KR102583053B1 - PVC antibacterial masterbatch and manufacturing method thereof - Google Patents

Abstract

The present invention discloses a polyvinyl chloride (PVC) antibacterial masterbatch containing: a PVC polymer resin; a plasticizer; an antibacterial agent; a stabilizer; and a colorant. Disclosed is a construction method in which the PVC antibacterial, non-polluting photocatalyst masterbatch produced in the way is heated to form a gel, which is injected into an extrusion molding machine with air suction and extruded into the mold (dies) at a constant pressure and speed and cooled by water cooling.

Description

PVC antibacterial masterbatch and manufacturing method thereof}

The present invention relates to a PVC antibacterial masterbatch and a manufacturing method thereof, and more specifically, to a PVC antibacterial masterbatch, a manufacturing method thereof, and a PVC window profile using the PVC antibacterial masterbatch.

Polyvinyl chloride (hereinafter PVC) is mainly used as a base material for window profiles, pipes, floor coverings and roof sheets, for example in the construction sector. Rigid and flexible films are likewise made from PVC. PVC is often used as an insulating material for electrical cables and electrical switch boxes, as shrink tube for cables, cable ducts or cable covers.

When using engineered wood for indoor or outdoor window frames, doors, or walls, PVC with wood grain printed is used as a finishing material to increase durability and create a wooden feel.

Compared to metal materials, PVC has a smaller specific gravity, is lighter, has excellent thermal conductivity, and has excellent insulation performance, so it is widely used as a window material. It is cheaper than metal materials, is easier to process, and is used as a profile material for manufacturing windows and doors of complex shapes. This is convenient.

PVC windows are widely used as exterior window finishing materials in construction, but the surface strength of the window material is weaker than that of metal aluminum window sashes.

Ultraviolet rays and oxygen in sunlight cause photo-oxidative decomposition of PVC, reducing its flexibility, ultimately making the structure on the PVC surface brittle, and the thermal expansion of PVC material and repeated friction when opening and closing windows make it less durable than metal.

There is a problem that scratches easily occur on the surface of these PVC windows due to thin photolysis.

In addition, due to this wear and tear, the replacement cycle is shortened, and harmful bacteria inhabit the scratched areas, and when PVC windows are opened and closed by multiple people's hands, cross-contact with harmful bacteria or bacteria occurs, which can be harmful to children and students with weak immune systems. , the elderly and vulnerable are exposed to risk.

In addition, due to the photodecomposition phenomenon of the PVC window sash surface caused by sunlight and ultraviolet rays, impurities in the atmosphere are adsorbed to the surface of the PVC window frame due to static electricity on the surface, polluting the building and making the building look bad.

Meanwhile, current PVC compositions have to sacrifice at least one property for another. For example, reinforcing additives can be applied to PVC compositions to improve physical properties such as tensile strength, but there is a problem that the elongation (%) is lowered or the overall physical properties are lowered due to excessive use of additives.

Patent Document 1: Republic of Korea Patent 10-0521005

The present invention was devised to solve the above problems, and the purpose of the present invention is to prevent deterioration even in high temperature and high humidity environments, to have excellent wear resistance, scratch resistance, and durability of PVC plastic products, and to exhibit excellent antibacterial properties while maintaining high temperature and humidity. We produce PVC windows by extruding PVC window sash profiles by producing an excellent PVC antibacterial masterbatch that has antibacterial properties that do not cause contamination by light ultraviolet rays and can decompose contaminants with photocatalysts.

The object of the present invention is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

In order to achieve the above object, the present invention

Polyvinyl chloride (PVC) polymer resin; antibacterial agents; plasticizer; stabilizator; It provides a PVC antibacterial masterbatch containing; and a colorant.

