JP3878612B2 - Composition for suppressing active oxygen, and external preparation for skin and cosmetic containing the composition - Google Patents

Description

  The present invention relates to a composition for suppressing active oxygen, particularly a composition for suppressing hydroxy radicals having high influence on skin aging such as wrinkles and spots, rough skin, and skin cell damage such as inflammatory acne, and a composition thereof. The present invention relates to an external preparation for skin and a cosmetic.

  Active oxygen is a state in which oxygen molecules have radicals by high energy discharge, enzymatic reaction, etc., or ionization, and oxygen itself has radicals, and OH oxygen has radicals. So-called hydroxy radicals are also included in the broad sense of active oxygen.

  Among such active oxygen species, it is known that hydroxy radicals are generated in the skin by ultraviolet rays, electromagnetic waves or the like, and have an adverse effect on the skin. Specifically, it has been pointed out that it is deeply involved in inflammatory skin troubles such as acne, atopic dermatitis, and rough skin, and wrinkles and spots caused by photoaging. Hydroxyl radicals have high cytotoxicity and lipid peroxide generation, but the skin damage reaction proceeds in a very short time. Therefore, a technique for suppressing hydroxy radicals almost completely in a short time is required.

Conventionally, SOD (superoxide dismutase), vitamin E (tocopherol), which is an antioxidant, and the like are known as those that suppress the generation of oxygen radicals. Further, a patent application such as Patent Document 1 below has been filed in which vitamin C (ascorbic acid) has an action of suppressing active oxygen.
Japanese Patent Laid-Open No. 2001-322990

  However, these SOD, vitamin E, vitamin C, and the like have a problem that the hydroxy radical suppressing effect is low, and stability and sustainability are weak.

On the other hand, it has also been pointed out that the extract from plants has an action of suppressing active oxygen. For example, as described in Patent Documents 2 to 4, patent applications relating to cosmetics for suppressing active oxygen and the like containing plant extracts are also available. Has been made.
Japanese Patent Laid-Open No. 2003-192566 JP 2003-226632 A JP2003-321337

  However, even if a plant extract is blended as in Patent Documents 2 to 4, the effect of suppressing active oxygen is not sufficient, and the stability and sustainability are weak.

  The present invention has been made to solve such conventional problems, and has a high stability and sustainability, and an active oxygen suppressing effect capable of suppressing active oxygen such as hydroxy radicals almost completely in a short time. It is an object of the present invention to provide an excellent composition, a skin external preparation and a cosmetic containing the composition.

The present inventors have such problems Toko filtrate that to the intensive study to solve the, and derivatives of chitin or chitosan, coexistence with amino acids, conjugated, especially derivatives of specific chitin or chitosan with an average molecular weight from 1000 to 5,000,000 Together with amino acids such as citrulline and theanine, the effect of suppressing active oxygen such as hydroxy radicals is effectively and synergistically increased, and the action on skin cells is further increased. Has been found to be solved, and the present invention has been completed.

That is, the first aspect of the present invention is an invention relating to compositions for active oxygen suppressing, characterized in that it contains the amino acid, and a derivative of chitin or chitosan. Derivatives of chitin or chitosan, partially myristoylated chitosan pyrrolidone carboxylate, carboxymethyl chitin, at least one of chitosan pyrrolidone carboxylate salt are used. Also, as the amino acid, citrulline, at least one of theanine is used.

Further, the invention of claim 2 is an invention of the skin external agent characterized by containing the composition for the active oxygen inhibition of claim 1 Symbol placement. Further, the invention of claim 3 wherein is a cosmetic composition of the invention which is characterized by containing a composition for active oxygen inhibition of claim 1 Symbol placement. Such external preparations for skin and cosmetics can be used for prevention and reduction of inflammatory skin sites, or can be used for prevention and reduction of wrinkles or spots caused by photoaging.

