KR20160031081A

KR20160031081A - complex comprising water-soluble polysaccharide and antioxidant

Info

Publication number: KR20160031081A
Application number: KR1020140120071A
Authority: KR
Inventors: 이종휘; 안수환; 칸타파; 이재휘; 박주현; 장석태
Original assignee: 중앙대학교 산학협력단
Priority date: 2014-09-11
Filing date: 2014-09-11
Publication date: 2016-03-22

Abstract

The present invention relates to a complex comprising a water-soluble polysaccharide and an antioxidant, a manufacturing method thereof, and a usage thereof. The water-soluble polysaccharide-antioxidant complex of the present invention chemically links a water-soluble polysaccharide and an antioxidant, while maintaining unique activities of each material. Also, the complex has excellent dissolvability and adhesion to water, thereby being used in various fields. The water-soluble polysaccharide-antioxidant complex has a water-soluble polysaccharide selected from the group consisting of hyaluronic acid and pectine, and an antioxidant having a hydroxy group linked by ether linkage.

Description

Complexes comprising water-soluble polysaccharides and antioxidants {

The present invention relates to a complex comprising a water-soluble polysaccharide and an antioxidant, a process for their preparation and their use.

The water-soluble polysaccharide is a natural water-soluble polymer which is a repeating unit constituted by a saccharide, and has been used in various fields due to its physiological activity. For example, hyaluronic acid has been widely used as a component of medicines, foods, or cosmetics due to its unique physiological activity. In addition, pectin is nutritionally known for its various physiological activities. As it dissolves in water, it functions as a water-soluble dietary fiber that is not degraded by digestive enzymes in the body, thereby lowering blood cholesterol and reducing glucose intolerance in diabetic patients (Tinker et al , 1994).

On the other hand, a reactive oxygen species (ROS) refers to a reactive, highly active oxygen species containing oxygen. Low concentration of active oxygen weakens cell proliferation, etc., but active oxygen above a certain concentration may cause mutations, cell death, carcinogenesis and aging. Photo-aging can be caused by ultraviolet light, especially at the body parts exposed to sunlight. When a large amount of ultraviolet light is exposed, a high concentration of active oxygen is produced in the skin, and then the antioxidant defense system collapses.

Antioxidants are used in various medicinal and cosmetic compositions because they act to capture free radicals. Antioxidants are classified into enzymes, macromolecules, small molecules and hormones. Various compounds such as glutathione oxidase, albumin, hesperidin, ascorbic acid, rutin, catechin, retinol, glutathione and melatonin are known. There are also antioxidant enzymes such as superoxide dismutase (SOD) to protect the body against reactive oxygen species in the human body, and there are also antioxidants such as vitamin E, vitamin C and glutathione which are ingested from food. They eliminate free radicals and inhibit the destruction of other cells. After eliminating free radicals, they regenerate antioxidant enzymes and double their antioxidant capacity. By supplementing antioxidants with excellent antioxidant ability from the outside, the antioxidant power can be increased to minimize the harmfulness of active oxygen.

Until now, there has not been known a complex in which water-soluble polysaccharides and antioxidants are chemically bonded, which can exert their intrinsic activity of water-soluble polysaccharides and antioxidants, respectively.

Accordingly, an object of the present invention is to provide a complex in which a water-soluble polysaccharide and an antioxidant are chemically bonded, capable of exerting intrinsic activity of each of a water-soluble polysaccharide and an antioxidant, a method for producing the complex, and a use thereof.

To achieve the above object, the present invention provides a water-soluble polysaccharide-antioxidant complex having a hydroxyl group-containing water-soluble polysaccharide and an antioxidant having a hydroxy group bonded through an ether bond.

The present invention also provides a process for preparing a water-soluble polysaccharide-antioxidant complex comprising reacting a water-soluble polysaccharide having a hydroxy group and an antioxidant having a hydroxy group with an epoxy crosslinking agent.

The present invention also provides a cosmetic composition comprising a water-soluble polysaccharide-antioxidant complex.

The water-soluble polysaccharide-antioxidant complex of the present invention has an advantage that the water-soluble polysaccharide and the antioxidant are chemically bonded and the intrinsic activity of the substance is maintained simultaneously. Further, it is excellent in water solubility and adhesiveness and can be utilized in various fields.

