KR102415253B1 - Antimicrobial composite material with immediate sterilization characteristics and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an antibacterial composite material having sterilization performance and a method for manufacturing the same, in which aluminum hydroxide is bonded to the surface of a copper compound in an island shape, wherein the antibacterial composite material has 5 against bacteria or viruses Not only does it show sterilization performance quickly for a quick time within minutes, but this sterilization performance is maintained for a long time and can be utilized in various areas requiring antibacterial to provide effective antibacterial and antiviral functions.

Description

Antimicrobial composite material with immediate sterilization characteristics and manufacturing method thereof

The present invention relates to an antimicrobial composite material having immediate sterilization performance and a method for manufacturing the same, and more particularly, to an antibacterial composite material that is a composite of a copper compound and aluminum hydroxide. The antibacterial composite material of the present invention not only exhibits immediate sterilization performance against bacteria or viruses, but also maintains such sterilization performance for a long time and can be utilized in various areas requiring antibacterial to provide effective antibacterial and antiviral functions.

An antibacterial or antiviral agent is a substance having an antibacterial function that inhibits and prevents the propagation of bacteria or viruses, and has a sterilizing function that ultimately leads to death.

These antibacterial or antiviral agents are coated on the surface of an already finished product or used mixed with materials in the process of making a product, thereby imparting antibacterial, antiviral and sterilizing effects to the product.

Antibacterial agents are largely divided into organic antibacterial agents and inorganic antibacterial agents.

Organic antibacterial agents include organic compounds and organometals having an antibacterial function, and when the surface with antibacterial function is exposed while acting closer to antibacterial rather than sterilizing, it can prevent the instantaneous propagation of bacteria or viruses, as well as being inexpensive due to its low price. is being used

However, organic antibacterial agents have problems such as weak durability, not suitable for use in a high-temperature environment, and harmful to the human body or the environment.

In the case of inorganic antibacterial agents, safety for the human body and the environment is high, there is no generation of resistant bacteria, and the antibacterial duration is longer than organic antibacterial agents, so the scope of its use is gradually expanding.

Copper has recently been spotlighted as such an inorganic antibacterial agent. Copper has malleability and ductility, and is a metal with excellent heat and electrical conductivity. In addition, since it binds to proteins and transfers electrons or plays an important role in oxidation and reduction, it is an essential element in various living things, including humans.

Copper has a characteristic of having an antibacterial action and has been widely used in real life, such as being used for wound disinfection or drinking water storage containers from a long time ago. The utilization of copper having an antibacterial action is increasing.

Copper has the best sterilization ability when pure copper is present, but it is also effective in the case of an alloy containing about 55 to 70% copper. In particular, copper has excellent antibacterial performance against superbacteria such as methicillin-resistant Staphylococcus aureus (MRSA) as well as excellent sterilization ability against common fungi and bacteria. has registered about 300 copper alloys as antimicrobial substances useful in public health.

This antibacterial action of copper appears when a trace amount of metal ions disturb the metabolism of microorganisms and kill them, which is called 'micro-action'. Trace action is also shown in copper, gold, silver, platinum, aluminum, mercury, nickel, lead, cobalt, zinc, etc., but among them, the sterilization effect is relatively fast, and copper and silver, which are harmless to the human body, are widely used in real life.

Conventional antibacterial materials using copper, silver, etc. require at least 24 hours until their performance is 99.9% (that is, when 99.9% of bacteria or viruses are killed). Therefore, there is a problem that not only continues to multiply while most of the bacteria or virus survives until most of them are killed, but also there is a high possibility that the bacteria or virus is constantly spread to other places through numerous contacts. The distribution of silver varies from hours to days depending on the type of substance or product.

For example, it remains in an aerosol state for up to 2 hours, on surfaces such as latex gloves and aluminum cans for about 2 to 8 hours, and on metal handles, glass windows, glasses and ceramic pots, etc. for up to 5 days. can do.

Since bacteria and viruses spread rapidly, it is important to kill them as soon as possible to block them. However, since existing antibacterial materials exhibit antibacterial properties after at least 24 hours, it is necessary to develop antibacterial materials with immediate sterilization performance. do.

Registered Patent No. 10-1725799 (Registered on April 5, 2017)

An object of the present invention is to provide an antibacterial composite material that not only exhibits immediate sterilization performance against bacteria or viruses, but also maintains such sterilization performance for a long time and is utilized in various areas requiring antibacterial to provide effective antibacterial and antiviral functions.

An embodiment of the present invention for achieving the above object relates to an antibacterial composite material having a sterilization performance, having a form in which aluminum hydroxide is bonded to the surface of a copper compound in an island shape.

The aluminum hydroxide is a highly crystalline boehmite composite particle comprising: a first boehmite in a gamma phase; and a second boehmite obtained by a dehydration reaction of aluminum hydroxide, and the first boehmite and The second boehmite may be bonded by hydrogen bonding.

Another embodiment of the present invention is a mixing step of preparing a raw material mixture by mixing an aluminum hydroxide composition and a copper compound; a spray drying step of spray-drying the raw material mixture to form an antibacterial composite material; and a cooling step of cooling the antibacterial composite material.

The antimicrobial composite material may have a form in which aluminum hydroxide is bonded to the surface of the copper compound in an island shape.

