KR102307227B1 - Manufacturing method detergent with subcritical water extract - Google Patents

Abstract

The present invention relates to a method of manufacturing a kitchen detergent by using a subcritical water extraction scheme, and more particularly, to a method of manufacturing a kitchen detergent by using a subcritical water extraction scheme, in which the kitchen detergent includes garlic and onion extracts as active ingredients, so that eco-friendly commercial use is possible, and an excellent cleaning power is obtained. According to the present invention, the method of manufacturing the kitchen detergent by using the subcritical water extraction scheme includes: an extraction raw material preparation step of washing an onion skin, a garlic skin, and a garlic stem, and performing fermentation and drying at 70 to 80 ℃ for 13 to 15 days; a grinding step of grinding a prepared extraction raw material, and filtering the ground extraction raw material through a 450 μm sieve; a mixing step of inserting the ground extraction raw material and water to a reactor, and mixing ethanol, a citric acid, sea salt, sodium benzoate, glyceryl caprylate, an EDTA· 2Na aqueous solution, and a natural surfactant; an additional mixing step of adding carboxymethyl cellulose (CMC) when the reactor is set to 40 ℃, and performing mixing at 200 to 850 rpm for 2 to 3 hours; a hydrolysis step of increasing a temperature of the mixed extraction raw material to 150 ℃ at a pressure of 30 bar to convert the extraction raw material into a subcritical water phase, and performing hydrolysis for 30 minutes; and a detergent manufacturing step of manufacturing a detergent by performing filtering and cooling after the hydrolysis.

Description

Dishwasher manufacturing method using subcritical water extraction method {MANUFACTURING METHOD DETERGENT WITH SUBCRITICAL WATER EXTRACT}

The present invention relates to a method for manufacturing a dishwashing detergent using a subcritical water extraction method, which contains extracts of garlic and onion as active ingredients, so that it can be used for eco-friendly commercial use and kitchen using a subcritical water extraction method with excellent cleaning power. It relates to a method for manufacturing a detergent.

Recently, due to the growing seriousness of environmental problems and growing interest in health, the need for developing low-pollution, high-functional detergents made using natural ingredients rather than synthetic detergents is increasing. In addition, the 'chemical phobia' phenomenon, which avoids chemical products itself, has intensified as safety problems with life-related chemical products such as humidifier sterilizers continue to occur. Paying attention to the product.

Among the existing technologies for manufacturing dishwashing detergent, hot water extraction method is used to extract ingredients by boiling in hot water, such as fermented skins, but the manufacturing method is primitive, causing problems in the uniformity and stability of quality. It is difficult to do research on improving product quality because it is not known exactly how much (or really is) of active ingredients in onion and garlic peels.

Conventional dishwashing detergents are manufactured using anionic surfactants as main components, and among these surfactants, sodium linear alkylbenzene sulfonate (LAS), alpha olefin sulfonate (AOS), sodium lauryl sulfate (SLS), sodium lauryl ethoxylated sulfate (SLES), alkyl ether sulfate (AES), and the like. While these have excellent foaming and cleaning power, their rinse properties are quite weak, and in particular, they have a low degree of biodegradation in general water systems, adversely affecting the water quality, and causing significant irritation to the skin of the human body. Therefore, the present invention intends to propose a method for manufacturing a detergent using natural ingredients such as onion and garlic.

A representative component of garlic is a sulfur compound called allin. Allin has no scent, but when garlic tissue is damaged, allin works with an enzyme called allinase in the tissue to become allicin, a self-defense substance. Allicin has a pungent taste and a strong odor. Odors come from the mouth as well as the whole body. Allicin has a strong sterilization and antibacterial action, killing food poisoning bacteria and even Helicobacter pylori bacteria that cause stomach ulcers. Allicin also aids digestion, boosts immunity, and lowers cholesterol levels. When allicin is combined with vitamin B1, it turns into allitiamine, which helps to recover from fatigue and boost energy.

Although onion accounts for 90% of water, it contains a large amount of nutrients such as protein, carbohydrates, vitamin C, calcium, phosphorus, and iron. Onion's component called quercetin helps prevent high blood pressure by inhibiting the accumulation of fat and cholesterol in blood vessels.

In order to supplement the above-mentioned problems, the inventors of the present invention have completed the present invention, recognizing that it is urgent to develop a natural dishwashing detergent that is environmentally friendly but has excellent cleaning power.

Korean Patent Publication No. 10-2017-0130690

The present invention has been devised to solve the above problems, and an object of the present invention is to provide a method for producing an eco-friendly dishwashing detergent containing active ingredients of garlic and onion by hydrolysis with subcritical water.

The technical problems to be solved by the invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. will be able

A method for manufacturing a dishwashing detergent using the subcritical water extraction method according to the present invention,

An extraction raw material preparation step of washing the onion skins, garlic skins and garlic stems, then fermenting and drying at 70 to 80° C. for 13 to 15 days;

a grinding step of grinding the prepared extraction raw material and filtering it through a 450 μm sieve;

A mixing step of adding the pulverized extraction raw material and water to a reactor, and mixing ethanol, citric acid, sea salt, sodium benzoate, glyceryl caprylate, EDTA·2Na aqueous solution and a natural surfactant;

An additional mixing step of adding carboxymethyl cellulose (CMC) when the reactor is set to 40° C. and mixing at 200 to 850 rpm for 00 to 00 hours;

a hydrolysis step of converting the mixed extract raw material to a subcritical water phase by raising the temperature to a pressure of 30 bar and a temperature of 150° C. and performing hydrolysis for 30 minutes;

It characterized in that it comprises; a detergent manufacturing step of manufacturing a detergent by cooling after the hydrolysis and filtering.