Fig. 1 shows the results of absorbance measurement of the hyaluronic acid-polyphenol complex prepared in Preparation Example 1. Fig.
Fig. 2 shows the results of the adhesion test of the hyaluronic acid-polyphenol composite prepared in Preparation Example 1. Fig.
Fig. 3 shows the results of absorbance measurement of the pectin-polyphenol complex prepared in Preparation Example 2. Fig.
FIG. 4 shows the results of an adhesion test of a pectin-polyphenol composite according to an example of the present invention.
FIG. 5 shows the results of absorbance measurement of the hyaluronic acid-ascorbic acid complex prepared in Comparative Example 1. FIG.
Fig. 6 shows the absorbance measurement results of the pectin-ascorbic acid complex prepared in Comparative Example 2. Fig.

The present invention provides a water-soluble polysaccharide-antioxidant complex in which a water-soluble polysaccharide having a hydroxy group and an antioxidant having a hydroxy group are bonded by an ether bond.

In the water-soluble polysaccharide-antioxidant complex of the present invention, the hydroxy group of the water-soluble polysaccharide and the hydroxy group of the antioxidant are bonded by an ether bond. For example, when the water-soluble polysaccharide is pectin or hyaluronic acid and the antioxidant is catechin, quercetin, rutin or a polyphenol of hesperidin, the water-soluble polysaccharide and antioxidant may be bonded by an ether bond as shown in the following reaction formula.

[Reaction Scheme 1] Hyaluronic acid-hesperidin complex

[Reaction Scheme 2] Hyaluronic acid-catechin complex

[Reaction Scheme 3] Hyaluronic acid-quercetin complex

[Reaction Scheme 4] Hyaluronic acid-rutin complex

[Reaction Scheme 5] Pectin-catechin complex

Scheme 6 Pectin-quercetin complex

[Reaction Scheme 7] Pectin-Rutin complex

Scheme 8 Pectin-Hesperidin complex

In one embodiment, the water-soluble polysaccharide having a hydroxy group includes, but is not limited to, hyaluronic acid, hyaluronate, poly-gamma-glutamic acid, polygamat glutamate, agar, Alginic acid, alginate, carrageenan, furcellaran, pectin, arabic gum, karaya gum, tragacanth gum ( gum arabicum, tragacanth gum, ghatti gum, guar gum, locust bean gum, psyllium seed gum, gleatin, chitin, dextran, Chondroitin-4-sulfate, chondroitin-6-sulfate, and starch. The term " chondroitin-4-sulfate, chondroitin- It can be more than one.

In one embodiment, the antioxidant having a hydroxy group may be, but is not limited to, polyphenol. Polyphenols include, but are not limited to, hesperidin, quercetin, rutin, catechin, and the like. When polyphenol is used as an antioxidant, the water-soluble polysaccharide-antioxidant complex of the present invention can be referred to as a water-soluble polysaccharide-polyphenol complex.

In one embodiment, the ether linkage may be by an epoxy crosslinking agent, although not limited thereto.

In one embodiment, the epoxy cross-linker includes, but is not limited to, epichlorohydrin, epibromohydrin, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, Ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycolide diglycidyl ether (polyethylene glycol diglycidyl ether) glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, Glycerol polyglycidyl ether, trimethlypropane polyglycidyl ether, bis (2,3-epoxypropoxy) ethylene, pentaerythritol Polyglycidyl ether, sorbitol polyglycidyl ether, and the like. &Lt; Desc / Clms Page number 7 >

In one embodiment, the antioxidant may be included in an amount of 3 to 60 wt% based on the total weight of the composite. When the content of the antioxidant is within the above range, the intrinsic activity of the water-soluble polysaccharide and the antioxidant ability of the antioxidant can be effectively maintained. If the content of the antioxidant is less than 3% by weight, the antioxidative effect can not be expected. If the content is more than 60% by weight, the water-soluble polysaccharide, that is, pectin or hyaluronic acid backbone may become unstable.