In the raw material mixture, the aluminum hydroxide composition and the copper compound may be mixed in a weight ratio of 1: 0.7 to 1.2.

The aluminum hydroxide composition may be obtained through a milling process after aluminum hydroxide is mixed with ultrapure water in a concentration range of 5 to 15% by weight.

The average particle size of the copper compound particles may be 6 to 20 μm, and the average particle size of the aluminum hydroxide may be 10 to 500 nm.

The aluminum hydroxide may include a first boehmite of a gamma phase (γ-phase); and a second boehmite obtained through a dehydration reaction of aluminum hydroxide, wherein the first boehmite and the second boehmite may be bonded by hydrogen bonding.

The spray drying step may be a step of spray drying the raw material mixture in a temperature range of 180 ~ 220 ℃.

The cooling step may be a step of cooling the antibacterial composite material particles obtained through the spray drying step to a temperature of 90 ~ 120 ℃.

Another embodiment of the present invention relates to an antibacterial composite material having immediate sterilization performance prepared by the above method.

The antibacterial composite material of the present invention not only exhibits immediate sterilization performance against bacteria or viruses, but also maintains such sterilization performance for a long time and can be utilized in various areas requiring antibacterial to provide effective antibacterial and antiviral functions.

1 is an SEM photograph of an antibacterial composite material manufactured according to an embodiment of the present invention.
2 is an XRD result of the antibacterial composite material prepared according to an embodiment of the present invention.
3A and 3B are SEM photographs of cotton fibers coated with an antimicrobial composite material prepared according to an embodiment of the present invention.
4A and 4B are SEM photographs of samples used in Experimental Example 2.
5 is a photograph showing the experimental results of Experimental Example 4.

Before describing in detail through preferred embodiments of the present invention, terms or words used in the present specification and claims should not be construed as being limited to conventional or dictionary meanings, and meanings consistent with the technical spirit of the present invention and should be interpreted as a concept.

Throughout this 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.

Throughout this specification, "%" used to indicate the concentration of a specific substance is (weight/weight) %, solid/liquid (weight/volume)%, and liquid, unless otherwise specified. /liquid means (volume/volume)%.

In each step, the identification code is used for convenience of description, and the identification code does not describe the order of each step, and each step may be performed differently from the specified order unless the specific order is clearly stated in the context. have. That is, each step may be performed in the same order as the specified order, may be performed substantially simultaneously, or may be performed in the reverse order.

In the present specification, antibacterial means a function of inhibiting and preventing the propagation of bacteria or viruses, and sterilization means a function of killing bacteria or viruses while including an antibacterial function.

Hereinafter, an embodiment of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments, and those skilled in the art can implement various modified forms of the contents described herein within the scope of the present invention.

The present invention relates to an antibacterial composite material having immediate sterilization performance and a method for manufacturing the same. It can be killed within a short time of

In addition, there is an effect that this sterilization effect is maintained for a longer time compared to the conventional antibacterial agent.

The antimicrobial composite material having immediate sterilization performance according to an embodiment of the present invention has a shape in which aluminum hydroxide is bonded to the surface of a copper compound in an island shape. Specifically, the aluminum hydroxide particles having a smaller particle size than the copper compound on the surface of the copper compound particles having an average particle size of 6 to 20 μm are combined in an island shape. A plurality of aluminum hydroxide particles may be bonded to the surface of the copper compound, and the average particle size of the aluminum hydroxide particles may be 10 to 500 nm.

The aluminum hydroxide is a highly crystalline boehmite composite particle comprising: a first boehmite in a gamma phase; and a second boehmite obtained by a dehydration reaction of aluminum hydroxide, and the first boehmite and The second boehmite may be bonded by a hydrogen bond.

Another embodiment of the present invention relates to a method of manufacturing an antibacterial composite material having immediate sterilization performance, and the antibacterial composite material manufactured through this embodiment is an antibacterial composite material having immediate sterilization performance according to an embodiment of the present invention. can

The manufacturing method according to this embodiment includes a mixing step of mixing an aluminum hydroxide composition and a copper compound to prepare a raw material mixture; a spray drying step of spray-drying the raw material mixture to form an antibacterial composite material; and a cooling step of cooling the antibacterial composite material.

The antibacterial composite material has a form in which aluminum hydroxide is bonded to the surface of the copper compound in an island shape.

First, the mixing step is a step of preparing a raw material mixture by mixing an aluminum hydroxide composition and a copper compound.

In this step, the aluminum hydroxide composition and the copper compound may be mixed in an amount of 1: 0.7 to 1.2 parts by weight. Here, the aluminum hydroxide composition is an aqueous solution in which aluminum hydroxide is contained in an amount of 5 to 15% by weight in ultrapure water, and has a sol form in which aluminum hydroxide particles are dispersed in a colloidal state in ultrapure water as a solvent.

The immediate sterilization effect and the long-lasting sterilization effect of the antimicrobial composite material according to the present invention is an effect that appears when the aluminum hydroxide composition and the copper compound are included in the above-described weight range, and the aluminum hydroxide composition and the copper compound are included in the raw material mixture as described above. When included in an amount exceeding the weight range, only a general sterilization effect in which the sterilization effect is expressed after several hours is shown, and the sterilization effect does not appear immediately after being made within a few minutes, and the effect of extending the sterilization effect cannot be obtained. It is preferable to mix in one weight range.