In addition, the present invention

After melting 100 parts by weight of PVC polymer resin, 13-17 parts by weight of polymer resin represented by the following formula 1, 4-8 parts by weight of dioctyl phthalate, and silane surface-treated antimony trioxide (Sb) are added to 100 parts by weight of PVC polymer resin. ₂ O ₃ ) Preparing a first mixture by mixing 5-9 parts by weight, 3-7 parts by weight of chlorosulfonated polyethylene rubber, and 1-5 parts by weight of copper fiber;

In the first mixture, 4-8 parts by weight of dioctyl phthalate, 1-5 parts by weight of methylcellulose, 25-29 parts by weight of zinc oxide particles with a particle size of 20-30 nm, 15-19 parts by weight of cuprous oxide particles, and 5 parts by weight of plant extract. -9 parts by weight, 10,10'-oxybisphenoxarsine (OBPA) 0.5-2 parts by weight, Zinc 2-pyridinethiol-1-oxide (Zn PTO) 0.5- Preparing a second mixture by mixing 2 parts by weight, 0.3-0.7 parts by weight of sodium chloride, 0.3-0.7 parts by weight of hindered amine, and 6-10 parts by weight of a colorant;

Melting and extruding the second mixture at a temperature range of 220-250° C. while stirring; and

Comprising: manufacturing a masterbatch by cooling and cutting the extrudate formed by performing the melting and extrusion,

The plant extract is,

Washing, freeze-drying, and pulverizing mulberry trees, fir trees, and drooping mulberry trees to produce mulberry tree powder, fir tree powder, and drooping mulberry tree powder; 20 g of the mixed powder made by mixing the prepared mulberry powder, fir tree powder and drooping mulberry powder in a weight ratio of 1:1:1 was mixed with 200 ml of water and subjected to primary hot water extraction at a temperature of 80°C for 8 hours while stirring. performing steps; After the first hot water extraction, filtering with filter paper and then freeze-drying the filtrate to prepare a first mixed extract; After the first hot water extraction, filter through filter paper and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and perform the second hot water extraction at a temperature of 120°C for 12 hours while stirring. steps; After secondary hot water extraction, filtering through filter paper and then freeze-drying the filtrate to prepare a secondary mixed extract; After secondary hot water extraction, filter through filter paper, and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and then add [BMIm][TFSI] (1-Butyl-3-methylimidazolium Adding 1-2 g of bis(trifluoromethylsulfonyl)imide) and performing third hot water extraction at a temperature of 100°C for 8 hours while stirring; After the third hot water extraction, filtering through filter paper and then freeze-drying the filtrate to prepare a third mixed extract; and mixing the first mixed extract, second mixed extract, and third mixed extract. A method for producing a PVC antibacterial masterbatch is provided.

<Formula 1>

(In Formula 1, n is 20-30, m is 20-30, a is 20-30, b is 20-30, and x is 5-50.)

Additionally, the present invention provides a PVC antibacterial window sash containing the PVC antibacterial masterbatch.

In addition, the present invention provides a photocatalytic non-polluting PVC antibacterial window sash containing the above PVC antibacterial masterbatch.

In addition, the present invention

After melting 100 parts by weight of PVC polymer resin, 13-17 parts by weight of polymer resin represented by Chemical Formula 1, 4-8 parts by weight of dioctyl phthalate, and silane surface-treated antimony trioxide (Sb) are added to 100 parts by weight of PVC polymer resin. ₂ O ₃ ) Preparing a first mixture by mixing 5-9 parts by weight, 3-7 parts by weight of chlorosulfonated polyethylene rubber, and 1-5 parts by weight of copper fiber;

In the first mixture, 4-8 parts by weight of dioctyl phthalate, 1-5 parts by weight of methylcellulose, 25-29 parts by weight of zinc oxide particles with a particle size of 20-30 nm, 15-19 parts by weight of cuprous oxide particles, and 5 parts by weight of plant extract. -9 parts by weight, 10,10'-oxybisphenoxarsine (OBPA) 0.5-2 parts by weight, Zinc 2-pyridinethiol-1-oxide (Zn PTO) 0.5- Preparing a second mixture by mixing 2 parts by weight, 0.3-0.7 parts by weight of sodium chloride, 0.3-0.7 parts by weight of hindered amine, and 6-10 parts by weight of a colorant;

Melting and extruding the second mixture at a temperature range of 220-250° C. while stirring;

Cooling and cutting the extrudate formed by performing the melting and extrusion to produce a masterbatch; and

After making the masterbatch into a gel form, injecting it into an extrusion molding machine with air suction, extruding it into a mold at a constant pressure and speed to produce a PVC window profile through cooling using water cooling. A method of manufacturing a PVC window profile including a step. provides.