  According to the present invention, a composition having high stability and sustainability and capable of suppressing active oxygen such as hydroxy radicals almost completely in a short time, and a composition for external application to skin containing the composition. It became possible to provide cosmetics.

The amino acids contained in the composition of the present invention, Shitoruri down as described above, at least one of Te cyanine is used.

Chitin, derivatives of chitosan down, from the synergistic effect of the above amino acids, rather is preferable to use those having an average molecular weight from 1,000 to 5,000,000, as described above, For example other, carboxymethyl chitin, carboxymethyl chitosan, carboxy Butyl chitosan, hydroxypropyl chitosan, N-dicarboxymethyl chitosan, succinylated chitosan, phosphorylated chitin, phosphorylated chitosan, partially hydrolyzed chitin, sulfated chitin, sulfated chitosan, glycolate and ascorbate of chitin and chitosan And salts such as pyrrolidone carboxylate . Among these, carboxymethyl chitin and chitosan pyrrolidone carboxylate are used in the present invention.

Further, those in which 0.1 to 50.0% of a fatty acid group such as an acyl group having 8 to 20 carbon atoms is partially introduced are also used. 0.1 to 50.0% parts introduced material fatty acid group having 8-20 carbon atoms to an amino group and a hydroxyl group is not preferable to further increase the synergistic effect. Concrete in part myristoylated chitosan pyrrolidone carboxylate (product name PM- Chitosan: Pierce Co.) and partial acetyl-myristoyl chitosan pyrrolidone carboxylate salt, partially myristoylated chitin lactate, partially myristoylation quaternized chitosan glycolate -It is preferable to use a sulfate or the like. Of these, partially myristoylated chitosan pyrrolidone carboxylate is used in the present invention.
Here, “partial introduction” indicates how much fatty acid groups such as acyl groups are introduced per residue of the constituent monosaccharide. “Partial introduction of 0.1 to 50.0% of fatty acid groups” For example, in the case of chitosan, 1 to 500 fatty acid groups are introduced into 1000 residues of hexosamine, which is a constituent monosaccharide. Thus, chitin and chitosan derivatives into which fatty acid groups such as acyl groups having 8 to 20 carbon atoms are partially introduced exhibit amphipathic properties.

The average molecular weight in the above case is, for example, GPC-HPLC (gel filtration chromatography column: TSK-gel-G3000WXL + TSK-gel-G2500PWXL manufactured by Tosoh Co., Ltd.) connected with a data module GPC cartridge, solvent: 0.4 M acetic acid-acetic acid Na buffer (pH = 4.8)] determined by revealing the molecular weight distribution by analysis. As molecular weight standards, chitosan oligosaccharide (molecular weight: 413,1006), dextran sulfate (molecular weight: 5000, 8000) and pullulan molecular weight standard are used.
The average molecular weight can also be obtained from a viscosity measurement method or the like.

Chitosan is a highly deacetylated product of chitin, which is a natural polysaccharide, and it is preferable to synthesize derivatives based on deacetylated chitin that exhibits a degree of deacetylation of 50 to 100%. And amino acids, coexistence ratio of chitin, chitosan down the derivative is not particularly limited, chitin the amino acids 1 00 capacity, it is desirable that the volume ratio of chitosan down the derivative is 0.1 to 20 volume.

  Although the compounding quantity of the composition with respect to the external preparation for skin or cosmetics in this invention is not specifically limited, 0.0005-5 mass% is preferable at the dry solid weight in the whole quantity, such as an external preparation. If the amount is less than 0.0005% by mass, the effect of the present invention may not be sufficiently obtained. On the other hand, if the amount exceeds 5% by mass, an improvement in the effect commensurate with the increase is not recognized. From this viewpoint, 0.001 to 3 mass% is more preferable.

  The form of the external preparation for skin is not particularly limited and can be, for example, lotion, essence, gel, emulsion, emulsified lotion, cream and the like. More specifically, it can be provided as a preparation such as a skin care cream for preventing or reducing inflammation, an emulsion emulsion foundation, an emulsion makeup base, an emulsion mascara, etc., which does not contain a low molecular surfactant.