The aluminum hydroxide composition may include 85 to 95% by weight of ultrapure water and 5 to 15% by weight of aluminum hydroxide.

The aluminum hydroxide contained in the aluminum hydroxide composition is a powdery aluminum hydroxide particle having a nano size, and for nanoization of the aluminum hydroxide particle, the aluminum hydroxide composition is obtained through a milling process after mixing ultrapure water and aluminum hydroxide in the above weight ratio. can

The milling process can be performed by mixing ultrapure water and aluminum hydroxide, and putting a bead mill of 1 to 5 mm into the grinding chamber at a filling rate of 50 to 70 vol%, and a rotation speed of 2000 to 4000 RPM and a flow rate of 80 to 140 L/hr. A milling process may be performed under conditions.

When the milling process is performed under these conditions, the aluminum hydroxide particles are pulverized from micro to nano sizes of uniform size to improve binding force with copper compounds, so that the sterilization effect of the antibacterial composite material is stably maintained for a long time. can

In this step, the aluminum hydroxide composition and the copper compound may be mixed in the above weight ratio and then uniformly stirred. Stirring may be performed for 5 to 10 hours for the raw material mixture at a speed of 100 to 500 RPM, and if the stirring speed is excessively slow or the stirring time is insufficient, uniform dispersion is not achieved, and the stirring speed is excessively In the early case, since there is a problem in that the yield of the antibacterial composite material, which is a composite of a copper compound and aluminum hydroxide, is lowered in the spray drying step, which is a subsequent step, because bubbles are generated, it is preferable that stirring is performed under the above-described process conditions.

As described above, the antibacterial composite material of the present invention has a form in which aluminum hydroxide particles are bonded to the surface of the copper compound particles in an island shape. Specifically, it has a form in which aluminum hydroxide particles having a particle size smaller than that of the copper compound are bonded to the surface of the copper compound particles having an average particle size of 6 to 20 μm, and a plurality of aluminum hydroxide particles may be bonded to the surface of the copper compound. The average particle size of the aluminum hydroxide particles may be 10-500 nm.

As described above, since a plurality of aluminum hydroxide particles having a size significantly smaller than the particle size of the copper compound are formed on the surface of the copper compound particles in a combined form, a sterilizing effect can be displayed immediately.

When the average particle size of the copper compound particles is formed below the above range, bonding to a plurality of aluminum hydroxide particles becomes difficult, making it difficult to form composite particles having an immediate sterilization effect. Due to this decrease, the sterilization effect may be reduced, or the application may not be possible depending on the type of product to which the antibacterial composite material is applied.

In addition, when the average particle size of the aluminum hydroxide particles is less than the above range, the influence of the aluminum hydroxide particles is lowered, and the immediate sterilization effect of the antibacterial composite material is reduced. The formation rate of particles containing aluminum hydroxide alone is increased through spray drying without forming an antibacterial composite material, and thus the yield of the antibacterial composite material is reduced.

Therefore, it is preferable to use a copper compound and aluminum hydroxide having the above-mentioned average particle size range.

The copper compound may be at least any one or more of copper hydroxide, copper sulfate, copper chloride, and hydrates thereof, but in particular, copper hydroxide (Cu(OH) ₂ ) is preferably used. When copper hydroxide is used, the human body and This is because the environmental safety is excellent and hydrogen bonding with aluminum hydroxide through a hydroxyl group (-OH) is made more easily.

The aluminum hydroxide particles may be generally used aluminum hydroxide particles, but preferably, boehmite particles may be used.

When boehmite particles are used, conventional boehmite particles such as γ-boehmite, α-boehmite, and pseudo-boehmite may be used. In this case, more preferably, highly crystalline boehmite composite particles including one boehmite having a gamma (γ) phase and a second boehmite grown in a reactor through a dehydration reaction of aluminum hydroxide may be used.

The first boehmite and the second boehmite of the highly crystalline boehmite composite particle have a physically or chemically bonded structure, and preferably have a structure bonded in the form of a hydrogen bond by a hydroxyl group (-OH) on the surface. can have Through this bonding with the second boehmite, the structure or shape of the micropores formed on the surface and inside of the first boehmite is changed.

As the highly crystalline boehmite composite particles, those in which second boehmite particles are bonded through hydrogen bonding around the surface of the first boehmite, which are seed crystals, may be used, and those whose particle size is adjusted by pulverizing may be used. have. Since such highly crystalline boehmite composite particles have a low specific surface area, the content of moisture or impurities contained in the particles is small, and thus the quality and stability are excellent.

The highly crystalline boehmite composite particles may be prepared through the following method.

First, γ-boehmite and aluminum hydroxide used as seed particles are separately pulverized to prepare raw materials. In this case, gibbsite or bayerite may be used as the aluminum hydroxide.

In this case, the pulverization may be accomplished through a conventional milling process (ball mill, dynomyl, etc.), and in the case of the γ-boehmite used as the first boehmite, not only dry pulverization but also pulverization and pulverization in a dispersed state in water. It is also possible to go through the process of dispersing at the same time.