The PVC antibacterial masterbatch according to the present invention does not deteriorate even in high temperature and high humidity environments, has excellent wear resistance, scratch resistance, and durability of PVC plastic products, and exhibits excellent antibacterial properties while maintaining excellent antibacterial properties. In addition, it is not polluted by solar ultraviolet rays and pollutants can be decomposed by photocatalysts, making it possible to manufacture excellent PVC window sash profiles.

In addition, the PVC window profile according to the present invention has excellent appearance characteristics including a surface coating layer, and is excellent in adhesion, impact resistance, and hardness.

Figure 1 shows an extrusion molding device used in the method of manufacturing a PVC window profile according to an embodiment of the present invention.

Hereinafter, various embodiments will be described in more detail with reference to the attached drawings. The embodiments described herein may be modified in various ways. Specific embodiments may be depicted in the drawings and described in detail in the detailed description. However, the specific embodiments disclosed in the attached drawings are only intended to facilitate understanding of the various embodiments. Accordingly, the technical idea is not limited to the specific embodiments disclosed in the attached drawings, and should be understood to include all equivalents or substitutes included in the spirit and technical scope of the invention.

Terms containing ordinal numbers, such as primary, secondary, first, second, etc., may be used to describe various components, but these components are not limited by the above-mentioned terms. The above-mentioned terms are used only for the purpose of distinguishing one component from another.

In this specification, terms such as 'include' or 'have' are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof. When a component is said to be 'connected' or 'connected' to another component, it is understood that it may be directly connected or connected to the other component, but that other components may exist in between. It should be. On the other hand, when a component is mentioned as being 'directly connected' or 'directly connected' to another component, it should be understood that there are no other components in between.

In this specification, the term masterbatch is used synonymously with compound and plastic product, and is understood to mean the introduction of additives into a polyvinyl chloride (PVC) polymer matrix. The at least one polymer or polymer is preferably formed at least 50% by weight, preferably at least 80% by weight from the monomer vinyl chloride. This primarily applies to cases where the polymer is a PVC copolymer formed not only from vinyl chloride but also from other monomers, for example vinyl acetate or butylacrylate. In such cases, the copolymer is preferably formed at least 50% by weight, more preferably at least 80% by weight from the monomer vinyl chloride. This is secondarily the case when the polymer comprises a mixture or blend of various polymers, one of which is a PVC homopolymer or a PVC copolymer. In such cases, the mixture or blend is preferably formed at least 50% by weight, more preferably at least 80% by weight from the monomer vinyl chloride. The polymer is preferably PVC.

In addition, when describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof is abbreviated or omitted.

The present invention relates to polyvinyl chloride (PVC) polymer resin; antibacterial agents; plasticizer; stabilizator; It provides a PVC antibacterial masterbatch containing; and a colorant.

The theoretical melting point of PVC is 220℃, but thermal decomposition begins at 100℃, which is much lower than that, and has the disadvantage of causing degradation even by ultraviolet rays. Additionally, its softening point is relatively low, so its mechanical strength decreases around 80℃. There is a disadvantage in that it drops sharply. However, it has excellent chemical resistance and flame retardancy that extinguishes the flame as soon as the flame is removed. It is compatible with various additives such as plasticizers, stabilizers, and fillers, and mixes quite well with other polymer materials, so its processing range is very wide. Therefore, although it has poor thermal stability, it is widely used for various processability.

PVC plastic products are used as structural materials for window frames (sashes), pipes, rainwater, and gutters, and soft products are used to manufacture wire coverings, medical tubes, toys, floor decorations, and disposable gloves. It is also used in automobile interior materials, sealants, and molded products, and its uses are countless. Additionally, because it has excellent transparency, it is used for transparent plastic bottles, films, sheets, etc. The processing characteristics of PVC resin include poor thermal stability, low activity, low plasticizer absorption, and excellent compatibility with additives. Due to these characteristics of the resin itself, PVC cannot be used alone and is sometimes used in combination with various additives. In addition, it has excellent compatibility with various additives, making it possible to produce products with various physical properties, and has the advantage that various processing methods can be used.

The polyvinyl chloride (PVC) polymer resin preferably has a degree of polymerization of 800 to 1200. If the degree of polymerization is less than 800, physical properties such as water resistance, acid resistance, and alkali resistance are lowered, and if the degree of polymerization is more than 1200, there is a problem of deterioration in processability, so the degree of polymerization is adjusted by paying attention to the range presented in the present invention.