By means of solving the above problems, the present invention can be hydrolyzed to subcritical water to manufacture an eco-friendly dishwashing detergent containing the active ingredients of garlic and onion.

In addition, the present invention can easily extract active substances such as polyphenols such as onion skins, flavonoids, kaempferol, quercetin and strong antiacetylcholine through the subcritical water extraction method.

In addition, the present invention recycles the by-product of garlic/onion that is thrown away as garbage and causes environmental pollution and uses it as a raw material for detergent. savings are possible

In addition, the present invention is an eco-friendly product that does not stimulate the human body and prevents environmental pollution by using vegetable raw materials obtained from nature for both product raw materials and additional materials (pine needle oil, ethanol, citric acid, lactic acid, sea salt, etc.) It is possible to prepare a detergent containing naturally derived surfactants without adding anionic synthetic surfactants (SLES, SLS), which are the main culprits in the

In addition, the present invention has the effect that the remaining by-products can be used as fertilizers because the components remaining after extraction in the detergent manufacturing are by-products that do not affect soil erosion.

1 is a flowchart showing a detergent manufacturing method using the subcritical water extraction method of the present invention;
Figure 2 is a photograph showing the pulverization of the extraction raw material carried out in the second step according to an embodiment of the present invention.
3 is a photograph showing a subcritical water hydrolysis system implemented according to an embodiment of the present invention.
4 is a photograph showing the subcritical water hydrolyzate for each temperature carried out according to an embodiment of the present invention.
5 is a photograph showing the dried hydrolyzate residue carried out according to an embodiment of the present invention.
6 is a graph showing the yield of onion skin (OSK) subcritical water hydrolysis according to the temperature carried out according to an embodiment of the present invention.
7 is a graph showing the antioxidant activity (ABTS and DPPH inhibition) of onion skin (OSK) subcritical water hydrolyzate according to the temperature carried out according to an embodiment of the present invention.
8 is a graph showing the total phenol (TPC) and total flavonoid (TFC) content of onion peel (OSK) subcritical water hydrolyzate according to the temperature carried out according to an embodiment of the present invention.
9 is a graph showing the antioxidant activity (ABTS and DPPH inhibition) and total phenol (TPC) and total flavonoid (TFC) contents of onion peel (OSK) subcritical water hydrolyzate according to the mixing ratio carried out according to an embodiment of the present invention; This is the graph shown.
Figure 10 shows the antioxidant activity (ABTS and DPPH inhibition) and total of subcritical water hydrolysates according to the types of samples (OSK, GSK, GST, MIX) run at 150° C. and 30 g/60 mL according to an embodiment of the present invention. A graph showing the phenol (TPC) and total flavonoid (TFC) content.
Figure 11 shows the antioxidant activity (ABTS and DPPH) according to the types of samples (OSK, GSK, GST, MIX) performed with hot water extract (HWE) and subcritical water hydrolyzate (SWH) as a control group according to an embodiment of the present invention; inhibition) and a graph showing the total phenol (TPC) and total flavonoid (TFC) content.
12 is a photograph showing the results of an antibacterial test of 5 mg of subcritical water hydrolyzate of onion peel (OSK) performed according to an embodiment of the present invention.
13 is a photograph showing the results of an antibacterial test of 10 mg of subcritical water hydrolyzate prepared by mixing (MIX) onion peel, garlic peel and garlic stem according to an embodiment of the present invention.
14 is a photograph showing the results of an antibacterial test of 15 mg of subcritical water hydrolyzate prepared by mixing (MIX) onion peel, garlic peel and garlic stem according to an embodiment of the present invention.
13 is a photograph showing the results of an antibacterial test of 5 mg of subcritical water hydrolyzate of garlic rod (GST) performed according to an embodiment of the present invention.
14 is a photograph showing the results of an antibacterial experiment of 15 mg of a subcritical water hydrolyzate of garlic rod (GST) performed according to an embodiment of the present invention.
15 is a photograph showing the results of an antibacterial test of 10 mg and 15 mg of subcritical water hydrolyzate of garlic peel (GSK) performed according to an embodiment of the present invention.

Terms used in this specification will be briefly described, and the present invention will be described in detail.

The terms used in the present invention have been selected as currently widely used general terms as possible while considering the functions in the present invention, but these may vary depending on the intention or precedent of a person skilled in the art, the emergence of new technology, and the like. Therefore, the term used in the present invention should be defined based on the meaning of the term and the overall content of the present invention, rather than the name of a simple term.

In the entire specification, when a part “includes” a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the embodiments of the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Specific details including the problem to be solved for the present invention, the means for solving the problem, and the effect of the invention are included in the embodiments and drawings to be described below. Advantages and features of the present invention, and a method for achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

The present invention relates to the hydrolysis power and organic matter of water close to the critical point (374.2℃ 22.1MPa) under the conclusion that research on a stable extraction method of active substances is essential for product quality improvement and stabilization, thereby securing consumer trust. It is a technology that uses the sub-critical water extraction method (ECO method) to extract active substances using solvent power to extract active ingredients from by-products such as onion skins.