Each raw material pulverized by the pretreatment process is preferably mixed with water before being put into the reactor and supplied to the reactor in a slurry state. At this time, the raw material in the slurry state may be supplied to the reactor through a pressurized spraying method, and the dehydration reaction of gibbsite or bayerite is induced through this pressure spraying method, and γ-bohemite, which is a seed particle, is Hydrogen bonding with the hydroxyl group (-OH) on the surface proceeds rapidly, so that the time required for crystallization can be significantly shortened.

The pressure spraying process is preferably performed at a pressure of 50 to 100 atmospheres and a flow rate of 6 to 200 ml/sec, and more preferably, the amount of the first boehmite added in the mixture to be sprayed under pressure is in the range of 1 to 50 wt %. Since the composition ratio of these raw materials affects the physical properties of the high-crystalline boehmite composite particles, which are the final products, it is desirable to precisely control them.

The highly crystalline boehmite composite particles may be prepared by a method different from the above-described method, if necessary.

Specifically, the first boehmite, γ-boehmite, is prepared in a slurry state (about 10 to 35% by weight) mixed with water, mixed with pulverized aluminum hydroxide, and then the prepared mixture is sprayed into the reactor under pressure. It can be manufactured in a way that is supplied through

The content of γ-boehmite included in the mixture present in the form of a slurry together with aluminum hydroxide may be in the range of 1 to 50 wt%, and, if necessary, additional dispersion so that γ-boehmite and aluminum hydroxide can be uniformly mixed with each other The process may be further performed.

The raw material mixture thus prepared is injected at a pressure of 50 to 100 atmospheres into a reactor (eg, an autoclave) maintained at high temperature and high pressure (10 to 100 bar), and the injection flow rate is in the range of 6 to 200 ml/sec. is preferable After all the raw materials are fed into the reactor, the reactor is aged for a certain time for crystallization.

The crystallization reaction time may vary from 5 minutes to 2 hours depending on the feed composition of the raw material, and is most preferably performed within 1 hour.

During the crystallization reaction, aluminum hydroxide supplied in the form of a slurry undergoes a dehydration reaction under high temperature and high pressure conditions in the reactor, and at the same time, a dehydration reaction of γ-boehmite (first boehmite) and aluminum hydroxide as seed particles. It is physically and chemically bound by the OH- group present on the surface of pseudo-bohemite formed through

The formed pseudo-boehmite is mainly combined around the surface of the first boehmite, and at this time, it is preferable to maintain the pressure inside the reactor in the range of 10 bar to 100 bar.

After the highly crystalline boehmite composite particles prepared in this way are discharged to the outside of the reactor, it is preferable to undergo a drying process at a temperature of about 90 to 150 ° C. It is also possible

Going through this water washing process not only removes impurities contained in the highly crystalline boehmite composite particles, which are the reaction product, but also because the slurry containing the reactants discharged from the reactor has basicity, the pH range can be adjusted through the water washing process. This is to change to the neutral region.

Thereafter, a milling step for controlling the particle size of the highly crystalline boehmite composite particles may be additionally performed, but since the particle size can be adjusted according to the process conditions of the pressure spraying process, this step is performed only when additional particle size control is required. It is further preferred to perform further.

These highly crystalline boehmite composite particles can form a stronger bonding force with copper compounds than conventional boehmite particles, have excellent thermal conductivity and oil absorption, and have a skin soothing effect. It has the effect of reducing the occurrence of irritation.

On the other hand, the spray-drying step is a step of spray-drying the raw material mixture prepared through the mixing step. At this time, the spray drying temperature may be 180 ~ 220 ℃.

The cooling step is a step of cooling the antibacterial composite material manufactured through the spray drying step, and the cooling temperature in this step may be 90 ~ 120 ℃.

The temperature conditions in the spray drying step and the cooling step are temperature conditions for maximizing the yield of an antibacterial composite material, which is a composite of aluminum hydroxide and copper compound, by improving the binding efficiency of aluminum hydroxide and copper compound, and at the same time, an antibacterial complex of a uniform size. Since it is for obtaining a raw material, it is preferable that the temperature in these steps is adjusted to the above-mentioned range.

The average particle size of the antimicrobial composite material finally manufactured through the cooling step may be 5 to 15 μm, and the antimicrobial composite material manufactured according to the above-described method may be applied to various fields.

For example, it can be applied to polymer films, non-woven fabrics, fibers, decorative sheets, paints, rubber products, ABS products, cosmetics and ceramic products such as ceramics, toilets, tiles, and washbasins to impart antibacterial performance to the product.

The antibacterial composite material of the present invention may be applied to the product as it is in a particulate state, may be mixed with water or an organic solvent, and may be mixed and used in a raw material compound when manufacturing polymer or rubber products, and may be used as a binder on the surface of an already finished product. It may be coated and used in the form of a mixed mixture, and the form applied to the product is not limited thereto.

Another embodiment of the present invention relates to a method for manufacturing an antibacterial fiber using the antibacterial composite material prepared according to the above-described method.

The antibacterial fiber manufacturing method, a swelling step of immersing the fiber in an immersion solution for a predetermined time; an antibacterial agent input step of injecting the antimicrobial composite material of the present invention into the immersion solution; A heating step of heating the immersion liquid to which the antibacterial composite material is added to produce an antibacterial fiber; and a washing step of washing the antibacterial fiber that has undergone the heating step.