In one embodiment, the cohesive strength of the composite is superior to that of the water-soluble polysaccharide, and specifically may be 2, 3, 4, or 5 times or more. Within the above-mentioned range, when used as a cosmetic preparation, it is possible to obtain a stable feeling when applied to skin or the like, and it is easy to transfer the whitening and wrinkle-improving ingredients contained in the cosmetic into the skin. In addition, it can increase drug delivery efficiency when used for drug delivery, and can be used for removing other metals.

The present invention also provides a process for preparing a water-soluble polysaccharide-antioxidant complex comprising reacting a water-soluble polysaccharide having a hydroxy group and an antioxidant having a hydroxy group with an epoxy crosslinking agent. For example, the water-soluble polysaccharide-antioxidant complex can be prepared according to the above-mentioned Reaction Schemes 1 to 8, wherein the chloride portion of the epoxy crosslinking agent and the hydroxyl group of the antioxidant react to form an ether bond, and the epoxide group And the hydroxyl group of the water-soluble polysaccharide may react to form an ether bond. In the production method according to the present invention, the structure of the antioxidant is not destroyed during the reaction, so that the antioxidant ability of the antioxidant can be maintained.

In one embodiment, the antioxidant having a hydroxy group can be a polyphenol selected from the group consisting of hesperidin, quercetin, rutin, and catechin.

In one embodiment, the antioxidant may be included in an amount of 3 to 60 wt% based on the total weight of the composite.

The present invention also provides the use of the water soluble polysaccharide-antioxidant complexes. The water-soluble polysaccharide-antioxidant complex of the present invention can exert both the intrinsic activity of the water-soluble polysaccharide and the antioxidant power of the antioxidant, as shown in the following Experimental Examples, and can be utilized in various fields. For example, the complex of the present invention may be used as an active ingredient per se, or may be used as a carrier of an active ingredient by carrying the active ingredient in the complex. When used as a carrier, deterioration due to oxidation of the active ingredient can be prevented, which is effective.

In one embodiment, the water soluble polysaccharide-antioxidant complex of the present invention can be used as a cosmetic composition. Accordingly, the present invention provides a cosmetic composition comprising a water-soluble polysaccharide-antioxidant complex. In one embodiment, the complex of the present invention can be utilized as a material for skins, mask packs, and the like. As described above, the complex of the present invention can exhibit physiological activity and antioxidative power inherent to the water-soluble polysaccharide, and can be used as an effective ingredient of the cosmetic composition itself. In addition, it can be utilized as an encapsulation material for supporting an active ingredient. In this case, oxidation of the active ingredient can be prevented and the preservability can be improved.

Hereinafter, the present invention will be described in detail with reference to examples. The following examples illustrate the invention and are not intended to limit the scope of the invention. These embodiments are provided so that the disclosure of the present invention is not limited thereto and that those skilled in the art will fully understand the scope of the present invention and that the present invention is not limited by the scope of the claims Only.

[ Manufacturing example 1] Production of hyaluronic acid-polyphenol complex

0.53 mol (0.20 g) of hyaluronic acid was dissolved in distilled water at 0.67 wt% and maintained at 40 DEG C to prepare a hyaluronic acid solution. 1.59 moles of polyphenol (hesperidin, rutin, quercetin, catechin) was dissolved in sodium hydroxide (NaOH), and epichlorohydrin was added thereto. . When the first reaction was completed, the first reaction product and the hyaluronic acid solution were mixed and maintained at 40 ° C., followed by a second reaction for 5 hours with stirring. In this case, 5-20 mmol of thiourea can be used as a stabilizer. After the completion of the reaction, the mixture was precipitated with ethanol (1 L) and dissolved again in water (3 times). The dialyzate was then dialyzed with distilled water to a membrane with a molecular aliquot (MWCO) of 14k (3 days) to remove the low molecular weight reactant and oligomer. The purified solution was dried by lyophilization to give hyaluronic acid-hesperidin conjugates (HAHS-3), hyaluronic acid-catechin conjugates (HACH-3), hyaluronic acid-quercetin conjugates (HAQH-3) -rutin < / RTI > conjugates).

