KR101490089B1 - Skin protector material containing liquid citron by-product and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a skin-protecting material containing liquid citron by-product and to a manufacturing method thereof. The skin-protecting material containing liquid citron by-product according to the present invention comprises: 100 parts by weight of purified liquid citron by-product; 20 to 30 parts by weight of sodium hydroxide or potassium hydroxide at normality of 0.1 to 0.5 that has been diluted with water; and 1 to 10 parts by weight of citric acid. The skin-protecting material is manufactured by making glycosides into aglycones via hydrolysis and decompression-concentrating the product at 20 to 50 times higher concentration.

Description

TECHNICAL FIELD [0001] The present invention relates to a skin protective agent containing a liquid citron by-product and a method for producing the skin protective agent.

The present invention relates to a skin protecting agent material containing liquid citron by-products and a method for preparing the same, and more particularly, to a skin protecting agent material containing liquid citron by-products using a citron extract obtained from the processing of citron, And a manufacturing method thereof.

Among the byproducts generated in the process of processing citron, liquid citron by-products containing fruit juice have excellent functions such as physiological activity and contain a large amount of vitamin C, which is a sufficiently valuable raw material as a raw material for food or medicine. Research has been going on. In order to make functional products of citron by-products in the liquid state of citron in the prior art for use as such foods or already-used raw materials, the citron by-products of the liquid phase are firstly separated into powder or solid , And then concentrated using an organic chemical solvent such as ethanol, methanol, hexane and the like, and then subjected to a re-concentration process to remove the solvent. This re-condensation process has a problem in that the process is complicated and takes a lot of time, and the yield is low and the production efficiency is low. In addition, there is a problem that it is difficult to utilize citrus byproducts having high functionality due to the environmental pollution problem by using an organic chemical solvent in the extraction process after concentrating the liquid citron by-products.

KR 10-1325092 B1

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an eco-friendly functional materialization method which does not cause environmental pollution problem through a simple manufacturing process, And to provide a skin protecting agent material containing the liquid citron by-products and a method for producing the same.

In order to solve the above-mentioned problems, the skin protective agent containing the liquid citron by-product according to the present invention comprises 100 parts by weight of purified liquid citron by-products, 20 to 30 parts by weight of sodium hydroxide or potassium hydroxide aqueous solution diluted with water at a concentration of 0.1 to 0.5 normal And 1 to 10 parts by weight of citric acid. The glycoside is hydrolyzed to non-saccharified and then concentrated under reduced pressure.

Wherein the skin care agent material containing the liquid citrus by-products comprises at least one component selected from the group consisting of non-glycosylated flavonoids hesperetin and naringenin as main components, and their glycoside flavonoids selected from among naringin, isonarginine, hesperidin and neohesperidin And it is preferable that they contain at least one of them.

Wherein the skin care agent containing the liquid citrus by-products is applied to a cosmetic composition, a dermatological composition or a skin cleansing composition comprising alone or at least one other active compound, and when added to any one of the compositions, The anti-aging effect by wrinkle improvement using the function of inhibiting elastase which decomposes elastin which maintains the skin structure by adding 0.1 to 10 parts by weight of the anti-aging effect, Radical), and an effect of suppressing skin inflammation by inhibiting the expression of iNOS that produces nitric oxide (NO), which is an inflammatory factor that occurs during skin irritation.

Meanwhile, the method for preparing a skin care agent containing liquid citron by-products according to the present invention is characterized in that the citron by-product obtained in the process of citron processing is filtered using a filter paper or nonwoven fabric having an inner diameter of 0.5 to 50 μm to collect the liquid citron filtrate Liquid citron filtrate; collecting the collected liquid citron filtrate using a centrifuge at 300 to 3000 rpm to remove solid citron by-products remaining in the collected citron filtrate to obtain purified citron liquid by- 20 to 30 parts by weight of sodium hydroxide or potassium hydroxide aqueous solution having a concentration of 0.1 to 0.5 normal (N) diluted with water per 100 parts by weight of the purified liquid citron by-product are added to the prepared citron by-product, and the mixture is stirred at 70 to 90 ° C for 1 to 5 hours A step of preparing a hydrolyzate by heating the hydrolyzate to produce a hydrolyzate, Wherein the hydrolyzate is neutralized by adding 1 to 10 parts by weight of citric acid per 100 parts by weight of the hydrolyzate to the hydrolyzate to neutralize the hydrolyzate, and the concentrated hydrolyzate is concentrated to 20 to 50 times under reduced pressure to obtain a concentrated liquid citrus by- And a step of completing the skin care agent material to complete the skin care agent contained therein.

