KR20230140941A - Graphene-containing sterilization and deodorant manufacturing method and sterilizing and deodorizing agent - Google Patents

Abstract

The present invention relates to a method for manufacturing a sterilizing and deodorizing agent containing graphene, which has excellent sterilizing and odor removal efficiency through compatibility with cypress tree leaf extract and graphene, and to the sterilizing and deodorizing agent. In the present invention, cypress tree leaves are washed to remove foreign substances. , a raw material preparation step of preparing dried cypress tree leaves by drying them to a moisture content of 15% or less; and a raw material extraction step of extracting the cypress tree leaves from the raw material preparation step in an extractor to obtain a cypress tree leaf extract; and, the raw materials. A drying step of drying the cypress tree leaf extract from the extraction step in a reduced pressure dryer at a temperature of 40 to 50°C for 120 to 90 minutes; preparing graphene and oxidizing the nitrogenous functional groups on the graphene using a graphene surface modification method. Graphene synthesis step of synthesizing reduced graphene (r-GO-n); and the redox graphene of the graphene synthesis step and the cypress tree leaf extract prepared in the drying step are added to the mixer, and 3~3 times at room temperature. Sterilization containing graphene comprising a primary stirring step of primary stirring for 5 hours; and, after the primary stirring is completed, secondary stirring for 24 to 18 hours at a temperature of 50 to 60°C. A deodorant manufacturing method and a sterilizing and deodorizing agent manufactured by the manufacturing method are disclosed.

Description

Graphene-containing sterilization and deodorant manufacturing method and sterilizing and deodorizing agent}

The present invention relates to a method for manufacturing a sterilizing and deodorizing agent containing graphene, which has excellent sterilizing and odor removal efficiency through compatibility with cypress tree leaf extract and graphene, and to the sterilizing and deodorizing agent.

Pollution of the natural environment is mainly caused by chemical products used in the mass production of goods, but recently, a lot of pollution is also occurring in the disposal of goods discarded after mass consumption. Pollution to the natural environment only refers to air pollution, water pollution, and soil pollution depending on the object of pollution, but recently, in addition to air, water, and soil pollution, noise, odor, and exhaust that have a negative impact on humans have also been mentioned. It is currently recognized as a part of pollution.

Among the above types of pollution, odor can be defined as anything that is harmful to the human body or has a negative effect on the human body, ranging from a simple unpleasant odor through the nose, one of the human sense organs.

In order to reduce the above-mentioned odors, ventilation and dilution methods are used to control and spread the odors using hoods, ducts, and/or high chimneys; absorption methods are used to remove odorous substances by passing them through a washer and absorbing them into a cleaning solution; and a cooler. A condensation method that condenses and removes odorous substances using a combustion oxidation method that removes odorous substances by burning them through high-temperature heating, a catalytic oxidation method that oxidizes odorous substances using a catalyst, and ozone (O3) and/or chlorine compounds. There are chemical oxidation methods that chemically oxidize odorous substances. In addition, a method of spraying ingredients with a strong aroma and camouflaging the odor is a camouflage method using fragrances such as vanillin, rosin oil, and benzyl acetate, and a method of deodorizing or reducing odor by mixing substances that emit different odors. Neutralization methods are being used.

Republic of Korea Patent Publication No. 10-2017-0108587 Republic of Korea Patent Publication No. 10-2314116 Republic of Korea Patent Publication No. 10-2022-0012774 Republic of Korea Patent Publication No. 10-1670953 Republic of Korea Patent Publication No. 10-1075779

The present invention is to provide a sterilizing and deodorizing agent with excellent sterilizing and deodorizing efficiency. More specifically, the function as a sterilizing and deodorizing agent and applicability as a disinfectant are confirmed through exploration of physiological activity through cypress tree leaf extract and graphene compatibility. The problem is to provide a method for manufacturing a sterilizing and deodorizing agent containing graphene, which has excellent deodorizing efficiency, and a sterilizing and deodorizing agent containing the same.