[ Manufacturing example 2] Production of pectin-polyphenol complex

1.02 mmol (based on monomer) of pectin was dissolved in sodium hydroxide (NaOH) at 2.5 wt% and maintained at 40 캜 to prepare a pectin solution. 3.06 mmol of polyphenol (hesperidin, rutin, quercetin, catechin) was dissolved in sodium hydroxide (NaOH), and epichlorohydrin was added thereto. . After the first reaction, the first reaction product and the pectin solution were mixed and maintained at 40 ° C, followed by a second reaction for 5 hours with stirring. In this case, 0.001 wt% to 1 wt% of thiourea and sodium thiosulfate can be used as stabilizers. After the completion of the reaction, the mixture was precipitated with ethanol (1 L) and dissolved again in water (3 times). The dialyzate was then dialyzed with distilled water to a membrane with a molecular aliquot (MWCO) of 14k (3 days) to remove the low molecular weight reactant and oligomer. (Pectin-catechin conjugates), pectin-quercetin conjugates (PQH-3), and pectin-rutin conjugates (PRT-3) &Lt; / RTI > was obtained.

[ Comparative Example 1] hyaluronic acid-ascorbic acid ( Ascrobic acid ) Composite Manufacturing

0.53 mol of hyaluronic acid was dissolved in distilled water at 0.67 wt% and maintained at 40 DEG C to prepare a hyaluronic acid solution. 1.59 mol of ascorbic acid was dissolved in sodium hydroxide (NaOH), and epichlorohydrin was added thereto. And the first reaction was carried out for 30 minutes. When the first reaction was completed, the first reaction product and the hyaluronic acid solution were mixed and maintained at 40 ° C., followed by a second reaction for 5 hours with stirring. In this case, 5-20 mmol of thiourea can be used as a stabilizer. After the completion of the reaction, the mixture was precipitated with ethanol (1 L) and dissolved again in water (3 times). The dialyzate was then dialyzed with distilled water to a membrane with a molecular aliquot (MWCO) of 14k (3 days) to remove the low molecular weight reactant and oligomer. The purified solution was dried by lyophilization to obtain a complex named HAAA (hyaluronic acid-Ascrobic acid conjugates).

[ Comparative Example 2] pectin-ascorbic acid ( Ascrobic acid ) Composite Manufacturing

1.02 mmol of pectin was dissolved in sodium hydroxide (NaOH) at 2.5 wt% and maintained at 40 ° C to prepare a pectin solution. 3.06 mmol of ascorbic acid was dissolved in sodium hydroxide (NaOH), epichlorohydrin was added thereto, and the reaction was carried out for 30 minutes. After the first reaction, the first reaction product and the pectin solution were mixed and maintained at 40 ° C, followed by a second reaction for 5 hours with stirring. In this case, 0.001 wt% to 1 wt% of thiourea and sodium thiosulfate can be used as stabilizers. After the completion of the reaction, the mixture was precipitated with ethanol (1 L) and dissolved again in water (3 times). The dialyzate was then dialyzed with distilled water to a membrane with a molecular aliquot (MWCO) of 14k (3 days) to remove the low molecular weight reactant and oligomer. The purified solution was dried by lyophilization to obtain a complex named PAA (pectin - Ascrobic acid conjugates).

[ Experimental Example 1] Structure confirmation of hyaluronic acid-polyphenol complex

The structure of hyaluronic acid-polyphenol complex was confirmed by UV-Vis spectroscopy.

The hyaluronic acid-polyphenol complex prepared in Preparation Example 1 was dissolved in water and the absorbance was measured. As a control, hyaluronic acid was used to compare the ultraviolet absorbance of the hyaluronic acid-polyphenol complex.

The absorbance comparison results are shown graphically in FIG. In Fig. 1, HA represents hyaluronic acid, HAHS represents HAHS-3, HACH represents HACH-3, HAQH represents HAQH-3, and HART represents HART-3. In the hyaluronic acid-polyphenol complex, the absorbance at 200-400 cm- ^{1 was} similar to that of the polyphenols.

Analysis of UV-vis spectroscopy data showed that polyphenol and hyaluronic acid form a complex through covalent bonding.