The finished skin protecting agent material contains at least one selected from among non-glycosylated flavonoids hesperetin and naringenin as main components, and at least one selected from the glycoside flavonoids such as naringin, isonarginine, hesperidin and neohesperidin And the like.

The pH of the hydrolyzate produced in the hydrolyzate preparation step is 7.5 to 10, and the pH of the hydrolyzate neutralized in the hydrolyzate neutralization step is preferably 5 to 8.

As described above, according to the skin protecting agent material containing the liquid citron by-products according to the present invention and the method for producing the same, the active ingredient of the glycoside having a low physiological activity effect is non-sugarized through hydrolysis to remove sugar, Antioxidant effect by wrinkle improvement by function of inhibiting elastase which decomposes elastin which maintains skin structure, antioxidant effect by reducing free radical of free radical in human body, There is provided a skin protecting agent material containing a liquid citron by-product having a function such as a skin protecting effect for suppressing the inflammation of the skin by inhibiting the expression of iNOS that produces NO (nitric oxide) .

In addition, it is not necessary to concentrate the solid material or the powder in the process of producing the skin care agent containing the liquid citron by-product, but the citron by-product of the liquid is hydrolyzed and then concentrated through the concentration step under reduced pressure. Thus, the conventional ethanol, methanol, It is not necessary to use an organic chemical solvent such as an organic solvent, Through environmentally friendly manufacturing processes There is an advantageous effect that mass production of a skin care agent material containing liquid citron by-products can be easily performed.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a manufacturing step of a method for manufacturing a skin care agent material containing a liquid citron by-product according to an embodiment of the present invention;
2 is a graph and a table for confirming the non-glycosylation of a glycoside in the production of a hydrolyzate by hydrolysis in the process of producing a skin protective agent containing liquid citron by-products according to Example 1 of the present invention,
FIG. 3 is a graph illustrating the anti-aging (wrinkle improvement) performance test of a skin protective agent containing liquid citron by-products according to Example 1 of the present invention,
FIG. 4 is a graph showing a comparative test of antioxidative activity of a skin protective agent containing a liquid citron by-product according to Example 1 of the present invention,
FIG. 5 is a graph showing a skin protection effect comparative test result of a skin protective agent containing a liquid citron by-product according to Example 1 of the present invention. FIG.

Specific details of other embodiments are included in the detailed description and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish them, will become apparent by reference to the embodiments described in detail below with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various other forms, and it should be understood that the present embodiment is intended to be illustrative only and is not intended to be exhaustive or to limit the invention to the precise form disclosed, To fully disclose the scope of the invention to a person skilled in the art, and the invention is only defined by the scope of the claims.

The embodiments described herein will be described with reference to the ideal manufacturing steps flowchart of the present invention shown in Fig.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a skin protective agent containing liquid citron by-products according to an embodiment of the present invention will be described in detail.

The skin protective agent containing the liquid citron by-product according to an embodiment of the present invention may include 100 parts by weight of purified liquid citron by-product, 20 to 30 parts by weight of sodium hydroxide or potassium hydroxide aqueous solution diluted with water at a concentration of 0.1 to 0.5 normal (N) And 1 to 10 parts by weight of citric acid. After the glycoside is hydrolyzed to non-saccharified, it is concentrated 20 to 50 times under reduced pressure.

The skin protective agent containing liquid citrus by-products according to an embodiment of the present invention contains at least one component selected from among non-glycosylated flavonoids hesperetin and naringenin as major components, and their glycoside flavonoids such as naringin, isonarginine, A cosmetic composition containing at least one selected from the group consisting of salicylic acid, hesperidin and neohesperidin and containing at least one other active compound, a medicament such as ointment or atopic cream, a liquid ointment, The present invention is applicable to a skin scientific composition or a skin cleansing composition which is applied to any one of the above compositions and is added in a weight ratio of 0.1 to 10 parts by weight per 100 parts by weight of the composition to decompose elastin Ela stasis), antioxidative effect using the function of reducing Free Radical of the active oxygen in the human body, nitric oxide (NO) which is an inflammation factor which occurs during skin irritation, It is possible to obtain at least one of the effects of inhibiting the expression of iNOS to be produced and protecting skin inflammation.