The plasticizer is included to improve the processability of the PVC polymer resin and to provide flexibility and elasticity so that the PVC polymer resin can be processed and molded below its decomposition point. A preferred example of the plasticizer is dioctyl phthalate.

It is preferable to use copper fiber, zinc oxide particles, and cuprous oxide particles as the antibacterial agent.

Zinc oxide particles, especially zinc oxide nanoparticles, are substances that decompose various bacteria and pollutants by promoting catalytic reactions (oxidation and reduction reactions) using sunlight as an energy source. Zinc oxide is an excellent photocatalyst material because it has a high absorption rate in ultraviolet rays, high oxidizing power, and physical-chemical stability. When zinc oxide is exposed to light, it undergoes an oxidation-reduction (REDOX) reaction and generates O ^2- or OH radicals that act as a strong oxidizing agent. These radicals break down harmful organic substances around them and convert them into carbon dioxide and water. The surface of contaminated PVC window sashes can be maintained in its original color due to the photocatalytic phenomenon of zinc oxide particles. Moreover, zinc oxide can also carry out a mechanism to kill and eliminate viruses and bacteria by inhibiting their metabolism. The nano-sized zinc oxide has an increased specific surface area and has a surface effect that bulk materials do not have. When a PVC plastic product comes into contact with moisture in the air, the zinc metal component of the zinc oxide present on the surface is ionized and eluted. As a result, it acts as an antibacterial agent against harmful microorganisms such as bacteria. It is preferable to use zinc oxide particles as the inorganic antibacterial agent with a particle size of 20-30 nm, and more preferably with a particle size of 24-26 nm.

Cuprous oxide is a copper compound that exhibits antibacterial activity and exhibits higher antibacterial activity compared to copper oxide (CuO). Since cuprous oxide is easy to leach copper ions, the eluted copper ions can easily inhibit the metabolic function of microorganisms by binding to enzymes or proteins and reducing their activity when they come in contact with microorganisms. Therefore, it is desirable to introduce cuprous oxide together with zinc oxide as an inorganic antibacterial agent. The cuprous oxide particles may have a crystal structure or an amorphous structure. When cuprous oxide particles have a crystal structure, regardless of the crystal structure, they can change the structure of the protein constituting the surface of the bacteria or virus by coordinating with it, thereby inactivating the bacteria or virus.

Copper is an inorganic antibacterial agent that has antibacterial properties and does not deteriorate even in high temperature and high humidity environments and has excellent antibacterial properties. In addition, it does not react with other inorganic antibacterial agents and can exhibit excellent wear resistance, scratch resistance, and durability of PVC plastic products. As an inorganic antibacterial agent, copper material is introduced into copper fiber. The copper fiber assists in antibacterial properties, and by applying copper in the form of fiber, it has excellent miscibility with PVC resin.

The antibacterial agent is preferably 10,10'-oxybisphenoxarsine (OBPA), zinc 2-pyridinethiol-1-oxide (Zn PTO), and plant extracts. .

Even when injection molded at high temperatures, the PVC antibacterial masterbatch does not deteriorate the physical properties such as impact resistance and thermal stability of the PVC polymer resin itself by using a mixture of antibacterial agents, especially organic antibacterial agents such as OBPA, Zn PTO, and plant extracts, and does not deteriorate the physical properties of the PVC polymer resin itself. In addition, it has the effect of improving antibacterial properties and antibacterial properties against mold.

The plant extract is a mixture of mulberry extract, fir extract, and mulberry extract in a weight ratio of 1:1:1. Antibacterial functionality can be imparted by applying plant extracts including the mulberry extract, fir extract, and mulberry extract.

The stabilizer uses a mechanical/thermal stabilizer to prevent damage to the PVC polymer resin due to mechanical processing or applied heat, and an ultraviolet ray stabilizer to prevent decomposition of the polymer due to ultraviolet rays. The stabilizer preferably uses sodium chloride (NaCl) as a mechanical/thermal stabilizer and hindered amine as an ultraviolet ray stabilizer.

The colorant is also called a pigment, and the colorant is applied to color PVC plastic products. The colorant may be a copper phthalocyanine pigment.

