KR102229098B1 - Manufacturing method of composition for antibiotic water pipe - Google Patents

Abstract

The present invention relates to a method of manufacturing an antibacterial copper fusion polyethylene water pipe. More particularly, the method includes the steps of: preparing a porous body formed therein with a microporous material by mixing, heating and then quenching a positive binding resin and a porous forming agent; impregnating an aqueous copper precursor solution in the microporous material by mixing the prepared porous body with the aqueous copper precursor solution; preparing a wet copper carrier by reducing copper ions in the aqueous copper precursor solution after adding reduced metal to the porous body in which the aqueous copper precursor solution is impregnated, and recovering the oxidized reduced metal; drying the prepared wet copper carrier; coating the dried copper carrier with an emulsion positive binding resin and drying the same; and preparing a water pipe by mixing the coated and dried copper carrier with a polyethylene resin. According to the present invention, the water pipe has excellent antibacterial and long-term antibacterial properties to decrease the formation of scale therein, erosion of the water pipe is prevented, and the antibacterial agent is not eluted, so that human stability is excellent even when applied as a water supply pipe.

Description

Manufacturing method of antibacterial copper fusion polyethylene water pipe {MANUFACTURING METHOD OF COMPOSITION FOR ANTIBIOTIC WATER PIPE}

The present invention relates to a method of manufacturing an antimicrobial copper fused polyethylene water pipe, and more particularly, a method of manufacturing an antimicrobial copper fused polyethylene water pipe having excellent antibacterial properties and excellent human safety due to no elution of copper, an antibacterial agent, and also excellent long-term antibacterial properties. It is about.

In general, water pipes are made of metal such as cast iron pipes or zinc pipes, but when used for a long time, the inner wall is easily corroded by the tap water flowing inside the pipe, so when used for a long time, the corroded rust mixes with tap water and generates contaminants such as red water or white water. Drinking becomes impossible, and water leakage occurs in the water pipe due to corrosion as described above, or the life of the pipe is remarkably shortened due to a decrease in water passing capacity.

Recently, water pipes made of synthetic resins such as PE and PVC have been used instead of metal pipes. The synthetic resin water pipe has the advantage of being easy to handle and transport because of its light weight, and that it is easy to adhere and repair through an adhesive or socket connection and butt fusion method.

However, PE water pipes easily propagate harmful microorganisms such as E. coli when water flows inside the water at a low speed or stay for a long time, and scale is formed on the inner wall of the water pipe or the water pipe is eroded due to the repetitive formation of bacterial membranes due to the reproduction of these microorganisms. There are disadvantages such as.

In addition, the PVC material water pipe has a problem that static electricity is generated on the surface of the pipe due to friction with the inside of the pipe, and thus foreign substances contained in the water are adsorbed to the inner wall of the pipe.

In order to solve this problem, Korean Patent No. 10-1128054 proposes a method of forming an inner diameter coating layer by mixing a PE resin with an antimicrobial ceramic material in a water pipe to have antibacterial properties. However, since PE resin does not adhere or chemically bond with other materials, when used as a water pipe, the antimicrobial ceramic material quickly elutes into the water flowing through the water pipe, and the antibacterial effect disappears easily.

KR 10-1128054 B1

An object of the present invention is to provide a method of manufacturing an antimicrobial copper fused polyethylene water pipe having excellent antimicrobial properties as well as excellent human safety due to no elution of copper, and excellent long-term antimicrobial properties.

The method of manufacturing an antimicrobial copper fusion polyethylene water pipe of the present invention for achieving the above object comprises the steps of preparing a porous body having microporous materials by mixing an amphoteric binding resin and a porosity forming agent, heating it, and then quenching it, The prepared porous material is mixed with an aqueous copper precursor solution to support an aqueous copper precursor solution on the microporous material, and a reducing metal is added to the porous material on which the aqueous copper precursor solution is supported to reduce copper ions in the aqueous copper precursor solution. Preparing a wet copper carrier, recovering the oxidized reduced metal, drying the prepared wet copper carrier, coating and drying the dried copper carrier with an emulsion amphoteric resin, and the coating and It characterized in that it comprises the step of manufacturing a water pipe by mixing the dried copper carrier with a polyethylene resin.