  Moreover, according to the form of a skin external preparation, the component generally used with cosmetics and an external preparation other than the said essential component can be mix | blended in the range which does not inhibit the effect of this invention. For example, polyhydric alcohols such as butylene glycol, dipropylene glycol and glycerin, higher alcohols such as cetanol and behenyl alcohol, nonpolar oils such as liquid paraffin and squalane, ester oils such as isopropyl palmitate and isopropyl myristate, Examples include vegetable oils such as wheat germ oil and olive oil, silicon compounds such as trimethylsiloxysilicic acid and methylphenylpolysiloxane, and fluorine compounds such as perfluoropolyether. Moisturizing and softening agents, antioxidants, astringents, whitening agents, antibacterial agents, anti-inflammatory agents, UV absorbers, UV scattering agents, vitamins, enzymes, etc. Ingredients such as standards, cosmetic raw material standards, Japanese pharmacopoeia, official standards for food additives, etc.

  Examples of the present invention will be described below.

Example 1
In this example, citrulline and partially myristoylated chitosan pyrrolidone carboxylate were mixed to prepare a composition for suppressing active oxygen. Specifically, a solution containing 1% citrulline and 0.01% partially myristoylated chitosan pyrrolidone carboxylate was prepared and used as a composition for suppressing active oxygen. As the partially myristoylated chitosan pyrrolidone carboxylate, PM-chitosan manufactured by Pierce Co., Ltd. was used.

  The scavenging activity of the hydroxy radical scavenging activity of the thus prepared active oxygen suppressing composition was measured and tested for scavenging action. On the other hand, a solution containing only 1% citrulline (Comparative Example 1-1) and a solution containing only 0.01% partially myristoylated chitosan pyrrolidone carboxylate (Comparative Example 1-2) were prepared, and similarly, hydroxyl radical scavenging activity was obtained. It was measured and compared with the composition for suppressing active oxygen which is the above mixture.

  The reaction composition contains 40mM K-Pi buffer (pH 7.4), 0.26mM ascorbic acid, 0.15mM FeEDTA, 0.6mM hydrogen peroxide, 2mM salicylic acid and the target solutes such as citrulline and partially myristoylated chitosan. Was made into 400 mL, and a hydroxy radical was generated by an ascorbic acid-hydrogen peroxide system. After incubating at 25 ° C. for 90 minutes, hydroxylated salicylic acid was derivatized to develop color, and the absorbance was detected at 510 nm to detect radicals. For the control, purified water was added instead of the sample, and the blank was measured using a solution excluding ascorbic acid, FeEDTA, and hydrogen peroxide.

The hydroxy radical elimination rate was calculated according to the following formula.
Hydroxy radical scavenging rate (%) = [1- (sample OD−blank OD) / (control OD−blank OD)] × 100
In this formula, OD indicates absorbance at 510 nm. Table 1 and FIG. 1 show the erasure rate for the generated hydroxy radical.

  As is clear from Table 1 and FIG. 1, about 17% scavenging activity was obtained in Comparative Example 1-1 of the solution containing only citrulline, and about Comparative Example 1-2 of the solution containing only partially myristoylated chitosan. An erase activity of 3% was obtained. In contrast, in the case of a solution containing both, an erasing activity of about 28% was obtained. From this result, in the case of a liquid containing both citrulline and partially myristoylated chitosan, the value of the erasing activity of the solution containing only citrulline and the value of the erasing activity of the solution containing only partially myristoylated chitosan were combined. It was found that the above erasing activity can be obtained. From this, it was confirmed that the inclusion of both citrulline and partially myristoylated chitosan synergistically increases the hydroxy radical scavenging activity in each case.