The method for manufacturing a sterilizing and deodorizing agent containing graphene according to the present invention, which solves the above problems, includes a raw material preparation step of preparing the dried cypress tree leaves by washing the cypress tree leaves to remove foreign substances and drying them to a moisture content of 15% or less. ; And, a raw material extraction step of extracting the Cypress tree leaves of the raw material preparation step in an extractor to obtain a Cypress tree leaf extract; And, the Cypress tree leaf extract of the raw material extraction step is heated to 120° C. in a reduced pressure dryer at a temperature in the range of 40 to 50° C. A drying step of reduced pressure drying for ~90 minutes; A graphene synthesis step of preparing graphene and synthesizing redox graphene (r-GO-n) by adding functional groups to the graphene and using a graphene surface modification method; A primary stirring step in which the redox graphene from the graphene synthesis step and the cypress tree leaf extract prepared in the drying step are placed in a mixer and first stirred at room temperature for 3 to 5 hours; and the first stirring is completed Afterwards, secondary stirring is performed for 18 to 24 hours at a temperature of 50 to 60°C.

Here, in the drying step, the interior of the reduced pressure dryer is characterized in that the vacuum degree is formed within the range of 90 to 100 mmHg.

Here, the cypress tree leaf extract obtained in the raw material extraction step is characterized by containing 0.6 to 1.0% by weight of phytoncide as an active ingredient.

Here, the redox graphene of the graphene synthesis step and the cypress tree leaf extract added in the first stirring step are added and mixed at a weight ratio of 0.01 to 0.05:0.6 to 1.

Additionally, the present invention provides a sterilizing and deodorizing agent manufactured according to the above manufacturing method. Here, the sterilizing and deodorizing agent is characterized in that it contains redox graphene and cypress tree leaf extract in a weight ratio of 0.01 to 0.05:0.6 to 1.0.

The method for manufacturing a sterilizing and deodorizing agent containing graphene according to the present invention provides a sterilizing and deodorizing agent with excellent sterilizing and deodorizing effects by improving the sterilizing, deodorizing and deodorizing effects of the cypress tree leaf extract and the excellent sterilizing action of redox graphene. You can.

Figure 1 illustrates the process of combining cypress tree leaf extract and graphene in the sterilizing and deodorizing agent according to the present invention.
Figure 2 is a graph showing the results of an experiment on increasing the bacterial deodorizing function of the sterilizing and deodorizing agent provided according to the present invention.

Hereinafter, the present invention will be described in more detail.

The purpose of the present invention is to provide a method for manufacturing a sterilizing and deodorizing agent containing graphene, which improves sterilizing and odor removal efficiency through compatibility between cypress leaf extract and graphene, and a sterilizing and deodorizing agent thereof,

The method for manufacturing a sterilizing and deodorizing agent containing graphene according to the present invention, which achieves the above object, includes a raw material preparation step of preparing the dried cypress tree leaves by washing the cypress tree leaves to remove foreign substances and drying them to a moisture content of 15% or less; , a raw material extraction step of extracting the cypress tree leaves from the raw material preparation step in an extractor to obtain a cypress tree leaf extract; and, heating the cypress tree leaf extract from the raw material extraction step in a reduced pressure dryer at a temperature in the range of 40 to 50° C. A drying step of drying under reduced pressure for 90 minutes; A graphene synthesis step of preparing graphene and synthesizing redox graphene (r-GO-n) by adding nitrogenous functional groups to the graphene by a graphene surface modification method; A primary stirring step in which the redox graphene from the graphene synthesis step and the cypress tree leaf extract prepared in the drying step are placed in a mixer and first stirred at room temperature for 3 to 5 hours; and after the primary stirring is completed , secondary stirring for 18 to 24 hours at a temperature of 50 to 60°C.