In the step of preparing a porous body in which microporous materials are formed by mixing the amphoteric binding resin and the porous mass former, heating it, and then rapidly cooling it, the amphoteric binding resin is maleic anhydride ethylene copolymer, ethylene vinyl acetate Copolymer (Ethylene vinyl Acetate Copolymer) and chlorinated polyethylene (Chlorinated Polyethylene) is at least one type, the porous forming agent is aluminum hydroxide, the amphoteric binding resin and the porous forming agent are mixed in a weight ratio of 1: 2 to 10, 180 After heating to ~330℃ and then quenching to -200~-1℃, aluminum hydroxide, which is a porous material in the heating process, separates water molecules in the water vapor state by condensation reaction, and the water molecules in the water vapor state are quenched. It is characterized in that the porous body is manufactured in a state in which water particles are included in the porous body.

In the step of mixing and stirring the prepared porous material with an aqueous copper precursor solution to support the aqueous copper precursor solution on the microporous material, the copper precursor is at least one of copper nitrate, copper chloride, and copper sulfate, and included in the microporous material. It is characterized in that water particles are substituted with an aqueous copper precursor solution.

The reduced metal is one or more of aluminum, zinc, and iron, and the particle size is 1-100㎛, and the emulsion amphoteric resin is ethylene vinyl acetate copolymer emulsion, and the coating and drying The step of preparing a water pipe by mixing the obtained copper carrier with a polyethylene resin is characterized in that the coated and dried copper carrier is mixed with a polyethylene resin in a weight ratio of 0.2 to 2:9.

According to the method of manufacturing an antimicrobial copper fused polyethylene water pipe of the present invention, it has excellent antibacterial and long-term antibacterial properties, which reduces the formation of scale inside the water pipe, prevents erosion of the water pipe, and does not dissolve the antimicrobial agent, so that the human body stability is improved It has the advantage of being excellent.

1 is a flow chart showing a method of manufacturing an antimicrobial copper fusion polyethylene water pipe according to the present invention.
2 is an electron micrograph of a porous body manufactured according to Example 1 of the present invention.

Hereinafter, the present invention will be described in detail.

In the present invention, the water pipe includes both a water supply pipe and a sewer pipe.

The conventional method of manufacturing an antibacterial water pipe by simply mixing an antibacterial agent into a water pipe made of polyethylene (PE) material has poor binding with the antibacterial agent due to the characteristics of the polyethylene resin, so that the antibacterial agent is easily eluted when used as a water pipe, so the human body stability and antibacterial persistence are good There was a problem.

Accordingly, the present invention is characterized in that a water pipe is manufactured by fusing a polyethylene resin and an antibacterial agent, thereby preventing the dissolution of the antimicrobial agent, thereby improving human stability, antibacterial activity, and antibacterial persistence.

More specifically, the method of manufacturing an antimicrobial copper fusion polyethylene water pipe according to the present invention includes the steps of preparing a porous body having microporous material by mixing an amphoteric binding resin and a porous mass-forming agent, heating it, and then rapidly cooling it, and the preparation Wet copper by mixing the obtained porous material with an aqueous copper precursor solution to support the aqueous copper precursor solution on the fine porous material, and by adding a reducing metal to the porous material on which the aqueous copper precursor solution is supported to reduce copper ions in the aqueous copper precursor solution. Preparing a carrier, recovering the oxidized reduced metal, drying the prepared wet copper carrier, coating and drying the dried copper carrier with an emulsion amphoteric resin, and drying the coated and dried copper carrier. It characterized in that it comprises the step of manufacturing a water pipe by mixing a copper carrier with a polyethylene resin.

Hereinafter, the present invention will be described in detail step by step with reference to FIG. 1.

Mixing an amphoteric binding resin and a porous mass-forming agent, heating the same, and then rapidly cooling the mixture to prepare a porous body having fine porous masses.

First, the amphoteric binding resin and the porous mass former are mixed.

As the amphoteric binding resin, at least one of maleic anhydride ethylene copolymer, ethylene vinyl acetate copolymer, and chlorinated polyethylene may be used. Because it is copolymerized with ethylene, it is easy to bond with polyethylene resin, and maleic anhydride, vinyl acetate, and vinyl chloride, which are polymeric components, can be bonded to metal materials such as copper. That is, by first bonding copper as an antimicrobial agent to the amphoteric binding resin, and then combining the polyethylene resin and the amphoteric resin, the polyethylene resin without adhesion and binding of other substances and copper as an antimicrobial agent are unitarily and firmly combined. Since it can be combined, there is no elution of copper, which is an antimicrobial agent, even if it is used for a long time.