If less than 0.1 part by weight of the skin protecting agent material containing the liquid citron by-product according to the embodiment of the present invention is added to 100 parts by weight of the composition, anti-aging, antioxidant or skin protection effect can not be obtained effectively. Can lead to changes in the physical properties of the composition due to skin toxicity and formulation stability problems. The skin care product material containing the liquid citron by-products according to the present invention can be manufactured into a cleansing product or a soap preparation containing a cosmetic composition, a dermatological composition and a surfactant using a method disclosed in the related art.

Hereinafter, a method for manufacturing a skin care agent containing liquid citron by-products according to an embodiment of the present invention will be described in detail with reference to FIG.

FIG. 1 is a flow chart showing a manufacturing step of a method for manufacturing a skin care agent containing a liquid citron by-product according to an embodiment of the present invention.

A method for preparing a skin care agent containing a liquid citron by-product according to an embodiment of the present invention starts with a step (S10) of collecting liquid citron filtrate.

That is, in the processing such as pulverization, cutting and segregation of the harvested citron, the citron by-products of the liquid phase are collected by filtration using a filter paper or a nonwoven fabric having a pore size of 0.5 to 50 μm and the aggregated starch molecules are aggregated in a size of 0.5 to 50 μm or more Separate the solid citron filtrate.

If the filter paper or the nonwoven fabric has a pore size of less than 0.5 μm, the filtrate may not be filtered because the solid citron filtrate does not pass through the filter paper or the nonwoven fabric by blocking the inner filtration of the filtrate or nonwoven fabric. On the other hand, , The amount of the solid citron filtrate to be removed first becomes small. In the secondary centrifugation, the centrifugation for obtaining the citron by-product in the purified liquid is difficult due to the many solid citron by-products.

Then, it is subjected to a preparation step (S20) of refined liquid citron by-product.

That is, the liquid citron filtered firstly collected by filtration is subjected to second separation of the solid citron filtrate having a crystal size of less than 0.5 to 50 μm in which the starch molecules contained in the liquid citron filtrate are aggregated by using a centrifuge at 300 to 3000 rpm To obtain purified liquid citron by-products.

When the rotation speed per minute of the centrifugal separator is less than 300 rpm, the solid citron filtrate is not separated and sedimented. When the centrifugal separator is operated at a rate of more than 3000 rpm, the active ingredient contained in the liquid citron by-product other than the solid citron filtrate is separated A problem may be caused to be removed.

Then, the hydrolyzate preparation step (S30) is performed.

That is, 20 to 30 parts by weight of sodium hydroxide or potassium hydroxide aqueous solution of 0.1 to 0.5 normal concentration (N) diluted with water per 100 parts by weight of the prepared purified liquid citrus by-products are added and heated at 70 to 90 ° C for 1 to 5 hours to adjust the pH Is in the range of 7.5 to 10. In this process, sodium hydroxide or potassium hydroxide aqueous solution of less than 0.1 normal concentration is not hydrolyzed due to low alkalinity, and when it exceeds 0.5 normal concentration, relatively weak bonds of active ingredient in the citrus by-product of refined liquid are broken due to excessive basicity The components can be destroyed.

The non-solubilizing of the glycosides contained in the purified liquid citron by-products proceeds in the production of the hydrolyzate through the hydrolysis reaction, thereby increasing the efficacy of the functional active ingredient.

Thereafter, the hydrolyzate neutralization step (S40) is performed.

That is, 1 to 10 parts by weight of citric acid per 100 parts by weight of the purified liquid citron by-products is added to the hydrolyzate to neutralize the hydrolyzate to a pH of 5 to 8. The reason why the hydrolyzate is neutralized so as to have a pH of 5 to 8 is that when the pH is less than 5, the physical properties such as viscosity and properties of the composition can be changed when contained in the functional composition, and when the pH exceeds 8, There is a risk that the active ingredient in the refined liquid citron by-products can be decomposed by the above-mentioned method.

Thereafter, the hydrolyzate neutralized is removed from the hydrolyzate neutralized through an environmentally-friendly depressurization-concentrating process, not an organic chemical solvent, and concentrated under reduced pressure at 20- to 50-fold concentration to obtain a solution containing concentrated liquid or gel- The skin protecting agent material is completed (S50).

It is preferable that the skin protecting agent material prepared through this process is stored at -10 to 5 ° C.

