved and/or dispersed in oily substances in which polyphenols are dissolved. It is a composition that has The compositions include creams (e.g. skin creams, face creams, hand creams).

foundation cream, emollient cream, etc.)
, Makeup department (makeup base, etc.).

Hair cosmetics (e.g. hair cream, pomade).

lip cosmetics (e.g., lipstick, lip balm, etc.), ointments, external skin preparations, etc.

Pharmaceutical 8 answers are given.N1 Usually, solid, paste-like.

It is in the form of a solution, a gel-like dispersion, a solid solution, a water-in-oil emulgene, etc. However, the above is not limited to ζ.

In addition, water in which the above-mentioned polyphenols are dissolved.

Other substances (components) mentioned above that are dissolved and/or dispersed in the water-ethanol mixture or oily substance include porphyrin-copper complexes, organic reducing agent ponds, e.g. Alcohol (e.g. glycerin, etc.), oily substance, fragrance, dyestuff, surfactant, P
H regulator, viscosity regulator, preservative, sequestering agent, antioxidant, ultraviolet absorber, skin nutrient, film forming agent, anti-dandruff agent, humectant, ointment base, disinfectant, aerosol propellant, alone or in combination of two or more thereof.

The amount of the polyphenol used (blended amount) in the present invention fζ, that is, the amount dissolved in the water, water-ethanol or oily substance, is determined from the minimum necessary amount to exhibit the properties and effects of the polyphenol, (maximum solubility in water, water-ethanol mixture or oil-based substance) Usually 0.001 for the total amount of the composition (total amount of prescription ingredients t) lζ
-20% by weight.

The amount of the porphyrin-copper complex used (m<formulation 1) is usually 0.001 to 0.1% by weight relative to the total amount of the composition, and O,OO1 to 100ff! relative to the polyphenol.
Amount % is preferred.

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

(Effects) (1) The present invention provides a system in which polyphenols are dissolved (ζ), a porphyrin-copper complex and an organic reducing agent coexist (
By adding (blending), the above-mentioned properties and effects of polyphenols are inhibited, and the polyphenols are also stabilized, thereby making it possible to prevent the above-mentioned coloration and discoloration.

(2) By applying the method of the present invention, coloration or discoloration due to polyphenol 1 is unlikely to occur even after long-term storage. In addition, it has an astringent effect on the skin, a skin conditioning effect, a skin roughness prevention and treatment effect, a hemostatic effect, a sebum secretion suppressing effect, a protective effect, an antimutagenic effect, a hair protection and repair effect, a chapped lips, a crack prevention effect, and an inflammation ( It is possible to obtain cosmetics and pharmaceuticals that have good effects on normalizing and treating skin affected by burns, burns, eczema, etc.

(Example) Examples will be described below. The parts shown in the examples mean parts by weight. Example 1 ζ The jB shown indicates the color difference, which was measured using a color difference meter (Model 1001 DP manufactured by Nippon Denshoku Kogyo ■) using a quartz cell (cell length 1 om), a, b
It is calculated from the value using equation (1). Unit of color difference (kohaNB
8 units are used, and this corresponds well to the perceptual color difference and is recognized to be highly practical.

Δn= (ΔL)2+(Δa)2+(Δb)”
(1) ΔL, ja, and Δb are n, respectively, and represent the difference between the measured values during preparation and storage at 45°C.

The relationship between ΔE and the perceptual hue change due to Iζ with the naked eye is shown in Table 1.

Table 1: ΔE (the larger the color difference value, the larger the color change;
This indicates that the polyphenol is oxidized or colored or discolored due to heat history, indicating that it is unstable.

Among the characteristics of the cosmetics shown in the examples, astringency was evaluated by 10 expert examiners based on sensory evaluation. Furthermore, 10 expert examiners evaluated the durability of the makeup effect of the makeup cosmetics on the face by applying the cosmetics of the present invention to only the right half of the face (ζ
After application, makeup was applied to the entire face, and the makeup effect on the left and right faces was observed 2 hours later. This effect is mainly due to the protein aggregation effect of polyphenols that tightens the skin and suppresses excessive sebum secretion. Furthermore, regarding skin conditioning and protection effects, 10 expert examiners similarly examined the state of healing of rough skin before and after use.

In this case, the expert inspectors selected and tested people with rough skin.

The effect of each n was expressed by the average score of the following evaluation scores.

``Excellent''...5 points, ``Good''...4 points, ``Average''...8 points, ``Poor''...2 points.
"Very bad"...1 point.