At this time, the raw material extraction step of obtaining the cypress tree leaf extract can be performed by hot water extraction or solvent extraction. Preferably, in the case of hot water extraction, 500 g of cypress tree leaves and 4 liters of distilled water are added to a steam distillation device to obtain essential oil. was extracted. The temperature was gradually increased and volatile components were collected at 100-200°C for 18-24 hours. The natural volatile components generated were collected in the form of condensate. Essential oil in the form of condensate is extracted three times by adding 100 ml of ethyl acetate, concentrated through a rotary evaporator to obtain the final essential oil, and then stored in the refrigerator at 1-4°C before use because it does not require the use of any chemicals.

In addition, in the graphene synthesis step, the synthesis of redox graphene (r-GO-n) is the first process of synthesizing graphene oxide. 5 g of graphite is put in a ball mill, injected with 10 bar of CO ₂ as a reactant, and then rotated at 500 rpm. It was obtained through a ball mill process at a speed of 56 hours, and nitrogen-functionalized redox graphene (rGO-n) was manufactured by injecting 10 bar of nitrogen gas (N) into the produced graphene oxide and operating it at a speed of 500 rpm for 48 hours, followed by filtering and drying. It is preferable to use redox graphene (rGO-n) functionalized through a 48h process.

According to the present invention, preferably in the drying step, the interior of the reduced pressure dryer is preferably formed at a vacuum level within the range of 90 to 100 mmHg. At this time, limiting the internal vacuum of the vacuum dryer is to increase drying efficiency and increase the extraction rate of active ingredients from raw materials. In particular, the internal vacuum of the vacuum dryer is important because it destroys useful components of natural substances and reduces their value as natural substances. It is to prevent this. Therefore, internal vacuum treatment is necessary during the extraction process to save polyphenols, proteins, sugars, starches, oils, and aroma components from the plants used for extraction. It also has effects such as increasing extraction efficiency and speed, lowering extraction temperature, saving solvent, and reducing bacterial growth.

According to the present invention, the cypress tree leaf extract obtained in the raw material extraction step contains 0.6 to 1.0% by weight of phytoncide as an active ingredient.

According to the present invention, it is preferable to mix the redox graphene from the graphene synthesis step and the cypress tree leaf extract added in the first stirring step at a weight ratio of 0.01 to 0.05:0.6 to 1.0. If the mixing ratio is outside the critical range, the effect may be minimal or problems such as discoloration may occur.

Preferably, according to the present invention, in the first stirring step, 75 to 80% by weight of distilled water, 18.5 to 20% by weight of ethanol, 0.6 to 1.0% by weight of cypress oil, 0.1 to 0.3% by weight of tea tree oil and eucalyptus oil, and grapefruit and 0.1 to 0.25% by weight of castor oil, 0.1 to 0.2% by weight of glycerin, and 0.01 to 0.05% by weight of graphene.

According to the present invention, if the combining process of redox graphene and cypress tree leaf extract in the first and second stirring steps is explained through the combining process of cypress tree leaf extract and graphene in Figure 1, the cypress tree leaf It is formed when the methyl group of phytoncide, the active ingredient of the extract, is bonded to the edge carboxylic acid group of the redox graphene.

<Figure 1> below shows that terpenes, which have various isomers among the components contained in phytoncide, contribute to various odors and flavors. The most surprising thing about these compounds is that they are all made of the same molecular unit, isoprene (C5H8). With isoprene (C5) as the structural unit, it is called monoterpene (C10), sesquiterpene (C15), and diterpene (C20) depending on the number of units. Isoprene itself is a hemiterpene compound, as it contains alcohols, aldehydes, ketones, and carboxylic acids that have the same carbon skeleton.

<Figure 1: Terpene structure of phytoncide>

In particular, as shown in <Figure 2> below, graphene can be covalently bonded to any material through surface modification, and thus its strong methyl function is activated through bonding with terpene, thereby increasing its antibacterial function.

<Figure 2: Covalent bond structure through surface modification of graphene>

According to the above manufacturing method, in the present invention, redox graphene and cypress tree leaf extract with improved sterilization and deodorization efficiency are combined with phytoncide, an active ingredient of cypress tree leaf extract, in a range of 0.01~0.05:0.6~. It is possible to provide a sterilizing and deodorizing agent comprised of a weight ratio of 1.0.