≪ Example 1 >

The citron by-products of the liquid produced in the process of citron processing (cutting, crushing, seed selection) were firstly subjected to primary filtration using a 0.5 mm nonwoven fabric and the secondary filtered citron filtrate was centrifuged at 1500 rpm To separate the solid citron filtrate remaining in the liquid citron-filtered water to obtain a purified liquid citron-filtered byproduct. 20 kg of a 1 N aqueous sodium hydroxide solution diluted with water was added to 100 kg of the obtained purified liquid citron by-product and the mixture was heated to 90 ° C for 3 hours to obtain a hydrolyzate. The hydrolyzate is then neutralized by adding 1 kg of citric acid to the hydrolyzate to a pH of 7. Subsequently, the neutralized hydrolyzate is concentrated to 4 kg through an environmentally friendly depressurization and concentration process to complete the skin protective agent material containing the concentrated liquid citron by-products. Then, 4 kg of a skin protective agent containing liquid citron by-products concentrated in a 96 kg cream-based cosmetic composition is added to make a cream-based dermatological composition with a skin care agent containing liquid citron by-products.

FIG. 2 is a test graph and table for confirming the non-glycosylation of a glycoside in the production of a hydrolyzate by hydrolysis in the process of producing a skin protective agent containing liquid citron by-products according to Example 1 of the present invention, and FIG. FIG. 4 is a graph showing the anti-aging (wrinkle improvement) performance test results of a skin protective agent containing liquid citron by-products according to Example 1 of the present invention. FIG. FIG. 5 is a graph showing comparative test results of the skin protection effect of a skin protective agent containing liquid citron by-products according to Example 1 of the present invention. FIG.

≪ Test Example 1 > Confirmation of non-glycosylation of glycosides

In order to confirm the non-glycosylation of the glycoside through the hydrolysis reaction, the components before and after the hydrolysis reaction were analyzed by gas chromatography mass spectrometry (GC-MS) as shown in Fig. The results of the analysis are expressed as the ratio of the area of the active substance to the total area of the active substance (% of Area), and expressed as P1 (Naringin), P2 (Isonaringin), P3 (Hesperidin), P4 (Neohesperin), P5 ) Were compared before and after functionalization (hydrolysis reaction). Prior to functionalization, Naringin P1 and P3 (Hesperidin) were found to be the major constituents of 35.23% and 36.49%, respectively. These two components are glycosides containing sugars. However, after functionalization, Naringenin and Hesperidin were found to be the major constituents of 31.37% and 35.04%, respectively, and the ratio of P1, P2, P3 and P4 As a result, it was confirmed that the glycosylation by the hydrolysis reaction proceeded to the non - glycosylation.

<Test Example 2> Anti-aging (wrinkle improvement)

Elastase is an enzyme that breaks down Elastin, a protein that maintains skin structure. It is an enzyme that is involved in the wrinkle of skin. The presence of Elastin reduces the wrinkles of the skin and increases the elasticity of the skin. When Elastin is decomposed by Elastase, the wrinkles of the skin are increased and the elasticity of the skin is decreased. In order to confirm the anti-aging function, the improvement of the elastase inhibitory function of the skin protective agent containing the concentrated liquid citron by-product made according to Example 1 was compared and analyzed before and after the functional materialization.

For comparison, 1300 ul (micro liter) of a substrate solution containing N-succinyl-Ala-Ala-Ala-p-nitroanilide (1 mM) substrate was added to the buffer solution to maintain the pH of Tris-Cl After 10 minutes of preincubation, 100 ㎕ of Elastase was added to each of the functional protective material and non-functionalized liquid citron byproducts for 10 minutes, followed by addition of enzyme elastase for 10 minutes. Incubation was performed to induce optimum reaction through constant temperature and humidity, and then the absorbance was measured at 410 nm. The skin protective material of Example 1 and the nonporous liquid citron by-products, which were functional materials used in this experiment, were compared with each other by using 20 times concentrated concentrate. As shown in Fig. 3, it was confirmed that Elastase inhibitory function of the skin protective material (After) after the hydrolysis process was improved by about 15% compared to the non-functionalized citron liquid citron by-product (Before).

&Lt; Test Example 3 >

Antioxidant activity was measured by electron donating ability (EDA) by DPPH (1,1-diphenyl-2-picryl hydrazyl). It can be demonstrated that DPPH has the function of eliminating free radicals present in DPPH and thus has antioxidant activity to remove free radicals of free radicals present in the human body, Of DPPH solution, the absorbance was measured at 517 nm after the incubation for 30 minutes. The skin protective material of Example 1 and the non-functionalized liquid citron by-products, which were functional materials used in this experiment, were compared with each other by 20 times concentrated concentration. As a result of comparison analysis, it was confirmed that after the hydrolysis process, the anti-oxidizing rate of the functional protective material (After) was improved by about 10% as compared to the non-functionalized citron liquid citron by-product (Before).