In addition, the present invention

After melting 100 parts by weight of PVC polymer resin, 13-17 parts by weight of polymer resin represented by the following formula 1, 4-8 parts by weight of dioctyl phthalate, and silane surface-treated antimony trioxide (Sb) are added to 100 parts by weight of PVC polymer resin. ₂ O ₃ ) Preparing a first mixture by mixing 5-9 parts by weight, 3-7 parts by weight of chlorosulfonated polyethylene rubber, and 1-5 parts by weight of copper fiber;

In the first mixture, 4-8 parts by weight of dioctyl phthalate, 1-5 parts by weight of methylcellulose, 25-29 parts by weight of zinc oxide particles with a particle size of 20-30 nm, 15-19 parts by weight of cuprous oxide particles, and 5 parts by weight of plant extract. -9 parts by weight, 10,10'-oxybisphenoxarsine (OBPA) 0.5-2 parts by weight, Zinc 2-pyridinethiol-1-oxide (Zn PTO) 0.5- Preparing a second mixture by mixing 2 parts by weight, 0.3-0.7 parts by weight of sodium chloride, 0.3-0.7 parts by weight of hindered amine, and 6-10 parts by weight of a colorant;

Melting and extruding the second mixture at a temperature range of 220-250° C. while stirring; and

Comprising: manufacturing a masterbatch by cooling and cutting the extrudate formed by performing the melting and extrusion,

The plant extract is,

Washing, freeze-drying, and pulverizing mulberry trees, fir trees, and drooping mulberry trees to produce mulberry tree powder, fir tree powder, and drooping mulberry tree powder; 20 g of the mixed powder made by mixing the prepared mulberry powder, fir tree powder and drooping mulberry powder in a weight ratio of 1:1:1 was mixed with 200 ml of water and subjected to primary hot water extraction at a temperature of 80°C for 8 hours while stirring. performing steps; After the first hot water extraction, filtering with filter paper and then freeze-drying the filtrate to prepare a first mixed extract; After the first hot water extraction, filter through filter paper and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and perform the second hot water extraction at a temperature of 120°C for 12 hours while stirring. steps; After secondary hot water extraction, filtering through filter paper and then freeze-drying the filtrate to prepare a secondary mixed extract; After secondary hot water extraction, filter through filter paper, and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and then add [BMIm][TFSI] (1-Butyl-3-methylimidazolium Adding 1-2 g of bis(trifluoromethylsulfonyl)imide) and performing third hot water extraction at a temperature of 100°C for 8 hours while stirring; After the third hot water extraction, filtering through filter paper and then freeze-drying the filtrate to prepare a third mixed extract; and mixing the first mixed extract, second mixed extract, and third mixed extract. A method for producing a PVC antibacterial masterbatch is provided.

<Formula 1>

(In Formula 1, n is 20-30, m is 20-30, a is 20-30, b is 20-30, and x is 5-50.)

Hereinafter, the manufacturing method of the PVC antibacterial masterbatch according to the present invention will be described in detail at each step.

First, the method for producing the PVC antibacterial masterbatch according to the present invention is to melt 100 parts by weight of PVC polymer resin, and then add 13-17 parts by weight of polymer resin represented by Chemical Formula 1 and 4 parts by weight of dioctyl phthalate based on 100 parts by weight of PVC polymer resin. -8 parts by weight, 5-9 parts by weight of silane surface-treated antimony trioxide (Sb ₂ O ₃ ), 3-7 parts by weight of chlorosulfonated polyethylene rubber, and 1-5 parts by weight of copper fiber to prepare a first mixture. Includes steps.

In the above step, PVC polymer resin, which is the main polymer resin applied to the PVC antibacterial masterbatch, and dioctyl phthalate, which is a polymer resin represented by Chemical Formula 1 and a plasticizer, are mixed in an amount of 50% by weight of the total amount used, and the silane surface-treated A first mixture is prepared by mixing antimony trioxide, chlorosulfonated polyethylene rubber, and copper fiber.

The polyvinyl chloride (PVC) polymer resin preferably has a degree of polymerization of 800 to 1200. If the degree of polymerization is less than 800, physical properties such as water resistance, acid resistance, and alkali resistance are lowered, and if the degree of polymerization is more than 1200, there is a problem of deterioration in processability, so the degree of polymerization is adjusted by paying attention to the range presented in the present invention.