Hereinafter, it will be described in more detail through an experimental example to examine the sterilizing and deodorizing effect of the sterilizing and deodorizing agent combining redox graphene and cypress tree leaf extract provided in the present invention. step. The following experimental examples are examples for illustrating the present invention and do not limit the present invention to the content and results of the following experimental examples, and may be modified by those skilled in the art without departing from the scope of the invention disclosed in the patent claims. It is possible.

[Experimental example]

<Experiment overview>

Chamaecyparis obtusa (CO) is a hinoki tree. Bioflavonoids extracted from the hinoki tree are known to have neuroprotective effects, and include monoterpenoids, sesquiterpenoids, Flavonoids and bioflavonoids are also well known as various types of biologically active substances (bactericidal, anti-inflammatory, insecticidal, deodorizing, immune-boosting, stress-regulating, etc.) extracted from cypress leaves. Therefore, looking at the content analysis results for the six components of the cypress tree leaf extract, α-Terpinene 3.03 mg/g, α-Terpineol 9.48 mg/g, limonene 5.96 mg/g, borneol 59.78 mg/g, myrcene 4.85 mg/g, sabinene was found to be 11.31mg/g. Additionally, graphene oxide (GO) contains more than 50% oxygen by mass, and the oxygen functional group is known to promote sterilization effects through physical and chemical processes that destroy phospholipids in cell membranes. In addition, it is known to promote sterilization by increasing oxidative stress in bacteria and pests, causing oxidative damage to cell proteins, lipids, and nucleic acids.

Therefore, this experiment was conducted to confirm its function as a sterilizing and deodorizing agent and its applicability in the future industrialization of functional disinfectants, moisturizers, cosmetics, and ointments by exploring the physiological activity through compatibility with cypress tree leaf extract and graphene.

<Sterilization and deodorization experiment>

The Cypress tree leaf extract is extracted using a hot water extraction method, and the Cypress leaf extract solution provided by Maxbay Global Co., Ltd. is placed in a decompression dryer and decompressed at a temperature of 50℃ with a vacuum degree in the range of 90 to 100 mmHg for 120 to 90 minutes. It was prepared by drying.

The synthesis of oxidized and reduced graphene (r-GO-n) is the first process of synthesizing graphene oxide. 5 g of graphite is put in a ball mill, injected with 10 bar of CO ₂ as a reactant, and then ball milled for 56 hours at a speed of 500 rpm. Obtained, Nitrogen-functionalized redox graphene (rGO-n) was manufactured by injecting 10 bar of nitrogen gas (N) into the graphene oxide, operating it at 500 rpm for 48 hours, and then filtering and drying for 48 hours. Redox graphene (rGO-n) was prepared.

The above-prepared cypress leaf extract and redox graphene were synthesized by stirring and mixing under the conditions shown in Table 1 below.

Cypress tree leaf extract r-GO 1st stirring 2nd stirring Phytoncide
(Terpene) r-GO-n 3h (room temperature) 24h (50~60℃)

1) Tepene and Graphene sterilization experiment_01

Before combining graphene and terpene, in order to test each sterilizing power, the r-GO-n experimental group (DY_01) with modified graphene edges was rubbed with a cotton swab several times on a household cutting board with a commercially available agar medium and the untreated control group (SM_00). After soiling the bacteria, they were cultured in a thermostat according to the conditions in Table 2 below and confirmed after 4 to 6 hours. When the number of bacteria visible on the microscope was more than 500, the experimental results showed that there were more than 500 bacteria in the control group, but the number of bacteria was reduced in the modified r-GO-n 001% test group.

When the same experiment was conducted on terpene (cypress extract), the experimental results showed that when terpene was not added, there were more than 500 bacterial groups, but when 1% of terpene was added, the number of bacterial groups was reduced.

division control group
(SM_00) test group
(DY_01) condition note temperature humidity Contrast bacterial sample 30℃ 70% middle For commercial use
Use of badge

○ Sterilization experiment results

As a result of this sterilizing power comparison experiment, the sterilizing power effects of terpene and graphene were measured to be similar. In other words, in individual bacterial populations that did not mix terpene and r-GO-n, it decreased by about 1/3. However, when (r-GO-n 001%) + (Terpene 04%) solution was added, the number of fungal organisms was found to be reduced by more than 99%. This is believed to have increased the sterilization effect of graphene and terpene.