More specifically, above the critical point of water (374.2℃ 22.1MPa) is called super-critical water, which is neither liquid nor gas. It is called sub-critical water. Because water in a state corresponding to the region above the boiling point and below the critical point, the physical properties (reduction of relative permittivity, increase of magnetic diffusion coefficient, decrease of dynamic viscosity and surface tension) are easily deformed depending on temperature and pressure. It is efficient for hydrolyzing high molecular substances into low molecular weight or extracting active ingredients. Since subcritical water has strong hydrolysis and organic matter dissolving power, the technology used for extracting dairy components is the subcritical extraction method.

The subcritical water extraction method is a method of extracting active ingredients through low molecular weight by hydrolysis and material transformation by thermal decomposition and oxidative decomposition. It is eco-friendly and harmless to the human body because it is treated only with water, heat and pressure without solvents such as acids or alkalis, and the working time is short of a few seconds to minutes, and the extraction yield is improved.

In the conventional case, hot water extraction or enzyme extraction was used as a method for preparing a natural raw material extract. In the case of hot water extraction, high energy is required because extraction is required at a high temperature for a long time, and it takes a long time to achieve low efficiency and difficult quality control. In the case of enzyme extraction, it is impossible to use in vegetable and fruit cleaners that are one of the standards and specifications of the Ministry of Food and Drug Safety.

On the other hand, the subcritical water extraction method used in the present invention is a safe extraction method that can ensure harmlessness to the human body when compared to extraction with chemical solvents that have the possibility of genetic alteration, the presence of residual solvents and the harmfulness of the organic solvent itself.

The representative antioxidant of onion peel is quercetin, one of the phytochemicals, which has low solubility in water and oil. Since hot water extraction used in the past can extract only polar compounds, it is impossible to determine whether quercetin is contained in existing products.

Garlic peel is rich in polyphenols and flavonoids, and has antibacterial, anticancer, antiviral, antiallergic and anti-inflammatory effects, and is known to inhibit oxidation in the body. Onion peel is rich in quercetin and has anti-oxidation, anti-inflammatory, anti-platelet, anti-thrombotic, and anti-allergic effects. The main components of garlic and onion peels are antibacterial, antiviral, and antiallergic components, and it can be seen that they have excellent efficacy as the main components of cleaning agents.

The method for manufacturing a dishwashing detergent using the subcritical water extraction method of the present invention is preferably performed in the order shown in FIG. 1 .

First, in the first step (S10), the onion skins, garlic skins and garlic stems are washed and then fermented and dried at 70 to 80° C. for 13 to 15 days to prepare an extraction raw material.

More specifically, the garlic peel may be a silver peel surrounding the outer surface of the garlic, and the garlic stem means a long portion formed on the upper part of the garlic. It may also further include garlic root. The garlic peel, garlic root and garlic stem may be purchased and used in the market.

In addition, the onion peel may be a yellow or orange peel surrounding the outer surface of the onion, and may further include an onion root. The onion skins and onion roots may be purchased and used in the market, or directly cultivated and used.

In the first step (S10), “fermentation” refers to a phenomenon in which organic matter is decomposed and changed by the action of microorganisms, and refers to a process of decomposing organic matter using enzymes possessed by microorganisms.

In the present invention, in the first step (S10), the garlic skins, garlic stems and onion skins may be fermented at a temperature of 70°C to 100°C. More specifically, when the garlic skins, garlic stems and onion skins are fermented at less than 70° C., an excessively long time is required, which makes commercial use difficult, and when the garlic and onions are fermented at a temperature exceeding 100° C., high Due to the temperature, harmful substances present in the garlic and onion may be generated and spoiled, so it is preferable to ferment at 70° C. to 100° C.

In addition, the garlic peel, garlic stem and onion peel may be fermented for 13 to 15 days. More specifically, if the garlic peel, garlic stem, and onion peel are fermented for less than 13 days, fermentation may not be completely made and organic matter may not be completely decomposed, and if fermented for more than 15 days, the garlic peel, garlic stem and Since harmful substances present in the onion skins may be generated and decay, the garlic skins, garlic stems and onion skins are preferably fermented for 13 to 15 days.

Next, in the second step (S20), the prepared extraction raw material is pulverized and filtered using a 450 μm sieve.

As shown in Figure 2, the present invention was used by crushing onion peel (OSK), garlic peel (GSK) and garlic stem (GST). It is preferable to carry out under the above conditions because it is easier to extract the solid nutrients when the extraction raw material is pulverized and extracted in a powder form of 450 μm or less.

In addition, the pulverized extraction raw material is preferably mixed with 1 part by weight of the garlic peel powder and 1 part by weight of the garlic stem powder with respect to 1 part by weight of the onion peel powder. Allicin, the main component of the garlic peel and garlic stem, and quercetin, the main component of the onion peel, are mixed in the same ratio to obtain simultaneously. When obtaining a by-product of garlic and onion, since there is a limit in obtaining when selecting one component to obtain, three components must be obtained at the same time, which is advantageous in terms of economy. In addition, considering both the efficacy and economic feasibility of the subcritical extract, the result of the mixed extract containing all three components showed the highest effect, so it is carried out under the above conditions.