The swelling step is a step of forming a space between the fibers by swelling the fibers so that the antimicrobial composite material is easily attached to the fibers.

In this step, water or an aqueous ethanol solution may be used as the immersion solution. In order to give a more effective swelling effect and to increase the penetration and adhesion to the fibers of the antibacterial composite material, an aqueous ethanol solution may be preferably used.

At this time, it is more preferable to immerse the fiber in the immersion solution and then heat it for 1 to 3 hours in a temperature range of 30 to 80°C. This is because, when immersed in an immersion solution at room temperature or low temperature, the swelling of the fibers is not sufficiently achieved and the time required for sufficient swelling is lengthened, so there is a problem in that the working time is excessively increased. Since fiber damage occurs when performed for a period of time, it is preferable that the swelling step be performed at the above-described temperature and time range.

The antibacterial agent input step is a step of adding and stirring the antimicrobial composite material having immediate sterilization performance prepared according to an embodiment of the present invention into the immersion solution in which the fibers are immersed.

In this step, the antibacterial composite material may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the immersion solution, when it is included in an amount of less than 1 part by weight, the antibacterial effect is insignificant, and when it is included in more than 10 parts by weight, the content is added Since the content of the antimicrobial composite material penetrating into the fiber is insignificant and economically undesirable, it is preferably included within the above-described weight range.

In the antibacterial agent input step, it is preferable to stir for 1 to 5 hours after the antibacterial composite material is added.

Next, the heating step is a step of bonding the fiber-impregnated antibacterial composite material to the fiber, and the immersion solution is heated to have a temperature range of 30 to 80° C. and can be maintained for 3 to 10 hours.

When the heating step is performed below the temperature range or less than the minimum time, sufficient bonding is not made, so the bonding efficiency is lowered compared to the amount of the antibacterial composite material input, and when the heating step is performed to exceed the temperature or exceed the above time Since fiber damage may occur, it is preferable that the heating step be performed to satisfy the temperature and time conditions described above.

The washing step is a step performed to remove the antimicrobial composite material remaining without being attached to the antibacterial fiber by washing the antibacterial fiber that has undergone the heating step, and to remove various foreign substances, using clean water or water containing detergent One or multiple washes may be performed.

Hereinafter, specific actions and effects of the present invention will be described through an embodiment of the present invention. However, this is presented as a preferred example of the present invention, and the scope of the present invention is not limited according to the embodiments.

[Production Example]

Preparation of aluminum hydroxide composition

As a first boehmite used as a seed crystal, gamma-phase boehmite (AOH, Ohsajiel Co., Ltd.) was dispersed in water to prepare a slurry. Gibbsite was used as aluminum hydroxide converted to second boehmite through dehydration reaction, and secondary particles were pulverized to a size range of 0.8 to 11.5 μm using a milling process. The gamma boehmite in the slurry state and the pulverized secondary particles were mixed, and the pressure was sprayed into an autoclave, a pressure vessel under high temperature and high pressure, at a pressure of 70 atmospheres and a flow rate of 100 ml/sec. Thereafter, a crystallization step of aging for 50 minutes was performed for crystallization to prepare highly crystalline boehmite composite particles.

Next, 10% by weight of the high-crystalline boehmite composite particles and 90% by weight of ultrapure water are mixed, and the high-crystalline boehmite composite particles having an average particle size of 80 to 200 nm using a bead mill (Wab dynomill ecm-ap2) are included. A nano-sol solution was prepared. At this time, a bead mill having a particle size of 3 mm was used by filling 65% by volume, and the rotation speed was set to 2380 RPM and the flow rate was set to 108 L/hr.

Antibacterial composite material manufacturing

The aluminum hydroxide composition prepared above and Cu(OH) ₂ powder having an average particle size of 6-15 μm were mixed in a weight ratio of 1:1 and stirred at a speed of 200 RPM for 7 hours to prepare a uniform colloidal solution, and then using an atomizer to obtain an antibacterial composite material powder by spray-drying under the process conditions of a pressure of 3 bar, an inlet temperature of 180 to 220 °C, and an outlet temperature of 90 to 120 °C.

It was confirmed that the obtained antibacterial composite material had physical properties of pH 6-7, EC 100-200 μs, particle size D10 of 3.24 μm, D50 of 7.80 μm, and D95 of 16.27 μm.

SEM pictures (5,000 times, 3,000 times, 1,000 times and 500 times magnifications) of the antibacterial composite material thus obtained were taken and shown in FIG. 1 , and XRD was taken and shown in FIG. 2 .

[Experimental Example 1]

First, the cotton fibers were immersed in a 20% aqueous solution of ethanol and heated at 50° C. for 2 hours to swell the cotton fibers. Next, the heating was stopped, and 8 parts by weight of the antibacterial composite material was added to the solution based on 100 parts by weight of the solution, followed by stirring for 3 hours. Thereafter, the antibacterial composite material was coated on the cotton fiber by heating at 65° C. for 6 hours, and washed twice to prepare the cotton fiber coated with the antibacterial composite material (Example 1). At this time, SEM photos of the fibers of Example 1 were taken and shown in FIGS. 3A and 3B, and the left side of each of FIGS. 3A and 3B is a cotton fiber before antimicrobial composite material coating, and the right side is a cotton fiber after antibacterial composite material coating. .