Reference example 1 Astringent persimmon (Diospyros KaKi Thunb)
The fruit was cut into small pieces, the juice was collected by squeezing, and the solid content was removed by filtration to obtain persimmon juice. Add an appropriate amount of ethanol to persimmon juice. Persimmon juice 1000 containing this ethanol
ky is catalytically adsorbed on a column packed with synthetic adsorbent Diaion HP20 (Mitsubishi Chemical Industries ■%) 10001, and after washing this column with quenching water 20001, it is eluted using aqueous ethanol 20001. Next this m
The extract was concentrated under reduced pressure and then freeze-dried to obtain 80J of reduced persimmon tannin (proanthocyanidin-based polymer) belonging to the polyphenol group.

Incidentally, this reduced type persimmon tannin was used in Example 1 and Example 2 described later.

Reference Example 2 1 ky of commercially available dry root powder of elm was extracted at room temperature with water-acetone (t:B mixture 31, P was removed, and concentrated to dryness under reduced pressure. This extract 501 was dissolved in 200 ml of ethanol, and Sephadex LH was added. -20 (1,54) was packed and adsorbed on a column by contact, washed with 1O1 ethanol, eluted with 70% acetone, and both portions were lyophilized to obtain 10 f of the district inspection tannin. It was used in Example 4 below.

Reference Example 8 1 kl of dried leaves of Gennoshi sotsuko was mixed with ethanol-water (1:
l) After extraction by immersion in mixed solution 511, the mixture is concentrated to dryness under reduced pressure to obtain crude extract 250f. Dissolve this extract in 111 cups of water,
Add 1110 ml of ethyl ether to the mixture and shake well to remove the ethyl ether layer.

After repeating this operation 8 times, add 0.81 ml of ethyl acetate to the remaining aqueous layer, shake and extract. Repeat this operation 8 times.
After repeating the process several times, combine the extracts and then reduce the pressure at room temperature to #
The mixture was condensed to dryness to obtain a Gennoshi 1 Uko extract.

15 days of this extract was subjected to [7ii countercurrent partition chromatography] using chloroform-methanol-water (45:50:
21) Using the mixed solution, develop using the descending method. 0.81
A fraction of ~0.41 was collected and concentrated under reduced pressure at 40°C, and the precipitate precipitated from water was collected to obtain 1.0 F/g of geraniin (the above-mentioned polyphenol) in the form of a yellow powder. This gelinin was used in Example 6.7 below.

Example 1 (Astringent lotion) Ingredients (1) and (2) are dissolved in (1) of the ingredients shown in Table 2, and then components (1) to (2) are dissolved. Finally, a solution of component (2) was added to component (2) and mixed uniformly to obtain an astringent lotion of the present invention.

Furthermore, each of the astringent lotions of Comparative Examples 1 to 8 was obtained in the same manner as above, except that component (1) or (2), or component (2) and (2) were not used.

Next, the stability (discoloration) of the astringent lotion by Ton et al.

We investigated the astringency and durability of the makeup effect (hereinafter referred to as makeup retention for convenience). As a result, (a) the astringent lotion according to the present invention has a color difference (jE) 82 days after preparation.
The value was 1.05, which was very small, and there was virtually no discoloration perceptually, and the storage stability was also very good. Moreover, the evaluation score for the astringency was 5.0 points, and the evaluation score for the makeup-wearing effect was 4.8 points, and both effects were extremely good.

(b) The astringent lotion of Comparative Example 1 is m! ! ! After 82 days, the color difference (Δ'E) value was 32.5, which was very thick (and had a large (significant) color change in terms of sensation), and the color change was due to the addition of sodium copper chlorophyllin (porphyrin-copper complex). No preventive effect was observed at all.The astringency evaluation score was 4.2 points, and the makeup retention effect evaluation score was 4.2 points.
It was 0 points.

(c) The astringent lotion of Comparative Example 2 had a large color difference (ΔB) value of 6.85 82 days after preparation, and also had a considerable discoloration perceptually, indicating that erythorbic acid (organic reducing agent) The effect of preventing discoloration by the formulation Cζ is extremely low and is not practical.

The evaluation score for the astringency was 4.8 points, and the evaluation score for the makeup-wearing effect was 4.2 points.

2) The astringent lotion of Comparative Example 8 had an extremely large color difference (jE) value of 82.4 82 days after preparation, and was also noticeably discolored to the senses. It is clear that Cζ is extremely susceptible to discoloration even in solution system Cζ. The evaluation score for the astringency was 4.8 points, and the evaluation score for the makeup lasting effect was 4.0 points.

(e) As is clear from these results, condensed rod tannins (polyphenol ) can prevent discoloration. Moreover, it has the characteristics of condensed bar tannins.