Next, in the third step (S30), the pulverized extraction raw material and water are put into the reactor, and ethanol, citric acid, sea salt, sodium benzoate, glyceryl caprylate, EDTA·2Na aqueous solution and a natural surfactant are mixed. .

It is preferable to mix 15 parts by weight of water with respect to 1 part by weight of the pulverized extraction raw material in the mixing step. In the present invention, only water is used as the solvent, and organic solvents other than water such as methanol, ethanol, propanol, ethyl acetate, or mixed solvents thereof are not used.

In addition, in the present invention, the dishwashing detergent may add a thickener, abrasive, neutralizer, sterilizer, antibacterial agent, surfactant, and metal ion prevention removal product. The ethanol is a cleaning aid to prevent freezing point. The citric acid is used as a PH control agent, cleaning aid and sterilization aid. The phosphate salt is used as a cleaning aid. The sodium benzoate and the glyceryl caprylate are used as preservatives. The EDTA·2Na aqueous solution is a metal ion sealing agent. The natural surfactant uses zwitterionic, cationic and nonionic surfactants.

0.5 to 1.0 parts by weight of ethanol, 0.02 to 0.1 parts by weight of citric acid, 0.3 to 1.0 parts by weight of sea salt, 0.1 to 0.5 parts by weight of sodium benzoate, 0.7 to 1.5 parts by weight of glyceryl caprylate, It is preferable to mix 0.05 to 0.1 parts by weight of EDTA·2Na aqueous solution and 30 to 45 parts by weight of a natural surfactant.

Next, in the fourth step (S40), when the reactor is set to 40° C., an additional mixing step of adding carboxymethyl cellulose (CMC) and mixing at 200 to 850 rpm for 2 to 3 hours is performed. More specifically, if the reactor is stirred at 200 to 850 rpm after adding the carboxymethyl cellulose (CMC), if the carboxymethyl cellulose (CMC) increases, stop the stirring and wait for a certain period of time. to stir the carboxymethyl cellulose (CMC). Therefore, the stirring of the reactor is carried out for 30 to 40 minutes, except for the increase time of the carboxymethyl cellulose (CMC).

The carboxymethyl cellulose (CMC) is used as a viscosity agent, and it is preferable to mix 1.4 to 2.0 parts by weight of carboxymethyl cellulose (CMC) with respect to 100 parts by weight of the pulverized extract.

Since the carboxymethyl cellulose (CMC) can be dissolved at an appropriate temperature, it is preferable to add the solvent after setting the temperature of water to 40°C. In addition, the dough should be kneaded at 400 to 480 rpm for a certain period of time so that it does not form lumps and blends well with the rest of the ingredients. If the carboxymethyl cellulose (CMC) is agglomerated or the conditions for input are not met, the balance of the detergent is broken and a constant viscosity is not generated and a problem of thinning occurs.

Next, in the fifth step (S50), the mixed extraction raw material is heated to a pressure of 30 bar and a temperature of 150° C. to convert to a subcritical water phase and hydrolyze for 30 minutes.

Next, in the sixth step (S60), after the hydrolysis, the filter is cooled, and the detergent is prepared by putting it in a storage container. More specifically, in the sixth step (S60), the extract is filtered with a filter paper to remove the solid powder residue, and then the temperature of the extract is lowered at room temperature to cool naturally. After that, it is put into a storage container, refrigerated, and used when manufacturing detergent.

In the present invention, the dishwashing detergent may additionally include a natural flavoring agent. The natural flavoring agent may be thaumatin, rebaudioside A, glycyrrhizin, lavender extract, lemon oil, grapefruit extract, or a mixture thereof, but is not limited thereto. When the natural flavoring agent is included, it is preferable to mix 0.05 to 0.2 parts by weight of the natural flavoring agent with respect to 100 parts by weight of the pulverized extract raw material mixed in the third step (S30).

In the case of hot water extraction, the existing extraction method used in developing detergents derived from natural substances in line with the recent trend of developing eco-friendly products that avoid the use of chemicals and consider the environment and the needs of consumers, economic feasibility deteriorates due to long process time , and lack of scientific support for extracting useful ingredients. Therefore, in this study, hydrolyzed extracts of onion peels, garlic peels, garlic stems and MIX (each 1:1:1 mixture) were prepared using subcritical water hydrolysis, an eco-friendly process, and the hydrolyzate contained in the hydrolyzate. Useful substances were quantified and biological activities were searched for. By checking the hydrolysis yield, antioxidant activity (ABTS, DPPH), total phenol content (TPC), and total flavonoid content (TFC) according to temperature, the optimal extraction conditions were explored and the antibacterial activity of the hydrolyzate extracted under the optimal conditions was identified. . In addition, a comparative experiment with the hot water extract used in the past was conducted.

Below, the contents of the experiment with respect to the development contents and method of the present invention are described.

(1) Raw material pretreatment

Onion Skin (OSK), Garlic Skin (GSK), and Garlic Stem (GST) provided by BL Company were crushed and raw materials were pretreated into uniform particles using a 450 μm sieve.

(2) Subcritical water hydrolysis of samples according to temperature conditions

Onion skins were selected as a sample, the pressure, the ratio of solids:water, and the treatment time were the same, and then subcritical water hydrolysis was carried out with the treatment temperature as a variable.