And as the porous forming agent, aluminum hydroxide is used. The aluminum hydroxide is a material that loses water molecules at a temperature of 180 to 300°C and forms α-aluminum oxide, which is a stable ceramic material. This aluminum oxide increases the wear resistance of water pipes.

The mixing ratio of the amphoteric binding resin and the porosity forming agent is preferably 1: 2 to 10 weight ratio, which forms sufficient microporosity in the porous body to support a large amount of copper, which is an antimicrobial agent, while considering the binding property with copper.

Further, zinc stearate may be further mixed as a dispersant during the mixing, and the implementation is not limited. At this time, the mixing ratio is sufficient if the amphoteric binding resin, the porosity forming agent, and zinc stearate are about a weight ratio of 1:2-10:1-4.

Next, the mixture of the amphoteric binding resin and the porous forming agent is introduced into a cylinder of an extruder heated to 180 to 330°C. In the cylinder, the amphoteric resin is melted, and the porous forming agent, aluminum hydroxide, separates water molecules by a condensation reaction to become α-aluminum oxide, a stable ceramic material, and the separated water molecules are in a vapor state in the melt. It expands under pressure.

And it is rapidly cooled to -200 ~ -1 ℃ while discharging the melt to the outlet of the cylinder. Through such rapid cooling, the melt is solidified as it is, and water vapor inside is also solidified as it is, so that a porous body composed of aluminum oxide and an amphoteric resin containing water particles therein is manufactured. That is, the sites of the water molecule are microporous, the microporous has a diameter of 0.1 to 1000 nm, and the porous body has an outer specific gravity (excluding water) of 0.03 to 0.33.

In the present invention, the particle size of the porous body is not limited, but may be about 10 to 5,000 μm, and it is natural that the size of the discharge port is adjusted or the particle size is pulverized after discharge.

Mixing the prepared porous material with an aqueous copper precursor solution to support the aqueous copper precursor solution on the microporous material

Next, by mixing the prepared porous material with the aqueous copper precursor solution, water molecules contained in the porous material are substituted with the aqueous copper precursor solution so that the aqueous copper precursor solution is supported on the microporous material. That is, the aqueous copper precursor solution is finely distributed in the porous body.

Here, the copper precursor aqueous solution is for forming copper as an antimicrobial agent into fine particles in the water pipe, and at least one of copper nitrate, copper chloride, and copper sulfate may be used. At this time, the copper precursor is sufficient if the amount of the prepared porous material and 5 to 30:100 weight ratio is used, and the concentration of the aqueous copper precursor solution, that is, the amount of water used, is not limited.

Adding a reducing metal to the porous material carrying the aqueous copper precursor solution to reduce copper ions in the aqueous copper precursor solution to prepare a wet copper carrier, and recovering the oxidized reduced metal

Next, by adding a reducing metal to the porous body carrying the aqueous copper precursor solution, copper ions in the aqueous copper precursor solution are reduced to form copper (Cu) or copper oxide (CuO).

More specifically, the porous body on which the copper precursor aqueous solution is supported is present in the aqueous solution through mixing with the copper precursor aqueous solution, and a reduced metal is gradually added to the aqueous solution until the pH becomes 6.9 to 7.1. By reducing ions, a wet copper carrier is prepared. And the oxidized reduced metal is recovered by sedimentation.

As the reducing metal, it suffices to use a metal powder capable of reducing copper ions to a metal. For example, at least one of aluminum, zinc, and iron may be used. And the particle size is not limited, but about 1-100㎛ is sufficient for smooth reduction reaction.

Drying the prepared wet copper carrier

Next, the prepared wet copper carrier is dried. At this time, the drying method is not limited. Here, the reduced copper (Cu) or copper oxide (CuO) in the wet copper carrier is oxidized even in the drying process to become _{a stable metal oxide of Cu 2} O or CuO, thereby forming semi-permanent antibacterial properties. The reduced copper (Cu) or copper oxide (CuO) in the copper carrier is highly reactive because it exists as nanoparticles or submicroparticles, and thus easily becomes Cu ₂ O or CuO.

Coating the dried copper carrier with an emulsion amphoteric resin and drying

Next, the dried copper carrier is coated with an emulsion amphoteric resin, and dried to a moisture content of 0.1% or less.

The coating is intended to prevent this, since copper oxide in the copper carrier may be transferred to the polyethylene resin alone during the extrusion process of the water pipe, resulting in a low bonding state. That is, by coating the surface of the particles of the copper carrier with an emulsion amphoteric resin, during melt extrusion with the polyethylene resin, the amphoteric resin is first bonded to the copper oxide and then secondly melted and mixed with the polyethylene resin, so that perfect integral bonding is achieved. do.