In addition, using the same method as described above, copper hydroxide (Cu(OH) ₂ ) instead of the antibacterial composite material was used alone to prepare a copper hydroxide-coated cotton fiber (Comparative Example 1).

Then, the antibacterial experiment (AATCC-TM2019) of Example 1 and Comparative Example 1 was performed, and the results are described in Table 1. As a control, cotton fibers without any antibacterial treatment were used.

Specifically, the fiber sample was cut to have a diameter of 4.8±0.1 cm and a weight of 1.0±0.1 g, sterilized in an autoclave at a temperature of 121±2° C. for 15 minutes, and then 5wt% Nutrient Broth and 0.05wt% Trition After diluting with a mixed solution of X-100 and neutralizing using Dey Engley Broth, Staphylococcus aureus ATCC 6538 and Klebsiella pneumoniae ATCC 4352 were inoculated at a concentration of 1.8×10 ⁵ cells/mL, respectively. After incubation, the antibacterial properties were measured by measuring the number of bacteria according to time.

At this time, at 5 minutes after inoculation, swab using a cotton swab, smear on solid medium, secondary culture, measure the number of bacteria, and measure antibacterial activity at 5 minutes, and after 24 hours after inoculation, 1 By measuring the number of bacteria in the primary culture medium, the antibacterial activity was measured at the time point after 24 hours.

(cells/mL) control Comparative Example 1 Example 1 Staphylococcus aureus after 5 minutes 1.8×10 ⁵ 1.8×10 ⁵ 7.2×10 ³ after 24 hours 7.0×10 ⁶ < 100 < 100 pneumococcus after 5 minutes 1.8×10 ⁵ 1.8×10 ⁵ < 100 after 24 hours 3.9×10 ⁷ < 100 < 100

Looking at the results in Table 1, in Comparative Example 1, it was confirmed that the antibacterial effect was shown 24 hours after inoculation, but no antibacterial performance was shown after 5 minutes immediately after inoculation. On the other hand, in Example 1 In the case of , the antibacterial effect was shown immediately after strain inoculation, and it was confirmed that it had a very good antibacterial effect, especially against pneumococcus.

Therefore, from the results of this experiment, when the antibacterial composite material of the present invention, which is a composite of aluminum hydroxide and copper compound, is applied to the fiber, it can be confirmed that the sterilization effect appears immediately upon contact of the strain with the antibacterial fiber.

[Experimental Example 2]

EDS and ICP analysis of the fiber sample of Example 1 prepared in Experimental Example 1 was performed.

EDS analysis was analyzed for each of two different regions of the fiber of Example 1 as a sample, SEM pictures of two samples used are shown in FIGS. 4A and 4B, and the analysis results for each sample are shown in Table 2 described.

ICP analysis was performed using 5100 ICP-OES (Agilent Technologies) using three different regions of the fiber of Example 1 as samples, and the results are shown in Table 3.

element Intensity (c/s) Error (2-sigma) Concentration (wt%) Example 1-1 C 30.73 2.12 39.50 O 30.39 2.06 51.68 Al 19.17 1.88 7.01 Cu 1.51 0.73 1.81 Sum 100.00 Example 1-2 C 6.88 1.06 41.44 O 6.00 0.90 45.95 Al 5.35 0.98 8.40 Cu 0.82 0.59 4.20 Sum 100.00

Al (ppm) Cu (ppm) Examples 1-3 44,973.5 7,680.4 Examples 1-4 40,607.3 8,002.6 Examples 1-5 39,078.5 8,425.3 Average 41,553.1 8,036.1

As shown in the results of Tables 2 and 3, it can be seen that copper and aluminum are detected in the antibacterial fiber of Example 1, and it can be confirmed that the antibacterial composite material of the present invention is well bonded to the antibacterial fiber of Example 1 there was.

[Experimental Example 3]

A polypropylene nonwoven fabric is prepared, immersed in an aqueous solution containing the antibacterial composite material for a predetermined time, and then dried to obtain an antibacterial composite material at a concentration of 1.0 g/m ² , 1.5 g/m ² , and 3.0 g/m ² , respectively. The coated nonwoven fabrics of Examples 2, 3 and 4 were prepared, respectively. In this case, the concentration of the antibacterial composite material means the number of grams per area of the nonwoven fabric.

Thereafter, antibacterial experiments were performed on Staphylococcus aureus and pneumococcus in the same manner as in Experimental Example 1 for each nonwoven fabric sample, and the results are shown in Table 4. At this time, the strain before inoculation was inoculated at a concentration of 1.5 × 10 ⁵ cells/mL, and the cell concentration was measured 24 hours after inoculation, and the antibacterial properties were determined based on the results.