(Example 2)
In this example, the concentration of citrulline was 2%, and the concentration of partially myristoylated chitosan pyrrolidone carboxylate was 0.05%. A composition for suppressing active oxygen was prepared by mixing the two, and the preparation method is the same as in Example 1.
And the hydroxy radical scavenging activity was measured like Example 1 about the composition for active oxygen suppression of a present Example. On the other hand, a solution containing only citrulline 2% (Comparative Example 2-1) and a solution containing only 0.05% partially myristoylated chitosan pyrrolidone carboxylate (Comparative Example 2-2) were prepared, and similarly, hydroxyl radical scavenging activity was obtained. It was measured and compared with the composition for suppressing active oxygen of the present example, which is the above mixture.

Table 2 shows the elimination rate for the generated hydroxy radicals.

  As is clear from Table 2, the scavenging activity of about 22% was obtained in Comparative Example 2-1 of a solution containing only citrulline, and about 29% of Comparative Example 2-2 of a solution containing only partially myristoylated chitosan. Erase activity was obtained. On the other hand, in the case of a solution containing both, an erasing activity of about 57% was obtained. From this result, in the case of the liquid containing both citrulline and the partially myristoylated chitosan pyrrolidone carboxylate, it was confirmed that the hydroxy radical scavenging activity in each case increased synergistically.

(Example 3)
In this example, carboxymethyl chitin having a concentration of 0.1% was used as the chitosan derivative instead of the partially myristoylated chitosan pyrrolidone carboxylate of Example 2. The concentration of citrulline was the same as in Example 2. Both were mixed to prepare a composition for suppressing active oxygen. The preparation method was the same as in Examples 1 and 2.
About the composition for active oxygen suppression of a present Example, hydroxy radical scavenging activity was measured like Example 1, 2, and the solution (comparative example 3-1) containing only 2% of citrulline, and carboxymethyl chitin 0.1% The hydroxy radical scavenging activity of the solution containing only the salt (Comparative Example 3-2) was measured in the same manner and compared with the composition for suppressing active oxygen of this Example.

Table 3 shows the erasure rate for the generated hydroxy radicals.

  As apparent from Table 3, about 22% of the erasing activity was obtained in Comparative Example 3-1, and about 8% of the erasing activity was obtained in Comparative Example 3-2. On the other hand, in the case of a solution containing both, an erasing activity of about 35% was obtained. From this result, in the case of a liquid containing both citrulline and carboxymethylchitin, it was confirmed that the hydroxy radical scavenging activity in each case increased synergistically.

(Experimental example 4)
In this example, a chitosan pyrrolidone carboxylate having a concentration of 0.1% was used in place of the partially myristoylated chitosan pyrrolidone carboxylate of Example 2 as a chitosan derivative. The concentration of citrulline was the same as in Examples 2 and 3. Both were mixed to prepare a composition for suppressing active oxygen, and the preparation method was the same as in Examples 1 to 3.
For the composition for suppressing active oxygen of this example, the hydroxy radical scavenging activity was measured in the same manner as in Examples 1 to 3, and a solution containing only 2% citrulline (Comparative Example 4-1) and chitosan pyrrolidone carboxylate The hydroxy radical scavenging activity of a solution containing only 0.1% (Comparative Example 4-2) was measured in the same manner and compared with the composition for suppressing active oxygen of this Example.

Table 4 shows the elimination rate for the generated hydroxy radicals.

  As is apparent from Table 4, about 22% of the scavenging activity was obtained in Comparative Example 4-1 of the solution containing only citrulline, and about 15% in Comparative Example 4-2 of the solution containing only chitosan pyrrolidone carboxylate. The erasing activity was obtained. On the other hand, in the case of a solution containing both, an erasing activity of about 41% was obtained. From this result, in the case of a liquid containing both citrulline and chitosan pyrrolidone carboxylate, it was confirmed that the hydroxy radical scavenging activity in each case increased synergistically.