2) Deodorizing function experiment_01

In order to learn about the deodorizing function before and after combining graphene and terpene, a deodorizing function test was conducted anonymously on 20 company executives and employees and other customers to remove the unique smell of the vehicle interior before and after using the deodorant. The experimental method was conducted as a monitoring method for 30 days by providing alcohol as a control group and our company's sterilizing deodorant as an experimental group to the test subjects.

The monitoring results are shown in Table 3 below.

division collect sample
number 5 generations 5 generations 5 generations 5 generations Sum note Severe
(Query) middle
(Query) a little
(Query) almost
doesn't exist Alcohol 5-14 days 1 time SM_00 4 3 2 One 10 control group 15-30 days Episode 2 4 3 2 One 10 average 4 3 2 One 10 Sterilization
deodorant 5-14 days 1 time DY_01 One One One One 4 experimental group 15-30 days Episode 2 2 One One One 5 average 1.5 One One One 4.5

* There are various odors coming from inside a vehicle (cigarette, mold, food, dust, old people, sweat, pet odors, etc.) and are defined as follows.

* Attachments: Severe (4), Moderate (3), Slight (2), Almost None (1)

○ Deodorizing function test results

As a result of this deodorizing function comparison test, the deodorizing effect of our sterilizing and deodorizing agents (terpene and graphene) showed a significant difference compared to the control group. When the (r-GO-n 001%) + (Terpene 04%) solution is added and sprayed, the deodorizing effect lasts for more than 15 days, which indicates that the deodorizing effect of graphene and terpene is excellent.

3) Testing of deodorization function (gas diffusion speed, flight time, and scent)

An experiment was conducted to determine the gas diffusion rate, flight time, and scent intensity before and after combining graphene and terpene. In order to narrow and accurately determine the location where diffusion begins, the pipes were connected to an inner diameter of 12 cm, a length of 50 cm, and a height of 2 m, and both ends were separated by 10 cm, and a fogger (vapor pressure of about 100 mmHg) was attached to one side of the pipe. The mist diffusion speed, flight time, and scent intensity were each measured three times and averaged. As a result of a comparison test of the haze diffusion speed, flight time, and scent intensity, the diffusion speeds of terpene and graphene were measured to be similar. However, when the (r-GO-n 001%) + (Terpene 1%) solution was added, the diffusion speed, flight time, and scent intensity increased by more than 3 to 4 times.

<Deodorization function test method>

- Spreading speed: Measure the distance traveled 3 seconds after sample injection.

- Flight time: Measure the time from 3 seconds after sample injection until the aircraft disappears with the naked eye.

- Sensory test for scenting: Examine the filter 10cm in front of the sample spray for 1~2 seconds, smell the scent, and judge it as high, medium, or low.

The results of the experiment according to the deodorizing function test method are shown in Table 4 below.

Semple 1. Spreading speed
(m) 2.Hanging time 3. Go to the village
(sensual method) note
(Summary of inspection contents) DY_01 1 time 4 1 minute 15 seconds middle Same conditions indoors in the laboratory/factory building Episode 2 4 1 minute 30 seconds middle 3rd time 4 1 minute 20 seconds middle average 4 1 minute 22 seconds middle SM_00 1 time 3.8 53 seconds under Episode 2 3.8 1 minute 7 seconds under 3rd time 3.8 50 seconds under average 3.8 70 seconds under

○ Deodorizing function test results

As shown in Table 4 above, the experimental results showed that the diffusion speed, flight time, and scent intensity increased when graphene and terpene were added compared to the existing gas diffusion rate, flight time, and scent intensity. This is the function of graphene. It is judged that this is not the case.