As the emulsion amphoteric resin, it is preferable to use an ethylene vinyl acetate copolymer emulsion in consideration of binding properties, and a coating method and a drying method thereof are not limited.

Manufacturing a water pipe by mixing the coated and dried copper carrier with a polyethylene resin

Then, the coated and dried copper carrier is mixed with a polyethylene resin and melt-extruded to manufacture a water pipe. The melt extrusion method is according to the prior art.

At this time, the mixing ratio of the coated and dried copper carrier and the polyethylene resin is preferably 9:0.2 to 2 weight ratio, considering the physical properties and antibacterial properties of the water pipe.

In addition, the water pipe may be in the form of a double pipe or a triple pipe instead of a single pipe, and the inner layer is extruded with a polyethylene resin fused with a copper carrier as described above, and the other middle and outer layers are made of a general polyethylene resin. It can be extruded, but it is not limited thereto.

As described above, the water pipe of the present invention prepared as described above has excellent binding properties with polyethylene resin and excellent antibacterial activity by distributing copper in the form of oxide as ultrafine particles in the carrier of the amphoteric resin. Of course, even if it is used for a long time in water, it is not oxidized or eluted, so it has the advantage of forming a permanent antibacterial property.

Hereinafter, the present invention will be described in detail through specific examples.

(Example 1)

Ethylene maleate copolymer, aluminum hydroxide, and zinc stearate were mixed in a weight ratio of 1:4:2, and then put into a melt-type extruder cylinder heated to 260°C. The melt residence time of the screw in the cylinder was set to 3 minutes, and the melt was discharged to the outlet of the cylinder head by the discharge pressure of the screw and cooled to -18°C at the same time. The coolant was a composite material with water particles of 0.1 to 1000 nm formed therein, and was a porous body having an outer specific gravity (excluding moisture particles) of 0.25, and an average particle size of about 325 μm. 2 is an electron micrograph of the manufactured porous body.

Next, copper nitrate was pulverized to an average particle size of 450 μm and dissolved in water to prepare an aqueous copper nitrate solution. Then, the porous body was added thereto and stirred at room temperature for 60 minutes, thereby replacing the water particles inside the porous body with an aqueous copper nitrate solution. At this time, the copper nitrate, water, and porous material used were in a weight ratio of 1:15:10.

Then, zinc metal powder having a particle size of 10 μm as a reducing metal was gradually added to the aqueous solution in the state in which the porous body was added to make the pH of the aqueous solution 7 to prepare a wet copper carrier, and the nitrified zinc powder was precipitated and separated. I did. And it was dried at 60 ℃ for 8 hours to prepare a copper carrier.

Next, the copper carrier was immersed in an EVA emulsion (5% solid content) aqueous solution to remove it, and wet-coated, and dried at 65° C. so as to have a water content of 0.1%.

And it is mixed with high-density polyethylene (HDPE) (Daehan Emulsification P600) for manufacturing PE pipes in a weight ratio of 9:1 to prepare a copper fused polyethylene resin, and melt-extruded to form an inner layer with a thickness of 5.7 mm, and thus high-density polyethylene (HDPE) An antimicrobial copper fusion polyethylene water pipe having a diameter of 315 mm was manufactured by sequentially forming a 15 mm thick intermediate layer and a 5 mm thick outer layer using (Daehan Petrochemical P600).

In addition, in order to test antibacterial properties, specimens having a width of 50 mm, a length of 50 mm, and a thickness of 2 mm were prepared using only copper fused polyethylene resin.

(Example 2)

Conducted in the same manner as in Example 1, except that ethylene vinyl acetate copolymer was used in place of the ethylene maleate copolymer as the amphoteric binding resin, copper sulfate was substituted for copper nitrate as the copper precursor, and aluminum powder was substituted for zinc powder as the reducing metal. Was used.

(Comparative Example 1)

Specimens having a width of 50 mm, a length of 50 mm, and a thickness of 2 mm were prepared using only high-density polyethylene (HDPE) (Daehan Petrochemical P600).

(Test Example 1)

The antimicrobial properties of Examples 1 and 2 and Comparative Example 1 were tested.

The antimicrobial test was conducted by JIS Z 2801:2010, a film adhesion method, and Staphylococcus aureus ATCC 6538P (yellow staphylococcus) and Escherichia coil ATCC 8739 (Escherichia coli) were used as strains. The results were shown in Table 1 below.