In addition, an anti-mildness test was performed based on the experimental method AATCC 30:2017, TEST Ⅲ, and the results are shown in Table 4. Aspergillus niger ATCC 6275) was used as a strain during the Bangmi-do test, and the growth of the strain was observed after 2 weeks of culture. When no proliferation was observed, it was denoted as X, when observed under a 50-magnification microscope, as β, and when observed with the naked eye, it was denoted as O.

type of fungus control Example 2 Example 3 Example 4 antibacterial test
(cells/mL) Staphylococcus aureus 1.5×10 ⁷ < 100 < 100 < 100 pneumococcus 8.4×10 ⁷ < 100 < 100 < 100 Bangmi-do experiment koji fungus - △ X X

Looking at the results of Table 4, it was confirmed that the nonwoven fabric coated with the antibacterial composite material of the present invention had antibacterial properties against Staphylococcus aureus and pneumococci and antifungal properties against Koji mold. In particular, in the case of antibacterial property, it was confirmed that it appeared even when applied at a low concentration of 1.0 g/m ² , and in the case of antifungal property, it was confirmed that it appeared effectively when applied at a high concentration of 1.5 g/m ² or more.

[Experimental Example 4]

The antibacterial composite material prepared in Preparation Example was mixed with ethanol and then uniformly stirred to prepare an antibacterial composition having an antibacterial composite material concentration of 10% by weight.

Next, prepare a commercially available transparent hard-coating paint (DO-444, Haedong Polymer Industry Co., Ltd.) and mix it with the hard-coating paint so that the concentration of the antimicrobial composition is 5% by weight, and then PC (polycarbonate) film and It was coated on a PET film and dried to prepare a coated PC film and a PET film (Example 5).

Thereafter, the PET film was cut to a size of 5 × 5 cm, and an antibacterial experiment (KCL-FIR-1003: 2018) was performed for E. coli (Escherichia coli ATCC 8739) and Staphylococcus aureus ATCC 6538P (KCL-FIR-1003:2018), and the result is shown in Table 5.

Escherichia coli was inoculated at a concentration of 1.6×10 ⁵ CFU/mL, and Staphylococcus aureus was inoculated at a concentration of 3.6×10 ⁵ CFU/mL, and the cell concentration was measured after 24 hours and described in Table 5.

As a control, a sterile Stomarker film was used.

(CFU/mL) control Example 5 coli 9.1×10 ⁶ <10 Staphylococcus aureus 9.3×10 ⁶ <10

First, as a result of visually observing the coated PC film and the PET film, it was confirmed that the film was maintained in transparency. Also, from the results in Table 5, the antibacterial composite material of the present invention when applied to paint, E. coli and Staphylococcus aureus It was confirmed that it has excellent antibacterial activity against cocci.

[Experimental Example 5]

First, antibacterial composite material 1-4 wt%, styrene acrylic copolymer (Fine chem tech) 2 wt%, nonionic surfactant propylene glycol (SK Chemical) 0.5 wt%, anionic surfactant sodium dioctyl sulfosuccinate (Hannong chemical) 0.2% by weight, silicone-based antifoaming agent AFE-3150 (Dow chemical) 0.05% by weight and the remaining amount of pure water were mixed to prepare an antibacterial coating solution.

Next, the nonwoven fabric made of polypropylene was immersed in the antibacterial coating solution and dried in an oven at 50° C. for 2 hours to prepare an antibacterial coated nonwoven fabric.

Then, after performing the same antimicrobial test as the antibacterial test against Staphylococcus aureus of Test Example 3, the results are shown in FIG. 5 . In FIG. 5, the dilution concentration means a dilution concentration when the liquid culture solution is spread on a solid medium.

Referring to FIG. 5 , when the antibacterial composite material is included in an amount of 1 wt % or more, it was confirmed that it has antibacterial activity against Staphylococcus aureus.

[Experimental Example 6]

An antibacterial composite material was prepared using the same method as in Preparation Example, but the content of the aluminum hydroxide composition and Cu(OH) ₂ powder was adjusted as shown in Table 6 below to prepare the antibacterial composite material of Samples 2 to 6.

Antibacterial fibers of Samples 1 to 7 were prepared in the same manner as in Experimental Example 1 using each of the previously prepared samples. Here, Sample 1 and Sample 7 did not use the antibacterial composite material of the present invention, Sample 1 used the aluminum hydroxide composition prepared in Preparation Example alone as an antibacterial agent, and Sample 7 was Cu(OH) ₂ powder alone was used.

Aluminum hydroxide (parts by weight) Cu(OH) ₂ (parts by weight) sample 1 1.0 0.0 sample 2 1.0 0.5 sample 3 1.0 0.7 sample 4 1.0 1.0 sample 5 1.0 1.2 sample 6 1.0 1.4 sample 7 0.0 1.0

Thereafter, an antimicrobial test was performed in the same manner as in Experimental Example 1, and the results are shown in Table 7. At this time, Staphylococcus aureus was inoculated at a concentration of 2.1×10 ⁵ cells/mL, and pneumococcus at a concentration of 1.3×10 ⁵ cells/mL.

Staphylococcus aureus (cells/mL) pneumococcus (cells/mL) after 5 minutes after 24 hours after 5 minutes after 24 hours sample 1 2.1×10 ⁵ < 100 1.3×10 ⁵ < 100 sample 2 2.1×10 ⁵ 5.2×10 ³ sample 3 9.7×10 ³ <100 sample 4 6.9×10 ³ <100 sample 5 8.1×10 ³ <100 sample 6 2.1×10 ⁵ 1.3×10 ⁵ sample 7 2.1×10 ⁵ 1.3×10 ⁵

Looking at the results of Table 7, all of Samples 1 to 7 showed excellent antibacterial effects after 24 hours. In particular, in the case of Samples 3 and 5, the sterilization effect on both strains immediately appeared after 5 minutes immediately after strain inoculation. It was confirmed that, in particular, it was confirmed that the immediate sterilization effect against pneumococci was very good.