Condition Pressure 30 bar Mixing Ratio 30 g/600 mL (1:20) Time 30 min Temperature(℃) 120, 130, 140, 150, 160, 170, 180

After hydrolysis, the filtered residue was dried in an oven, and the weight was measured and compared with the sample weight to determine the yield (%) by [Equation 1] below.

As shown in Figure 4, the onion peel hydrolyzate according to the temperature is 120 °C in ①, 130 °C in ②, 140 °C in ③, 150 °C in ④, 160 °C in ⑤, 170 °C in ⑥, and 180 °C in ⑦. and the residue of the dried hydrolyzate is shown in FIG. 5 .

[Equation 1]

Hydrolysis rate (%) = Residue after hydrolysis (g) / Amount of sample used (g) X 100

(3) Measurement of antioxidant activity of hydrolyzate (ABTS, DPPH)

For ABTS, 10 mL of 7 mM ABTS solution and 10 mL of 2.45 mM potassium permanganate solution were mixed in a brown bottle, stored in a dark room for 12-16 hours, and absorbance was measured at 734 nm. 3.9 mL of ABTS solution and 0.1 mL of hydrolyzate were mixed, stored in a dark room for 6 minutes, and absorbance was measured at 734 nm using a UV Spectrometer. Trolox was used as a standard material.

Dilute DPPH to 0.1 mM in methanol to make DPPH solution, mix 3.9 mL of DPPH solution and 0.1 mL of hydrolyzate, store in a dark room for 30 minutes, and measure absorbance at 517 nm using UV Spectrometer to Inhibition (%) was calculated. Trolox was used as a standard material.

[Equation 2]

(where AC is the absorbance of the control and AS is the absorbance of the sample).

(4) Determination of total phenol and total flavonoid content of hydrolyzate (TPC, TFC)

To measure the total phenol content, add 1 mL of Folin-Ciocalteu reagent to 1 mL of hydrolyzate, _{add 0.8 mL of 7.5% Na 2} CO ₃ solution, mix well, and react in the dark for 2 hours. Absorbance values were measured at 765 nm in three replicates. Galic acid was used as a standard material. Results are expressed as mg GAE (Galic acid equivalent)/g.

For total flavonoid content, mix 75 μL of 5% (w / v) sodium nitrite solution with 125 μL of hydrolyzate, react for 6 minutes, add 150 μL of 10% alumunium chloride, and leave for 5 minutes. Then, 750 μL of 1 M sodium hydroxide solution and water were added to make the final volume 2.5 mL, and then reacted in the dark for 15 minutes, and then the absorbance was measured three times at 510 nm using a UV Spectrometer. Quercetin was used as a standard material, and the results were expressed as mg QE (QE (Quercetin equivalent)/g).

(5) Subcritical water hydrolysis of samples according to mixing ratio conditions

After setting the optimum temperature for hydrolysis according to temperature conditions (150 ℃), to search for the optimal ratio of sample and solvent (water), set the ratio as follows to determine antioxidant activity (ABTS, DPPH), total phenol (TPC), the total flavonoid (TFC) content was tested.

Mixing Ratio Condition Solid/Liquid (g/mL) 30/600 Pressure 30 bar 40/600 Temperature 150 ℃ 50/600 Time 30 Min 60/600

(6) Subcritical water hydrolysis according to the type of sample

Onion peel (OSK), garlic peel (GSK), garlic stalk ( GST), antioxidative activity (ABTS, DPPH), total phenol (TPC), and total flavonoid (TFC) content of the hydrolyzate obtained by applying the mixture (OSK, GSK, GST 1:1:1 Mix) were conducted.

(7) Comparison of activity of control (hot water extract) and subcritical water hydrolyzate

Antioxidative activity (ABTS, DPPH), total phenol (TPC), and total flavonoid (TFC) content of the hot water extract (control) and subcritical water hydrolyzate prepared by BL Company were tested.

- Experiment with a total of 5 samples (3 single samples + 2 mixed samples)

*<single sample>

C1-Onion peel extract / C2-Garlic peel extract / C3-Garlic stem extract

*<mixed sample>

C4 - Garlic Peel + Onion Peel Extract / C5 - Garlic Peel + Onion Peel + Garlic Stem Extract

(8) Comparison of antibacterial activity of control (hot water extract) and subcritical water hydrolyzate

The strains used in the experiment are shown in Table 3 below. The culture solution of each strain was dispensed on a plate medium and spread on the medium to prepare. After dissolving the extract powder in sterile distilled water, the concentrations of each extract were 1mg/disc and 5mg/disc (OSK) and 10mg/disc and 15mg/disc (GSK, GST, MIX), dispensed on paper discs with a diameter of 6 mm, and then oven After drying, incubated at 37 °C in close contact with a plate culture medium. After culturing for 24-48 hours, the diameter (mm) of the inhibition zone created around the disc was measured to evaluate the antimicrobial activity.

Bacillus cereus (KCTC 3624) Bacillus subtils (KCTC 1021) Staphylococcus aureus (ATCC 6538) Escherichia coli (ATCC 2592) Pseudomonas aeruginosa (ATCC 15692) Salmonela typhimurium (KCTC 1925) Salmonela enteritidis (KCCM 12021) Micrococus luteus (KCTC 1056)

Below, the experimental results of experiments according to the development content and method of the present invention described above are described.