[ Experimental Example 2] hyaluronic acid-polyphenol composite DPPH Radical Capture Ability check

1 mL of the hyaluronic acid-hesperidin complex solution dissolved in methanol was mixed with 3 mL of 0.1 mM DPPH solution in methanol. After 30 minutes, the absorbance at a wavelength of 517 nm was examined. The DPPH radical scavenging capacity was calculated according to the following equation (1). Data on DPPH radical scavenging ability according to concentration are shown in Table 1 below.

[Formula 1]

: Absorbance of antioxidants contained in the sample

: Absorbance of antioxidants dissolved in methanol

: Absorbance of DPPH solution

Table 1 shows the ability of the hyaluronic acid-hesperidin complex (HAHS-3) to absorb radicals.

As a result, as shown in Table 1, it was confirmed that the hyaluronic acid-hesperidin complex exhibited similar radical scavenging ability as that of hesperidin alone. These results indicate that antioxidative capacity inherent in hesperidin is maintained in the hyaluronic acid-hesperidin complex.

[ Experimental Example 3] Measurement of adhesion of hyaluronic acid-polyphenol complex

Catechol functional groups are known to have strong adhesion properties on organic / inorganic surfaces. Since the catechol functional group is also present in the phenol group present in the hyaluronic acid derivative, the uniaxial adhesion test was carried out to confirm the tackiness of the hyaluronic acid derivative. 1 wt% of the solution was applied to an OHP slide glass of 25 mm * 25 mm, laminated with another slide glass, and the force applied to separate the slide was measured. Shear strength was measured at room temperature and hydraulic test system was used. Instron 3344, instron, USA, shear mode was used to measure the strain rate at 5 mm / min, one side fixed to the load cell and the other side fixed to the actuator.

The results of adhesion measurement are shown in Fig. As shown in FIG. 2, all of the hyaluronic acid-polyphenol complexes exhibited adhesive strength three times higher than that of hyaluronic acid. This means that the catechol functionality of the hyaluronic acid in the hyaluronic acid-polyphenol complex is maintained intact.

[ Experimental Example 4] Identification of structure of pectin-polyphenol complex

UV-Vis spectroscopy confirmed the structure of the pectin-polyphenol complex.

The pectin-polyphenol complex prepared in Preparation Example 2 was dissolved in water and the absorbance was measured. As a control, pectin was used to compare the ultraviolet absorbance with the pectin-polyphenol complex.

The absorbance comparison results are shown graphically in FIG. 3, pectin represents pectin, PHS represents PHS-3, PCH represents PCH-3, PQH represents PQH-3, and PRT represents PRT-3.

The pectin used as a control group had a small ultraviolet absorbance, but the pectin-polyphenol complex showed a very high absorbance at a wavelength of 200-400 cm ^-1 similar to the reacted polyphenols.

Analysis of UV-vis spectroscopy data showed that polyphenol and pectin were successfully coupled through covalent bonding.

[ Experimental Example 5] pectin-polyphenol composite DPPH Radical Capture Ability check

The radical scavenging ability of the pectin-polyphenol complex was confirmed in the same manner as in Experimental Example 2. The results are shown in Table 2 below.

Concentration (mg / ml) 0.125 0.25 0.5 1.0 DPPH scavenging effect (%) PHS 3.0 4.7 5.7 9.7 PQH 7.5 13.1 19.7 27.2 PRT 10.8 14.8 22.9 34.8 PCHJ 14.2 20.6 27.1 38.9

Table 2 shows the radical scavenging ability of the pectin-polyphenol complex.

As a result, as shown in Table 2, it was confirmed that the pectin-polyphenol complex improved the radical scavenging ability as the concentration of the complex increased. These results indicate that the antioxidative ability inherent to polyphenol is maintained in the pectin-polyphenol complex.

[ Experimental Example 6] Measurement of Adhesion Capacity of Pectin-Polyphenol Composite

Catechol functional groups are known to have strong adhesion ability on organic / inorganic surfaces. The phenol group present in the pectin derivative also has this catechol functionality. The uniaxial adhesion test was conducted to test the adhesive ability of pectin derivatives. A 3 wt% solution was applied to an OHP slide glass of 25 mm * 25 mm, laminated with another slide, and the force applied to separate the slide was measured. The shear force was measured at room temperature and the hydraulic machine test system was used. Instron 3344, instron, USA, shear mode was used to measure the strain rate at 5 mm / min, one side fixed to the load cell and the other side fixed to the actuator.