&Lt; Test Example 4 >

In order to confirm skin protection, RAW264.7 cell line, which is a macrophage of mice, was used for skin irritation test, and skin irritation test was carried out using inflammatory cells expressed when skin inflammation occurred by various external environments . The RAW264.7 cell line was treated with LPS (Lipopolysaccharide), an inflammatory expression factor, to induce an inflammatory reaction. After 30 minutes of the inflammatory reaction, the skin protective agent of Example 1 and the lecithin by- And the concentration of the inflammatory factor was measured after 24 hours. The inflammatory factor was developed by using grease reagent, NO (Nitric Oxide), which is the final product of inflammation caused by iNOS, a transporter RNA activated by inflammation, and absorbance was measured by UV-Vis spectrophotometer.

As shown in FIG. 5, when the inflammation expression level of the control group (control) was set at 100%, the expression of the inflammation was about 40% in the cells (before) The expression of inflammation was 25% in the cells (After) containing the skin protecting agent of Example 1, and the expression rate of inflammation was 75% as compared with the untreated group. It was confirmed that the skin protection effect was improved by about 15% as compared to before.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (6)

100 parts by weight of purified liquid citron by-product,
20 to 30 parts by weight of sodium hydroxide or potassium hydroxide aqueous solution of 0.1 to 0.5 normal concentration (N) diluted with water,
Citric acid 1 to 10 parts by weight
, &Lt; / RTI &gt;
After the glycoside has proceeded to the non-glycosylation through hydrolysis, the glycoside is condensed under reduced pressure 20 to 50 times
Skin protective material containing liquid citron by-products. The method of claim 1,
The skin protective agent material containing the liquid citrus by-products
Wherein the composition contains at least one selected from among non-glycosylated flavonoids hesperetin and naringenin as main components, and contains at least one selected from the glycoside flavonoids: naringin, isonarginine, hesperidin and neoheperidine
Skin protective material containing liquid citron by-products. The method of claim 1,
The skin protective agent material containing the liquid citrus by-products
Is applied to a cosmetic composition, a dermatological composition or a skin cleansing composition comprising, alone or in combination with at least one other active compound,
The composition is added to any one of the above compositions in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the composition to improve the elasticity of the elastin, Anti-aging effect, antioxidant effect using the function of reducing Free Radical of free radical of human body, suppression of inflammation of skin by inhibiting the expression of iNOS that produces NO (nitric oxide), which is an inflammatory factor that occurs during skin irritation Or at least one of the skin protection effect
Skin protective material containing liquid citron by-products. A step of collecting liquid citron filtrate for collecting liquid citron filtrate by filtration using citron by-products obtained in the process of citron processing by filtration paper or nonwoven fabric having a pore size of 0.5 to 50 μm,
A step of preparing a purified liquid citron by-product by removing the solid citron by-products remaining in the collected citron filtrate using a centrifuge at 300 to 3000 rpm using the collected citron filtrate,
20 to 30 parts by weight of sodium hydroxide or potassium hydroxide aqueous solution having a concentration of 0.1 to 0.5 normal (N) diluted with water per 100 parts by weight of the purified liquid citrus by-products are added, and the mixture is heated at 70 to 90 DEG C for 1 to 5 hours, A hydrolyzate preparation step of preparing a hydrolyzate,
A hydrolyzate neutralizing step of adding 1 to 10 parts by weight of citric acid per 100 parts by weight of the purified liquid citron by-product to the hydrolyzate to neutralize the hydrolyzate,
And then the concentrated hydrolyzate is concentrated 20 to 50 times under reduced pressure to complete a skin protecting agent material containing the concentrated liquid citrus by-products
Containing
(JP) METHOD FOR PRODUCING SKIN PROTECTIVE MATERIAL COMPRISING LIQUID CASULE BY - PRODUCT 5. The method of claim 4,
The finished skin protecting agent material contains at least one selected from among non-glycosylated flavonoids hesperetin and naringenin as main components, and at least one selected from the glycoside flavonoids such as naringin, isonarginine, hesperidin and neohesperidin Containing
(JP) METHOD FOR PRODUCING SKIN PROTECTIVE MATERIAL COMPRISING LIQUID CASULE BY - PRODUCT 5. The method of claim 4,
The PH of the hydrolyzate produced in the step of producing the hydrolyzate is 7.5 to 10,
The pH of the hydrolyzate neutralized in the hydrolyzate neutralization step is 5 to 8
(JP) METHOD FOR PRODUCING SKIN PROTECTIVE MATERIAL COMPRISING LIQUID CASULE BY - PRODUCT

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