(1) Hydrolysis of onion skins using subcritical water

When the onion skins provided by BL Company were hydrolyzed using a subcritical water hydrolysis device, as shown in FIG. 4 , a photograph of the onion peel hydrolyzate according to temperature is shown, and FIG. 5 is the dried residue remaining after hydrolysis. . A graph showing the yield of onion peel hydrolyzate according to temperature using [Equation 1] is shown in FIG. 6 . As a result, the hydrolysis rate tends to increase as the temperature increases, and the hydrolysis rate from 25.0% at 120°C increased to 47.1% at 180°C, showing the best hydrolysis rate.

(2) Measurement of antioxidant activity of onion peel subcritical water hydrolyzate according to temperature conditions (ABTS, DPPH)

Antioxidant activity (DPPH, ABTS), total phenol content (TPC), and total flavonoid content (TFC) were measured to determine the physiological activity and active compound of onion peel subcritical water hydrolyzate at each temperature.

The antioxidant activity is shown in FIG. 7 below, and in the case of DPPH, the radical scavenging ability increased as the temperature increased, and the maximum scavenging ability at 150° C. was exhibited and then decreased. In the case of ABTS, there was no significant difference in scavenging ability according to temperature.

(3) Measurement of total phenol and total flavonoid content of onion peel subcritical water hydrolyzate according to temperature conditions (TPC, TFC)

The results of measuring the content of total phenolic compounds and total flavonoids, which are closely related to antioxidant activity in plant natural products, are shown in FIG. 8 . Phenolic compounds showed the highest content at 180℃, and flavonoids showed the highest value at 150℃. Through this, considering not only the quality of the product but also the economic point of view, the optimum temperature for hydrolysis of subcritical water is considered to be 150°C, and an experiment was conducted to explore the optimal mixing ratio of the sample and the solvent.

(4) Measurement of antioxidant activity (ABTS, DPPH) and total phenol and total flavonoid content (TPC, TFC) of onion peel subcritical water hydrolyzate according to mixing ratio conditions

The antioxidant activity, total phenol, and total flavonoid content of onion peel subcritical water hydrolyzate according to mixing ratio conditions are shown in FIG. 9 . First, in the case of antioxidant activity, the ABTS value showed the highest activity at 30g/600mL, but there was no significant difference according to the mixing ratio. On the other hand, in the case of DPPH, it can be seen that the maximum activity is shown at 40g/600mL, and the activity decreases as the mixing ratio increases.

In the case of total phenol and total flavonoid content, 37.67 mg GAE/g for TPC and 93.53 mg QE/g for TFC at 30 g/600 mL were shown, and the content decreased as the mixing ratio increased. It is considered that as the mixing ratio increases, the surface area of the material capable of reacting with water decreases, so that the extraction of useful substances is rather inefficient.

From an economical point of view, it is more economical to show high activity at a small mixing ratio, so 30g/600mL is considered the most efficient condition. was fixed to proceed with hydrolysis.

(5) Comparison of properties of subcritical water hydrolyzate according to the type of sample

Antioxidant activity of various samples (onion peel; OSK, garlic peel; GSK, garlic stem: GST and 1:1:1 mixture thereof; MIX) using the optimal conditions confirmed in the previous experiment (150℃, 30g/600mL) (ABTS, DPPH) and the results of measuring the total phenol and total flavonoid content are shown in FIG. 10 . First, in the case of onion peel, it seems to exhibit better antioxidant activity, TPC, and TFC compared to garlic peel and garlic stem, which is Quercetin contained in onion peel and its glycosides Quercetin-3,4`-diglucoside and Quercetin-4`. It is thought that this result was shown because it contains a large amount of -glucoside.

In addition, in the case of the MIX sample in which the three samples were mixed 1:1:1 compared with the single sample, higher antioxidant activity, TPC, and TFC than the onion peel showing the highest activity were confirmed. It seems that various useful substances contained in each sample are decomposed and extracted by subcritical water, showing a synergistic effect, and it is necessary to confirm it through future research.

Therefore, considering the antioxidant activity, TPC, and TFC according to the sample, it is judged that MIX, which is a mixture of the three samples, is the most suitable in light of the use of by-products.

(6) Comparison of properties between control (hot water extract) and subcritical water hydrolyzate

The characteristic comparison between the hot water extract (control group) and the subcritical water hydrolyzate previously used by the company is shown in FIG. 11 . In the case of the hot water extract, it was extracted in boiling water for 24 hours, and in the case of the subcritical water hydrolyzate, it was obtained through a reaction for 30 minutes at 150° C. and 30 g/600 mL. In the case of antioxidant activity, both ABTS and DPPH showed higher activity of subcritical water hydrolyzate than conventional hot water extraction method, and in particular, DPPH was found to be significantly higher. In addition, in the case of total phenol and total flavonoids, it was confirmed that the subcritical water hydrolyzate showed a significantly higher content. This is compared to the existing hot water extraction method, in the case of subcritical water, the basic properties of water are the same, but through appropriate control of temperature and pressure, the reaction efficiency with the sample and the reaction efficiency and increase due to changes in dielectric constant, viscosity, surface tension, and polarity, etc. It is considered that this is because it has a very short extraction reaction time compared to the overall process, so it is judged to be an excellent extraction method in terms of process efficiency.