(Experimental example 5)
In this example, theanine having a concentration of 2% was used as an amino acid instead of citrulline of Example 2. The type and concentration of the chitosan derivative were the same as in Example 2. Both were mixed to prepare a composition for suppressing active oxygen. The preparation method was the same as in Examples 1 to 4.
For the composition for suppressing active oxygen of this example, the hydroxy radical scavenging activity was measured in the same manner as in Examples 1 to 4, and a solution containing only 2% of theanine (Comparative Example 5-1) and partially myristoylated chitosan pyrrolidone The hydroxy radical scavenging activity of a solution containing only 0.05% carboxylate (Comparative Example 5-2) was measured in the same manner and compared with the composition for suppressing active oxygen of this Example.

Table 5 shows the extinction ratio with respect to the generated hydroxy radical.

  As is clear from Table 5, about 20% erasing activity was obtained in Comparative Example 5-1, and about 28% erasing activity was obtained in Comparative Example 5-2. On the other hand, in the case of a solution containing both, an erasing activity of about 56% was obtained. From this result, in the case of a liquid containing both theanine and partially myristoylated chitosan pyrrolidone carboxylate, it was confirmed that the hydroxy radical scavenging activity in each case increased synergistically.

(Experimental example 6)
In this example, theanine having a concentration of 2% was used as the amino acid, and the type and concentration of the chitosan derivative were the same as those in Example 3. Both were mixed to prepare a composition for suppressing active oxygen, and the preparation method was the same as in Examples 1 to 5.
About the active oxygen suppression composition of this example, the hydroxy radical scavenging activity was measured in the same manner as in Examples 1 to 5, and a solution containing only 2% of theanine (Comparative Example 6-1) and carboxymethyl chitin 0.1% The hydroxy radical scavenging activity of a solution containing only (Comparative Example 6-2) was measured in the same manner and compared with the composition for suppressing active oxygen of this Example.

Table 6 shows the erasure rate for the generated hydroxy radicals.

  As is clear from Table 6, about 20% erasing activity was obtained in Comparative Example 6-1 and about 8% erasing activity was obtained in Comparative Example 6-2. In contrast, in the case of a solution containing both, an erasing activity of about 33% was obtained. From this result, in the case of a liquid containing both theanine and carboxymethylchitin, it was confirmed that the scavenging activity of each hydroxy radical increased synergistically.

(Experimental example 7)
In this example, theanine having a concentration of 2% was used as the amino acid, and the type and concentration of the chitosan derivative were the same as those in Example 4. Both were mixed to prepare a composition for suppressing active oxygen, and the preparation method was the same as in Examples 1 to 5.
About the composition for suppressing active oxygen of this example, the hydroxy radical scavenging activity was measured in the same manner as in Examples 1 to 6, and a solution containing only 2% theanine (Comparative Example 7-1) and chitosan pyrrolidone carboxylate The hydroxy radical scavenging activity of a solution containing only 0.1% (Comparative Example 7-2) was measured in the same manner and compared with the composition for suppressing active oxygen of this example.

Table 7 shows the erasure rate for the generated hydroxy radicals.

  As is clear from Table 7, about 20% erasing activity was obtained in Comparative Example 7-1 and about 15% erasing activity was obtained in Comparative Example 7-2. On the other hand, in the case of a solution containing both, an erasing activity of about 40% was obtained. From this result, in the case of a liquid containing both theanine and chitosan pyrrolidone carboxylate, it was confirmed that the hydroxy radical scavenging activity in each case increased synergistically.

(Comparative Example 8)
Instead of the amino acids of Examples 2 and 5, arginine at a concentration of 2% was used. The type and concentration of the chitosan derivative were the same as in Examples 2 and 5. Both were mixed to prepare a composition for suppressing active oxygen, and the preparation method was the same as in Examples 1 to 7.
For the composition of Comparative Example 8, the hydroxy radical scavenging activity was measured in the same manner as in Examples 1 to 7 (Comparative Example 8-1), a solution containing only 2% of arginine (Comparative Example 8-2), and partial myristoylation The hydroxy radical scavenging activity of a solution containing only 0.05% chitosan pyrrolidone carboxylate (Comparative Example 8-3) was similarly measured and compared.