It does not impede the effect (in fact, it tends to improve it).

Example 2 (Roseilon agent for external use on the skin) The skin preparation of the present invention was prepared in the same manner as in Example 1 of the present invention, except that ethanol and disodium edetate were not used and 79.48 parts of purified water was used. A topical Rosilon preparation was prepared. The color difference (jE) value 40 days after the preparation of this Rosilon agent was 1.07, which was very small, and there was no sensuous discoloration (and the storage stability was also very good. In this way, even in aqueous systems, The combined use of erythorbic acid and copper chlorophyllin sodium has an extremely high discoloration prevention effect.

Comparative Example 4 (Roseilon preparation for external use on the skin) 1ζ was carried out in the same manner as in Example 1 of the present invention, except that ethanol, disodium edetate and erythorbic acid were not used, and 99.68 parts of purified water was used. A comparative dermatological lotion agent was prepared. The color difference (jE) value of this Loliton agent 40 days after its preparation was 35.5, which was very large, and the color was noticeably discolored.As shown above, even in aqueous systems, copper chlorophyllin sodium caused discoloration. No preventive effect was observed.

Comparative Example 5 (Roseilon agent for external use on the skin) A comparison was made in the same manner as in Example 1 of the present invention, except that ethanol, disodium edetate, and sodium copper chlorophyllin were not used, and 99.68 parts of purified water was used. A low-scene preparation for external use on the skin was prepared.

The color difference (j) of this low silane agent 40 days after preparation
E) The value is 7.12, which is large, and there is considerable discoloration perceptually, and the discoloration prevention effect of erythorbic acid is extremely low.

Comparative Example 6 (Rollagin for external use on the skin) Water was added to 99.7% without using ethanol, disodium edetate, erythorbic acid, and sodium copper chlorophyllin.
A comparative skin care preparation for external use was prepared in the same manner as in Example 1 of the present invention, except that 9 parts of the product were used. The color difference (jE)li of this Rosilon agent 40 days after preparation
! I was extremely large at 85.2, and the color was noticeably discolored. In this way, ζ-condensed persimmon tannins are extremely susceptible to discoloration even in water.

Example 8 (cream) ■ Cetyl alcohol 8.0 ■ Tri-2-ethylhexanoic acid glycerin 6.0 ■ Lipophilic type glyceryl monostearate 2.0 ■ Stearic acid
0.5■xanthan gum
0.1 ■ Sodium N-stearyl-L-glutamate 0.7 ■ Methyl paraoxybenzoate 0.2 ■ Disodium edetate
0.1 [Phase] Sodium citrate
0.1 ■ Sodium copper chlorophyllin
0.0050L-ascorbic acid
0.1 [Phase] Catechin (reagent) 0.1 0 Fragrance 0.1 [Phase] Purified water 68.0° (2
) Production method Uniformly dissolve the above components ① to ② at approximately 80℃ (Solution 1
). Approximately 8% of the water bathing components ■ to ■ and part of ■ of the above ingredients
Uniformly dissolve at 0″C (solution 2).

[Phase] to [Phase] are uniformly dissolved in the above component [Phase] at room temperature (Solution 8). Next, while stirring Solution 1 with a homomixer, Solution 2 is added and emulsified, followed by cooling.

In addition, component (■) was added at 70°C during the cooling process, and the
After the temperature was lowered to 1, Solution 8 was added and stirring was stopped.

The obtained cream of the present invention was filled into a glass container and heated at 40°C.
Even when stored for 30 days, there is a substantial change in hue! It had very good stability.

Furthermore, when 10 expert testers with rough skin conducted a continuous application test for two weeks, the evaluation score (average score) for skin conditioning and protective effects was 4.6, which was a good result.

In addition, as a result of continuous use of the cream of the present invention as a winter stiffness lip cream by applying 0.05 F per lip for 2 weeks, all of the expert examiners found that symptoms such as peeling and cracking of the lips were reduced from the 2nd to 4th day. Otherwise, it was confirmed that the lip was healed and its protective effect on the lips.

Comparative Example 7 (Cream) A comparative cream was prepared in the same manner as in Example 8 of the present invention, except that L-ascorbic acid was not used and 68.1 parts of purified water was used. When this cream was stored at 40° C. for 80 days, there was a noticeable change in hue (discoloration), and it was confirmed that copper chlorophyllin sodium has no effect on preventing discoloration.

Comparative Example 8 (Cream) A comparative cream was prepared in the same manner as in Example 8 of the present invention, except that sodium copper chlorophyllin was not used. When this cream was stored at 40° C. for 80 days, it changed color considerably, and it was confirmed that the effect of preventing L-ascorbic acid ζ from discoloration was extremely low.