(7) Comparison of antibacterial activity of subcritical water hydrolyzate and hot water extract of onion and garlic by-products

The antibacterial activity was compared with the subcritical water hydrolyzate of onion and garlic by-products and the control (hot water extract). First, in the case of subcritical water hydrolyzate, when 1 mg and 5 mg of hydrolyzate dry powder was placed on the disc, it was found that only 5 mg of OSK had antibacterial activity. was found to have the highest activity. 12 shows the results of the OSK 5mg antibacterial test.

strain concentration Zone of inhibition (mm) OSK GSK GST MIX Bacillus cereus
(KCTC 3624) 5mg disc ^-1 9 - - - 1mg disc ^-1 - - - - Bacillus subtilis
(KCTC 1021) 5mg disc ^-1 11 - - - 1mg disc ^-1 - - - - Staphylococcus aureus
(ATCC 6538) 5mg disc ^-1 - - - - 1mg disc ^-1 - - - - Escherichia coli
(ATCC 25922) 5mg disc ^-1 10 - - - 1mg disc ^-1 - - - - Pseudomonas aeruginosa
(ATCC 15692 5mg disc ^-1 13 - - - 1mg disc ^-1 - - - - Salmonella typhimurium
(KCTC 1925) 5mg disc ^-1 - - - - 1mg disc ^-1 - - - - Salmonella enteritidis
(KCCM 12021) 5mg disc ^-1 12 - - - 1mg disc ^-1 - - - - Micrococcus luteus
(KCTC 1056) 5mg disc ^-1 11 - - - 1mg disc ^-1 - - - -

After increasing the concentration, the results of measuring the antibacterial activity using 10 mg and 15 mg of hydrolyzate dry powder are shown in Table 5 and FIGS. 13 to 16 . GSK and GST showed antibacterial activity against Staphylococcus aureus (Staphylococcus aureus, dermatophytosis), which was not shown in OSK. was confirmed to be

strain concentration Zone of inhibition (mm) GSK GST MIX Bacillus cereus
(KCTC 3624) 10mg disc ^-1 - - 10 15mg disc ^-1 - 12 12 Bacillus subtilis
(KCTC 1021) 10mg disc ^-1 - - 10 15mg disc ^-1 - - 11 Staphylococcus aureus
(ATCC 6538) 10mg disc ^-1 13 11 16 15mg disc ^-1 15 15 18 Escherichia coli
(ATCC 25922) 10mg disc ^-1 - - 10 15mg disc ^-1 - - 10 Pseudomonas aeruginosa
(ATCC 15692) 10mg disc ^-1 - 10 12 15mg disc ^-1 - 12 13 Salmonella typhimurium
(KCTC 1925) 10mg disc ^-1 - - 11 15mg disc ^-1 - 10 11 Salmonella enteritidis
(KCCM 12021) 10mg disc ^-1 - - 11 15mg disc ^-1 - 13 13 Micrococcus luteus
(KCTC 1056) 10mg disc ^-1 - - 9 15mg disc ^-1 - 8 11

However, in the case of the control group, the hot water extract, it was found that no antibacterial activity was observed when the experiment was conducted at the same concentration.

To briefly summarize the previous results, the optimal extraction conditions obtained through hydrolysis yield, antioxidant activity (ABTS, DPPH) and TPC and TFC were confirmed to be 150°C at a temperature and a mixing ratio of 30g/600mL. As a result of subcritical water treatment of several samples, mixed MIX was found to be the best. After that, in a comparative experiment with the control group, the hot water extract and the subcritical water hydrolyzate, the subcritical water hydrolyzate showed excellent effects in all samples. g, TFC was 8.16mg QE/g, whereas in the case of subcritical water hydrolyzate, TPC 14.56mg GAE/g and TFC 127.89mg QE/g were high.

In the subsequent antibacterial experiment, the hydrolyzate of subcritical water was found to have antibacterial activity against 6 out of 8 strains at 5mg disc-1 of onion peel, and in the case of MIX, Staphylococcus, which did not show activity in onion peel at 10mg disc-1 aureus and Salmonela typhimurium were found to have antibacterial activity in all 8 out of 8 species. However, in the case of the control group, the hot water extract, antibacterial activity was not observed in all samples and concentrations.

Finally, when the subcritical water hydrolysis method, an eco-friendly process, is applied to the by-products of onions and garlic thrown away for the manufacture of natural detergents, the process time is shortened compared to the existing hot water extraction method, and the It is expected that economical, eco-friendly and competitive products can be manufactured through extraction of antibacterial active substances that were not previously available as well as extraction.

By means of solving the above problems, the present invention can be hydrolyzed to subcritical water to manufacture an eco-friendly dishwashing detergent containing the active ingredients of garlic and onion.

In addition, the present invention can easily extract active substances such as polyphenols such as onion skins, flavonoids, kaempferol, quercetin and strong antiacetylcholine through the subcritical water extraction method.

In addition, the present invention recycles the by-product of garlic/onion that is thrown away as garbage and causes environmental pollution and uses it as a raw material for detergent. savings are possible

In addition, the present invention is an eco-friendly product that does not stimulate the human body and prevents environmental pollution by using plant raw materials obtained from nature both as product raw materials and additional materials (ethanol, citric acid, lactic acid, sea salt, etc.) It is possible to prepare a detergent containing a naturally derived surfactant without adding anionic synthetic surfactants (SLES, SLS).