Table 8 shows the erasure rate for the generated hydroxy radicals.

  As is apparent from Table 8, about 16% erasing activity was obtained in Comparative Example 8-2, and about 28% erasing activity was obtained in Comparative Example 8-3. On the other hand, about 41% of erasing activity was obtained in Comparative Example 8-1 including both. From this result, it was confirmed that in the case of a liquid containing both arginine and partially myristoylated chitosan pyrrolidone carboxylate, the hydroxy radical scavenging activity in each case does not increase synergistically.

(Comparative Example 9)
The same arginine as in Comparative Example 8 was used, and the types and concentrations of chitosan derivatives were the same as in Examples 3 and 6. Both were mixed to prepare a composition for suppressing active oxygen, and the preparation method was the same as in Examples 1 to 7.
For the composition of Comparative Example 9, the hydroxy radical scavenging activity was measured in the same manner as in Examples 1 to 7 (Comparative Example 9-1), a solution containing only 2% of arginine (Comparative Example 9-2), and carboxymethyl chitin The hydroxy radical scavenging activity of a solution containing only 0.1% (Comparative Example 9-3) was similarly measured and compared.

Table 9 shows the erasure rate for the generated hydroxy radicals.

  As is apparent from Table 9, about 16% of the erasing activity was obtained in Comparative Example 9-2, and about 9% of the erasing activity was obtained in Comparative Example 9-3. On the other hand, in Comparative Example 9-1 including both, an erasing activity of about 22% was obtained. From this result, it was confirmed that in the case of a liquid containing both arginine and carboxymethyl chitin, the hydroxy radical scavenging activity in each case alone does not increase synergistically.

(Comparative Example 10)
The same arginine as in Comparative Examples 8 and 9 was used, and the type and concentration of the chitosan derivative were the same as in Examples 4 and 7. Both were mixed to prepare a composition for suppressing active oxygen, and the preparation method was the same as in Examples 1 to 7.
For the composition of Comparative Example 10, the hydroxy radical scavenging activity was measured in the same manner as in Examples 1 to 7 (Comparative Example 10-1), a solution containing only 2% of arginine (Comparative Example 10-2), and chitosan pyrrolidone carboxylic The hydroxy radical scavenging activity of a solution containing only 0.1% of the acid salt (Comparative Example 10-3) was measured and compared in the same manner.

Table 10 shows the elimination rate for the generated hydroxy radicals.

  As is clear from Table 10, about 16% erasing activity was obtained in Comparative Example 10-2, and about 15% erasing activity was obtained in Comparative Example 10-3. On the other hand, in Comparative Example 10-1 including both, an erasing activity of about 28% was obtained. From this result, it was confirmed that in the case of a liquid containing both arginine and chitosan pyrrolidone carboxylate, the hydroxy radical scavenging activity in each case alone does not increase synergistically.

The results of Examples 2 to 7 and Comparative Examples 8 to 10 are summarized in Table 11 below. In Table 11, ◯ indicates that a synergistic effect is observed, Δ indicates that a synergistic effect is not necessarily recognized, and Δ- ◯ indicates that a synergistic effect is substantially recognized.

  That is, as shown in Table 11, the hydroxy radical scavenging activity of a mixture of the amino acids citrulline or theanine and chitosan or chitin derivative increased synergistically compared to the single hydroxy radical scavenging activity, but arginine and The hydroxy radical scavenging activity of the mixture with chitosan or chitin derivative did not increase synergistically compared to the single hydroxy radical scavenging activity.