In addition, in the case of sample 2, it was confirmed that it showed an immediate sterilization effect against pneumococci.

From these results, it was confirmed that the composite in which the aluminum hydroxide composition including aluminum hydroxide particles and the copper compound were combined had an immediate sterilization effect.

In particular, it was confirmed that the weight ratio of the copper compound to 1 part by weight of the aluminum hydroxide composition in the preparation of the antibacterial composite material is preferably less than 1.2, and more preferably It was confirmed that the aluminum hydroxide composition and the copper compound were preferably included in a weight ratio of 1: 0.7 to 1.2.

[Experimental Example 7]

After leaving each antibacterial fiber sample prepared in Experimental Example 7 in an indoor space with a temperature of 20 to 25° C. and a relative humidity of 45 to 55%, an antibacterial test against Staphylococcus aureus after 1 month, 3 months, and 5 months has elapsed Thus, the results are shown in Table 8. The antimicrobial test was carried out in the same manner as in Experimental Example 7. At this time, Staphylococcus aureus was inoculated at a concentration of 2.0 × 10 ⁵ cells/mL.

strain type Staphylococcus aureus (cells/mL) Idle period (months) 1 month 3 months 5 months sample 1 <100 <100 1.2×10 ⁶ sample 2 <100 <100 1.4×10 ⁵ sample 3 <100 <100 <100 sample 4 <100 <100 <100 sample 5 <100 <100 <100 sample 6 <100 <100 8.1×10 ³ sample 7 <100 <100 5.4×10 ⁴

Looking at the results of Table 8, it was confirmed that each sample had excellent antibacterial properties up to 3 months after the antibacterial fibers were exposed to air. However, in the case of Sample 1 after 5 months, it was found that the antibacterial properties disappeared, In the case of Sample 2, Sample 6 and Sample 7, it was confirmed that very weak antibacterial activity remained.

On the other hand, in the case of Samples 3 to 5, it was found that the antibacterial properties were excellently maintained even after 5 months.

Therefore, from the results of this experiment, it was confirmed that the aluminum hydroxide composition and the copper compound were preferably included in a weight ratio of 1: 0.7 to 1.2 in the antimicrobial composite material of the present invention.

The present invention is not limited to the specific embodiments and descriptions described above, and without departing from the gist of the present invention claimed in the claims, any person skilled in the art to which the invention pertains can implement various modifications and such modifications shall fall within the protection scope of the present invention.

Claims (10)

Aluminum hydroxide is bonded to the surface of the copper compound in an island shape,
The aluminum hydroxide is a highly crystalline boehmite composite particle comprising: a first boehmite in a gamma-phase; and a second boehmite obtained through a dehydration reaction of aluminum hydroxide;
the first boehmite and the second boehmite are bonded to each other by a hydrogen bond;
An antibacterial composite material having immediate sterilization performance, characterized in that the aluminum hydroxide composition and the copper compound are mixed in a weight ratio of 1:0.7 to 1.2.
delete A mixing step of mixing the aluminum hydroxide composition and the copper compound to prepare a raw material mixture;
a spray drying step of spray-drying the raw material mixture to form an antibacterial composite material; and
A cooling step of cooling the antibacterial composite material;
In the antibacterial composite material, aluminum hydroxide is bonded to the surface of the copper compound in an island shape,
The aluminum hydroxide is a highly crystalline boehmite composite particle comprising: a first boehmite in a gamma-phase; and a second boehmite obtained by a dehydration reaction of aluminum hydroxide;
The first boehmite and the second boehmite are bonded by hydrogen bonds,
A method for producing an antibacterial composite material having immediate sterilization performance, characterized in that the aluminum hydroxide composition and the copper compound are mixed in a weight ratio of 1:0.7 to 1.2.
delete According to claim 3, wherein the aluminum hydroxide composition,
A method for producing an antibacterial composite material having immediate sterilization performance, which is obtained through a milling process after aluminum hydroxide is mixed with ultrapure water in a concentration range of 5 to 15% by weight.
4. The method of claim 3,
The average particle size of the copper compound particles is 6 ~ 20㎛, the method for producing an antibacterial composite material having an immediate sterilization performance, characterized in that the average particle size of the aluminum hydroxide is 10 ~ 500㎚.
delete According to claim 3, wherein the spray drying step,
A method for producing an antibacterial composite material having immediate sterilization performance, characterized in that the raw material mixture is spray-dried in a temperature range of 180 to 220 ° C.
According to claim 3, wherein the cooling step,
A method for producing an antibacterial composite material having immediate sterilization performance, characterized in that the particles of the antibacterial composite material obtained through the spray drying step are cooled to a temperature of 90 to 120 °C.
Claims 3, 5, 6, 8 and 9, wherein any one of the method of any one of the manufactured, antibacterial composite material having an immediate sterilization performance.

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