Test Example 1 result Strain state Comparative Example 1 Example 1 Example 2 Staphylococcus aureus Number of bacteria right after vaccination 1.0×10 ⁴ - - Number of bacteria after 24h 2.5×10 ⁴ <0.63 <0.63 Antibacterial activity - 4.7 (99.9%) 4.7 (99.9%) Escherichia coli Number of bacteria right after vaccination 1.0×10 ⁴ - - Number of bacteria after 24h 9.4×10 ⁵ <0.63 <0.63 Antibacterial activity - 0.62 (99.9%) 0.62 (99.9%) Test Methods Standard film: Stomacher®400POLY-BAG
Test conditions: Measure the number of bacteria after incubating the test bacteria solution at (35±1)℃, 90% .RH for 24 hours.
Antibacterial effect: more than 2.0 log of antibacterial activity

As shown in Table 1, it was confirmed that Examples 1 and 2 of the present invention have excellent antimicrobial properties.

(Test Example 2)

One side of the water pipe of Examples 1 and 2 was sealed, and the other side was sealed after adding 1L of tap water, and stored for 48 hours in a thermostat at 25°C, and whether or not the copper component was eluted. Whether or not the copper component was eluted was tested using AAS (Atomic Absorption Spectrometer, manufactured by Varian, USA).

The results were shown in Table 2 below.

Test Example 2 result (ppm) division Example 1 Example 2 Cu in tap water after 48 hours 0 0

As shown in Table 2, in Examples 1 and 2, it was confirmed that there was no elution of the copper component.

Although the above-described embodiments have been described for preferred examples of the present invention, the present invention is not limited thereto and can be implemented in various forms without departing from the technical spirit of the present invention. It is stated that it is natural for ordinary technicians to belong.

Claims (5)

Mixing an amphoteric binding resin and a porous mass-forming agent, heating the same, and then rapidly cooling it to prepare a porous body having microporous materials; and
Mixing the prepared porous material with an aqueous copper precursor solution to support the aqueous copper precursor solution on the microporous material; and
Adding a reducing metal to the porous material carrying the aqueous copper precursor solution to reduce copper ions in the aqueous copper precursor solution to prepare a wet copper carrier, and recovering the oxidized reduced metal;
Drying the prepared wet copper carrier,
Coating the dried copper carrier with an emulsion amphoteric resin and drying,
The method of manufacturing an antimicrobial copper fusion polyethylene water pipe, comprising the step of preparing a water pipe by mixing the coated and dried copper carrier with a polyethylene resin.
The method of claim 1,
In the step of preparing a porous body having fine porous mass by mixing the amphoteric binding resin and the porous mass forming agent, heating it, and then rapidly cooling it,
The amphoteric binding resin is one or more of maleic anhydride ethylene copolymer, ethylene vinyl acetate copolymer, and chlorinated polyethylene,
The porosity forming agent is aluminum hydroxide,
The amphoteric binding resin and the porous forming agent are mixed in a weight ratio of 1:2 to 10, heated to 180 to 330°C, and then rapidly cooled to -200 to -1°C. A method of manufacturing an antimicrobial copper fusion polyethylene water pipe, characterized in that the water molecules in the water vapor state are separated, and the water molecules in the water vapor state are rapidly cooled, thereby manufacturing a porous body in a state in which the water particles are contained in the microporous substance.
The method of claim 2,
In the step of mixing and stirring the prepared porous material with an aqueous copper precursor solution to support the aqueous copper precursor solution on the microporous material,
The copper precursor is at least one of copper nitrate, copper chloride and copper sulfate,
A method of manufacturing an antimicrobial copper fusion polyethylene water pipe, characterized in that the water particles contained in the microporous material are replaced with an aqueous copper precursor solution.
The method of claim 2,
The reduced metal is one or more of aluminum, zinc, and iron, and the particle size is 1-100㎛,
The emulsion amphoteric resin is an ethylene vinyl acetate copolymer emulsion (Ethylene Vinyl Acetate Copolymer Emusion), characterized in that the antimicrobial copper fusion polyethylene water pipe manufacturing method.
The method of claim 2,
The step of preparing a water pipe by mixing the coated and dried copper carrier with a polyethylene resin,
The method for producing an antimicrobial copper fusion polyethylene water pipe, characterized in that mixing the coated and dried copper carrier with a polyethylene resin in a weight ratio of 0.2 to 2:9.

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