(Example 8)
In this example, a DNA damage inhibitory action of a mixture of an amino acid and chitosan or chitin derivative was tested. The test substances 0.2% citrulline and 0.05% partially myristoylated carboxymethyl chitosan, 20 mM Tris-Hcl (pH 7.4), 80 ng / μL pUC18 plasmid DNA, 2 mM 50 μM EDTA-Na-Fe (III) A solution with a total amount of 20 uL was adjusted to 8 mM hydrogen peroxide and kept at 25 ° C. After 2 hours, 1/2 equivalent of gel loading buffer (0.25% BPB, 1 mM EDTA, 30% glycerol) was added to the reaction solution, and electrophoresis was performed using 1% agarose gel containing ethidium bromide and TBE (× 0.5). After the electrophoresis, the agarose gel was irradiated with ultraviolet rays, and a photograph of the electrophoresis result was taken. The size of each band was quantified by ATTO Lanc & Spot Analyzer.

On the other hand, electrophoresis was performed in the same manner without adding a test substance, a photograph of the electrophoresis result was taken, and the size of each band was similarly quantified. The inhibition rate of DNA damage was determined from the quantitative values when the test substance was added and when it was not added. The inhibition rate is expressed by the following equation.
Inhibition rate (%) = [1- (quantitative value of the band when the test substance is added) / (quantitative value of the band when the test substance is not added)] × 100

  By obtaining this inhibition rate, it can be confirmed how much the degree to which the pUC18 plasmid DNA is damaged by hydroxy radicals generated from hydrogen peroxide is inhibited by the test substance. The results are shown in Table 12.

In this example, as shown in Table 12, the inhibition rate was 25%, and a very excellent result was obtained.

Example 9
In this example, a mixture of 0.2% concentration of theanine and 0.05% concentration of carboxymethyl chitin was used as the test substance. A DNA damage inhibitory action was tested in the same manner as in Example 8. In this example, as shown in Table 12, the inhibition rate was 45%, and as in Example 8, a very excellent result was obtained.

(Comparative Example 11 )
Citrulline having a concentration of 0.2% was used as a test substance. The DNA damage inhibitory action was tested in the same manner as in Examples 8 and 9. In Comparative Example 11 , as shown in Table 12, the inhibition rate was 16%, and a certain degree of inhibition was observed, but the inhibition rate was inferior compared to Example 8.

(Comparative Example 12 )
Theanine having a concentration of 0.2% was used as a test substance. The DNA damage inhibitory action was tested in the same manner as in Examples 8 and 9. In Comparative Example 12 , the inhibition rate was 29% as shown in Table 12, and a certain degree of inhibition was observed, but the inhibition rate was inferior to Example 9.

(Comparative Example 13 )
Cysteine having a concentration of 0.2% was used as a test substance. The DNA damage inhibitory action was tested in the same manner as in Examples 8 and 9. In Comparative Example 13 , as shown in Table 12, the inhibition rate was 5% or less, and almost no inhibition effect was observed.

(Comparative Example 14 )
Arginine with a concentration of 0.2% was used as a test substance. The DNA damage inhibitory action was tested in the same manner as in Examples 8 and 9. In Comparative Example 14 , as shown in Table 12, the inhibition rate was 5% or less, and almost no inhibition effect was observed.

(Prescription Example 1)
This prescription example is a prescription example of an essence as an example of a cosmetic, and its composition is as follows.
Ingredient Amount (% by mass)
(1) Citrulline 2.0
(2) Partially myristoylated chitosan pyrrolidone carboxylate 1% aqueous solution (Product name: PM-chitosan) 20.0
(3) Acetylcitrulline 0.5
(4) Glycerin 10.0
(5) Hydroxyethyl cellulose 0.5
(6) Methylparaben 0.1
(7) Purified water remaining

  The components (1) to (3) are uniformly heat-treated, and are subjected to sonication or high-pressure emulsification treatment to be lyophilized to be combined. Essence was prepared by gradually adding and dissolving this complexed product into the stirred and melted product obtained by mixing and stirring the components (4) to (7).