In addition, the present invention has the effect that the remaining by-products can be used as fertilizers because the components remaining after extraction in the detergent manufacturing are by-products that do not affect soil erosion.

As such, those skilled in the art to which the present invention pertains will understand that the above-described technical configuration of the present invention may be implemented in other specific forms without changing the technical spirit or essential characteristics of the present invention.

Therefore, the embodiments described above are to be understood as illustrative and not restrictive in all respects, and the scope of the present invention is indicated by the following claims rather than the above detailed description, and the meaning and scope of the claims and their All changes or modifications derived from the concept of equivalents should be construed as being included in the scope of the present invention.

S10. Extraction raw material preparation step of washing onion skins, garlic skins and garlic stems and then fermenting and drying at 70 to 80°C for 13 to 15 days
S20. A grinding step of pulverizing the prepared extraction raw material and filtering it using a 450 μm sieve
S30. A mixing step of adding the pulverized extraction raw material and water to the reactor, and mixing ethanol, citric acid, sea salt, sodium benzoate, glyceryl caprylate, EDTA·2Na aqueous solution and a natural surfactant
S40. When the reactor is set to 40° C., an additional mixing step of adding carboxymethyl cellulose (CMC) and mixing at 200 to 850 rpm for 00 to 00 hours
S50. A hydrolysis step of converting the mixed extraction raw material to a subcritical water phase by raising the temperature to a pressure of 30 bar and a temperature of 150° C. and performing hydrolysis for 30 minutes
S60. Detergent manufacturing step of manufacturing detergent by cooling after filtering after the hydrolysis

Claims (5)

An extraction raw material preparation step of washing the onion skins, garlic skins and garlic stems, then fermenting and drying at 70 to 80° C. for 13 to 15 days;
a grinding step of grinding the prepared extraction raw material and filtering it into a powder form using a 450 μm sieve;
A mixing step of adding 15 parts by weight of water based on 1 part by weight of the pulverized extraction raw material to a reactor, and mixing ethanol, citric acid, sea salt, sodium benzoate, glyceryl caprylate, EDTA·2Na aqueous solution and a natural surfactant;
an additional mixing step of adding carboxymethyl cellulose (CMC) and mixing at 200 to 850 rpm for 2 to 3 hours when the reactor is set to 40°C;
a hydrolysis step of converting the mixed extract raw material to a subcritical water phase by raising the temperature to a pressure of 30 bar and a temperature of 150° C. and performing hydrolysis for 30 minutes;
A detergent manufacturing step of manufacturing a detergent by cooling after filtering after the hydrolysis;
In the mixing step, a thickener, an abrasive, a neutralizer, a sterilizer, an antibacterial agent, a natural flavoring agent, and a metal ion prevention removal product are mixed,
1.4 to 2.0 parts by weight of the carboxymethyl cellulose (CMC) and 0.05 to 0.2 parts by weight of the natural flavoring agent are mixed with respect to 100 parts by weight of the pulverized extract,
The total phenol/total flavonoid content ratio produced by hydrolysis with the subcritical water is 30 g/600 mL,
The prepared detergent is
Bacillus cereus (KCTC 3624), Bacillus subtilis (KCTC 1021), Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 25922), Pseudomonas aeruginosa (ATCC 15692, Salmonella typhimurium (KCTC 1925) and Micrococcus luteus luteus 12021), Salmonella enteritidis (KCTC 12021) (KCTC 1056) Dishwashing detergent manufacturing method using subcritical water extraction method, characterized in that it exhibits antibacterial activity.
The method of claim 1,
In the pulverized extract raw material,
1 part by weight of the garlic peel powder and 1 part by weight of the garlic stalk powder with respect to 1 part by weight of the onion peel powder.
delete The method of claim 1,
In the mixing step,
0.5 to 1.0 parts by weight of ethanol, 0.02 to 0.1 parts by weight of citric acid, 0.3 to 1.0 parts by weight of sea salt, 0.1 to 0.5 parts by weight of sodium benzoate, 0.7 to 1.5 parts by weight of glyceryl caprylate, A dishwashing detergent manufacturing method using a subcritical water extraction method, characterized in that 0.05 to 0.1 parts by weight of an EDTA·2Na aqueous solution and 30 to 45 parts by weight of a natural surfactant are mixed.
15 parts by weight of water is mixed with respect to 1 part by weight of garlic peel, onion peel and garlic stalk extract, and the temperature is raised to a pressure of 30 bar and a temperature of 150 ° C.
Bacillus cereus (Bacillus cereus, KCTC 3624), Bacillus subtilis (Bacillus subtilis, KCTC 1021), Staphylococcus aureus (Staphylococcus aureus, ATCC 6538), Escherichia coli (Escherichia coli, ATCC 25922), Pseudomonas aeruginosa (Pseudomonas aeruginosa, ATCC 15692), rat A dishwashing detergent using a subcritical water extraction method, characterized in that it exhibits antibacterial activity against typhoid bacteria ( Salmonella typhimurium, KCTC 1925), enteritis bacteria (Salmonella enteritidis, KCCM 12021) and luteus (Micrococcus luteus, KCTC 1056).

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