Example 4 (Toothpaste) (1) Prescription ■ Sodium carboxymethyl cellulose 0.5 ■ Carrageenan 0.5 ■ Glycerin 10.0 ■ Sorbitol 1O40 ■ Sodium lauryl sulfate 1.5 ■ Sodium saccharin 0.2 ■ Jyutannin
0.5■ Sodium copper chlorophyllin
0.01 [Phase] Sodium L-ascorbate 0.5■ Purified water
31.2 (2) Production method The above components (1) to (2) and a part of (2) are uniformly mixed and dispersed.

Next, a uniform solution of components (2) to (phase) was added to the remainder of component (1) and mixed uniformly to obtain a toothpaste of the present invention.

The resulting toothpaste of the present invention is! Even when packed in a 11/119-Uve and stored at 40°C for 60 days, there was virtually no perceptible change in hue, and it had good stability.

Actual example 5 (hair treatment shampoo) ■Propylene glycol 1000■Ethanol
4.0 ■ Dibutylhydroxytoluene 0.01 ■ Copper tetrasodium phthalocyanine tetrasulfonate 0.01 ■ Erythorbic acid
0.1 ■ Tannic acid (pharmacopoeia) 0.5 ■ Sodium citrate 0.12 [Phase] Purified water 55.26 (2
) Manufacturing method After uniformly mixing and dissolving the above components (1) to (2), a uniform 1ζ mixture and solution of components (1) to (phase) was added and uniformly mixed to obtain a hair treatment shampoo of the present invention.

Even when the obtained hair treatment shampoo of the present invention was filled in a propylene container and stored at 40'C for 60 days, it was stable with ΔE=1.82 and substantially no perceptible change in hue.

Actual example 6 (aftershave lotion) ■ Gelainin 0.2 ■ Sodium copper chlorophyllin 0.0020 Sodium erythorbate 0.2 ■ Dipropylene glycol
1. O ■Fragrance
0. o5 ■ Purified water
82.8 (2) Production method After uniformly dissolving 3 parts of the above ingredients ■ to ■, ■, and ■, add the remaining parts of ingredients ■, ■, and ■ uniformly mixed and dissolved, and mix uniformly. After filtration at -5°C, an aftershave bottle of the present invention was obtained.

Even when the obtained aftershave lotion of the present invention was filled in a glass container and stored at 45°C for 82 days, the Δ
At E=1.20, there was virtually no perceptible change in hue and it was stable.

Furthermore, when five male professional examiners used the aftershave lotion of the present invention after shaving with a razor, all six professional examiners recognized that it had a skin conditioning effect after shaving; The bleeding from the cut that had formed stopped immediately.

Example 7 (Ointment) ■ White beeswax 6.0 ■ White petrolatum 89.8 ■ dl-a
-) Copherol 0.1 ■ Copper chlorophyll 0.004 ■ Geraniin
0.1(2) Production method Uniformly dissolve components
). Next, the remainder of component (1), components (2) and (2) were heated, dissolved, and thoroughly mixed, and immediately before cooling began, A was mixed in to obtain the ointment of the present invention. The obtained ointment of the present invention exhibited good stability with almost no perceptible change in hue even when stored in an ointment pot at 80° C. for 60 days.

6. Contents of the amendment Procedural amendment (voluntary) 1. Indication of the case 1985 Patent Application No. 292182 Z Name of the invention Method for preventing discoloration of polyphenols 8. Person making the amendment Relationship to the case Patent applicant address Sumida, Tokyo 5-17-4 Sumida 5-17-90 Tomobuchi-cho, Bejima-ku, Osaka 584 Kanebo Co., Ltd. Patent Department Telephone (06) 921-1251 4. Number of inventions increased by amendment None 5. Amendment The "Detailed Description of the Invention" column of the subject specification is corrected to jlQmmJ.

(2) rDio described in the specification, page 18, line 17
spyros Kaki ThunbJ rDio
spyrosLotus L, J two corrections.

(3) “79.48” stated on page 19, line 10 of the specification.
" is corrected to "99.48".

(4) Akira ms, “99.7” written on the bottom line of page 20
9” is corrected to “99.78”.

Claims (1)

[Claims] (1) Organic reduction with a porphyrin metal complex having copper as a coordinating metal in a system in which at least one polyphenol having eight or more phenolic hydroxyl groups in the molecule is dissolved in water, a water-ethanol mixture, or an oily substance. A method for preventing discoloration of polyphenols, the method comprising blending a polyphenol with an agent.