Meanwhile, explaining the sterilization and deodorization mechanism, in the process of combining the Cypress extract and graphene in Figure 1, the active ingredient of the Cypress extract is bound to the edge carboxylic acid ring of the redox graphene, and the antibacterial action is shown in Figure 2. Mechanisms are broadly classified into two processes as follows.

1. Physical action

Graphene is basically a material that is thin and has a large area. Graphene, a relatively unlaminated form, has sharp edges that can cause physical damage to cell membranes. Wang's group suggested that if graphene exists in a few-layered form and is relatively sharper, it can penetrate the phospholipids of the cell membrane and kill bacteria more effectively.

2. Chemical action

The antibacterial effect through the chemical action of graphene material is explained by oxidative stress. The functional groups contained in graphene oxide generate highly unstable reactive oxygen species (ROS) within bacteria, which cause chemical damage to the structure of bacteria. The Akhavan group suggested that graphene oxide has a greater antibacterial effect against P. aeruginos than reduced graphene.

It is believed that sterilization and deodorization are achieved through these physical and chemical effects.

The results of improving the bacterial deodorization function are as shown in Figure 2.

When explaining the improved function of the sterilizing and deodorizing agent provided by the present invention through the above experiment,

First, improved sterilization function

Terpene's methyl group and graphene's oxygen functional group destroy the phospholipids of bacterial cell membranes through a physical and chemical process, and the graphene r-GO-n functional group further increases oxidative stress in bacteria and pests, resulting in a sterilizing effect. It is believed to have been promoted.

Second, improved deodorization and deodorization function

1) Formaldehyde: sick house syndrome

2) Ammonia: Toilet odor

3) Acetic acid, hydrogen sulfide: sweat odor

4) Trimethylamine, methyl mercaptan: Functions as a chemical deodorant (neutralization, oxidation, reduction, hydrolysis and ion exchange, etc.) of cypress terpene and graphene, such as food odors, and physical deodorization of graphene, which is a porous material. It is believed to be a result of synergistic effects such as diffusion and flight time due to adsorption.

Claims (6)

A raw material preparation step of preparing the dried cypress leaves by washing the cypress leaves to remove foreign substances and drying them to a moisture content of 15% or less;
A raw material extraction step of extracting the cypress tree leaves from the raw material preparation step in an extractor to obtain a cypress tree leaf extract;
A drying step of drying the cypress tree leaf extract from the raw material extraction step in a reduced pressure dryer at a temperature of 40 to 50° C. for 120 to 90 minutes;
A graphene synthesis step of preparing graphene and synthesizing redox graphene (r-GO-n) using a graphene surface modification method to add functional groups to the graphene;
A primary stirring step of adding the redox graphene from the graphene synthesis step and the cypress tree leaf extract prepared from the drying step into a mixer and first stirring for 3 to 5 hours at room temperature;
After the primary stirring is completed, secondary stirring for 24 to 18 hours at a temperature of 50 to 60 ° C. A method for producing a sterilizing and deodorizing agent containing graphene, comprising:
According to claim 1,
A method of manufacturing a sterilizing and deodorizing agent containing graphene, characterized in that in the drying step, the interior of the reduced pressure dryer is formed at a vacuum degree in the range of 90 to 100 mmHg.
According to claim 1,
A method for producing a sterilizing and deodorizing agent containing graphene, characterized in that the cypress tree leaf extract obtained in the raw material extraction step contains 0.6 to 1.0% by weight of phytoncide as an active ingredient.
According to claim 1,
Manufacture of a sterilizing and deodorizing agent containing graphene, characterized in that the redox graphene from the graphene synthesis step and the cypress tree leaf extract added in the first stirring step are added and mixed at a weight ratio of 0.01 to 0.05:0.6 to 1.0. method.
A sterilizing and deodorizing agent manufactured according to the manufacturing method according to any one of claims 1 to 4.
According to claim 5,
The sterilizing and deodorizing agent is characterized in that it consists of redox graphene and cypress tree leaf extract in a weight ratio of 0.01 to 0.05:0.6 to 1.0.