The results of adhesion measurement are shown in Fig. As shown in FIG. 4, all the pectin-polyphenol composites showed higher adhesive force than pectin. This means that in the pectin complex the catechol functionality of the pectin is maintained intact.

[ Experimental Example 7] hyaluronic acid-ascorbic acid ( Ascrobic acid ) Identification of the structure of the complex

The structure of hyaluronic acid-ascorbic acid complex (HAAA) was confirmed by UV-Vis spectroscopy.

The absorbance was measured after dissolving the hyaluronic acid-ascorbic acid complex (HAAA) prepared in Comparative Example 1 in water, and the UV absorbance of ascorbic acid (AA), the HART and the routine (RT) prepared in Preparation Example 1 were compared Respectively.

The absorbance comparison results are shown graphically in FIG.

AA (ascorbic acid) shows a large absorbance at a wavelength of 200-300 cm ^-1 , but HAAA bound to hyaluronic acid loses its absorption characteristics. This means that the chemical structure of AA is damaged during the reaction.

On the other hand, it can be confirmed that the routine (RT) maintains the UV characteristic even after being bound to hyaluronic acid (HART), which suggests that HART will have an antioxidative effect without damaging the chemical structure of RT.

[ Experimental Example 8] Pectin-ascorbic acid ( Ascrobic acid ) Identification of the structure of the complex

UV-Vis spectroscopy confirmed the structure of the pectin-ascorbic acid complex (PAA).

The pectin-ascorbic acid complex (PAA) prepared in Comparative Example 2 was dissolved in water and the absorbance was measured. Ascorbic acid, pectin, PRT prepared in Preparation Example 2, and Rutin trihydrate The UV absorbance was compared.

The absorbance comparison results are shown graphically in FIG.

AA (ascorbic acid) shows a large absorbance at 200-300 cm ^-1 wavelength, but PAA coupled with pectin loses its absorption characteristics. This means that the chemical structure of AA is damaged during the reaction.

On the other hand, Rutin trihydrate (RT) retains the UV characteristics even after conjugation with pectin (PRT), suggesting that PRT will have antioxidative effects without compromising the chemical structure of RT.

Claims

A water-soluble polysaccharide selected from the group consisting of hyaluronic acid and pectin, and a water-soluble polysaccharide-antioxidant complex in which an antioxidant having a hydroxy group is bonded by an ether bond.

The method according to claim 1,
The antioxidant is a polyphenol selected from the group consisting of hesperidin, quercetin, rutin and catechin.

The method according to claim 1,
Wherein the antioxidant is contained in an amount of 3 to 60% by weight based on the total weight of the composite.

The method according to claim 1,
Water-soluble polysaccharide-antioxidant complex is a water-soluble polysaccharide-antioxidant complex having an adhesive strength of at least twice that of a water-soluble polysaccharide.

A method for preparing a water-soluble polysaccharide-antioxidant complex comprising reacting a water-soluble polysaccharide selected from hyaluronic acid and pectin and an antioxidant having a hydroxy group with an epoxy crosslinking agent.

6. The method of claim 5,
An antioxidant is a polyphenol selected from the group consisting of hesperidin, quercetin, rutin, and catechin.

6. The method of claim 5,
The epoxy cross-linking agent is selected from the group consisting of epichlorohydrin, epibromohydrin, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, But are not limited to, 1,6-hexanediol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, But are not limited to, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyglycerol polyglycidyl ether, ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, Trimethylpentane polyglycidyl ether, bis (2,3-epoxypropoxy) ethylene, pentaerythritol polyglycidyl ether, and the like. And sorbitol polyglycidyl ether. The method for producing the water-soluble polysaccharide-antioxidant complex according to claim 1, wherein the water-soluble polysaccharide-antioxidant complex is at least one selected from the group consisting of sorbitol polyglycidyl ether and sorbitol polyglycidyl ether.

6. The method of claim 5,
Wherein the antioxidant is contained in an amount of 3 to 60% by weight based on the total weight of the composite.