(Prescription example 2)
This formulation example is a formulation example of a lotion as an example of cosmetics, and the composition thereof is as follows.
Ingredient Amount (% by mass)
(1) Theanine 1.5
(2) Acetylhistidine 0.5
(3) Carboxymethyl chitosan 0.2
(4) Partially myristoylated chitosan pyrrolidone carboxylate 1% aqueous solution (Product name: PM-chitosan) 10.0
(5) Butylene glycol 10.0
(6) Glycerin 5.0
(7) Citric acid 0.01
(8) Methylparaben 0.2
(9) Purified water remaining

  The components (1) to (4) are uniformly heat-treated, and are subjected to sonication or high-pressure emulsification treatment to be lyophilized to be combined. A lotion was prepared by gradually adding and dissolving this complexed product to the stirred and melted product obtained by mixing and stirring the components (5) to (9).

(Prescription Example 3)
This prescription example is a prescription example of an emulsified foundation as an example of a cosmetic, and its composition is as follows.
Ingredient Amount (% by mass)
(1) Liquid paraffin 2.0
(2) Isopropyl myristate 3.0
(3) Squalane 7.0
(4) Petrolatum 2.0
(5) Cetanol 1.5
(6) Partially myristoylated chitosan lactate 0.2
(7) Chitosan pyrrolidone carboxylate 0.1
(8) N-dicarboxymethyl chitosan 0.1
(9) Yellow iron oxide 4.0
(10) Talc 5.5
(11) Titanium oxide 5.0
(12) Citrulline 0.5
(13) Theanine 1.0
(14) Glycerin 5.0
(15) Methylparaben 0.1
(16) Remaining purified water

  The components (1) to (5) were added to the heat-treated components (6) to (13), and an emulsion foundation was prepared by emulsification by homomixer treatment (8500 rpm, treatment for 20 minutes).

(Prescription Example 4)
This formulation example is a formulation example of an emulsified mascara as an example of a cosmetic, and the composition thereof is as follows.
Ingredient Amount (% by mass)
(1) Liquid paraffin 5.0
(2) Beeswax 15.0
(3) Behenyl alcohol 1.0
(4) Petrolatum 2.0
(5) Cetanol 1.5
(6) Citrulline 1.0
(7) Partially myristoylated chitosan pyrrolidone carboxylate 1% aqueous solution (Product name: PM-chitosan [Pierce Co., Ltd.]) 20.0
(8) Glycerin 1.0
(9) Methylparaben 0.2
(10) Black iron oxide 5.0
(11) Talc 2.5
(12) Fine particle titanium oxide 1.0
(13) Nylon powder 4.0
(14) Hydroxyethyl cellulose 0.5
(15) Purified water remaining

  To the heat-treated components (6) to (15), the oil phase composition (+) of (1) to (5) dissolved by heating is added, and the mixture is adjusted to pH 4.8 by emulsification by homomixer treatment. A weakly acidic water-resistant O / W emulsion was prepared.

  The composition of the present invention is an external skin skin preparation for suppressing active oxygen, especially a skin skin aging agent such as wrinkles and stains, and a skin radical agent that suppresses hydroxy radicals having a high effect on skin cell damage such as rough skin and inflammatory acne. Can be widely applied to.

The graph which shows the synergistic effect of the elimination rate with respect to the hydroxyl radical of a citrulline and a partial myristoylated chitosan pyrrolidone carboxylate.

Claims (3)

Activity comprising at least one amino acid of citrulline or theanine and a derivative of chitin or chitosan of at least one of partially myristoylated chitosan pyrrolidone carboxylate, carboxymethyl chitin, or chitosan pyrrolidone carboxylate Composition for suppressing oxygen. A skin external preparation comprising the composition for suppressing active oxygen according to claim 1 . A cosmetic comprising the composition for suppressing active oxygen according to claim 1 .