The polymer resin represented by Formula 1 is a silicone-modified acrylic polymer resin, a compound synthesized using polydimethylsiloxane and hydroxyethyl methacrylate, methyl methacrylate, methacrylic acid, and vinyltriethoxysilane. An acrylic copolymer synthesized from monomers is applied. The polymer resin represented by Formula 1 has the above structure and can be applied as an acrylic polymer resin that can prevent neutralization and has high adhesive properties and excellent durability. In Formula 1, n is 23-27, m is 23-27, a is 23-27, b is 23-27, x is more preferably 5-30, n is 25, and m is is 25, a is 25, b is 25, and x is 15. It is more preferable to mix 14-16 parts by weight of the polymer resin represented by Formula 1.

The dioctyl phthalate is included to improve the processability of the PVC polymer resin and to provide flexibility and elasticity so that the PVC polymer resin can be processed and molded below its decomposition point. It is more preferable to mix 5-7 parts by weight of the dioctyl phthalate.

The silane surface-treated antimony trioxide (Sb ₂ O ₃ ) is applied as a flame retardant to improve flame retardancy.

Including the chlorosulfonated polyethylene rubber, properties such as tensile strength and heat resistance are improved.

The copper fiber assists in antibacterial properties, and by applying copper in the form of fiber, it has excellent miscibility with PVC resin.

Next, the method for producing the PVC antibacterial masterbatch according to the present invention is to add 4-8 parts by weight of dioctyl phthalate, 1-5 parts by weight of methylcellulose, and 25-29 parts by weight of zinc oxide particles with a particle size of 20-30 nm in the first mixture. parts by weight, 15-19 parts by weight of cuprous oxide particles, 5-9 parts by weight of plant extract, 0.5-2 parts by weight of 10,10'-oxybisphenoxarsine (OBPA), zinc 2-pyridinethiol-1-oxide Preparing a second mixture by mixing 0.5-2 parts by weight of (Zinc 2-pyridinethiol-1-oxide, Zn PTO), 0.3-0.7 parts by weight of sodium chloride, 0.3-0.7 parts by weight of hindered amine, and 6-10 parts by weight of colorant. Includes.

In the above step, a second mixture is prepared by applying all the plasticizers, thickeners, antibacterial agents, stabilizers, and colorants contained in the PVC antibacterial masterbatch presented in the present invention.

The methylcellulose is used as a thickener. It is more preferable to mix 2-4 parts by weight of the methylcellulose.

The method of realizing the antibacterial effect of the zinc oxide particles is not through a sterilizing effect through photocatalytic activity, but through a mechanism that kills and removes viruses or bacteria by inhibiting their metabolism. The nano-sized zinc oxide has an increased specific surface area and has a surface effect that bulk materials do not have. When the antibacterial fiber comes into contact with moisture in the air, the zinc metal component of the zinc oxide present on the surface is ionized and eluted. It acts as an antibacterial agent against harmful bacteria such as bacteria. The zinc oxide particles preferably have a particle size of 20-30 nm, and more preferably 24-26 nm. It is more preferable to mix 26-28 parts by weight of the zinc oxide particles.

Cuprous oxide is a copper compound that exhibits antibacterial activity and exhibits higher antibacterial activity compared to copper oxide (CuO). Since cuprous oxide is easy to leach copper ions, the eluted copper ions can easily inhibit the metabolic function of microorganisms by binding to enzymes or proteins and reducing their activity when they come into contact with microorganisms. Therefore, it is desirable to introduce cuprous oxide together with zinc oxide as an inorganic antibacterial agent. The cuprous oxide particles may have a crystal structure or an amorphous structure. When cuprous oxide particles have a crystal structure, regardless of the crystal structure, they can change the structure of the protein constituting the surface of the bacteria or virus by coordinating with it, thereby inactivating the bacteria or virus. The cuprous oxide particles preferably have a particle size of 90-100 nm, and more preferably 94-96 nm. It is more preferable to mix 16-18 parts by weight of the cuprous oxide particles.

The plant extract is a mixture of mulberry extract, fir extract, and mulberry extract in a weight ratio of 1:1:1. Antibacterial functionality can be imparted by applying plant extracts including the mulberry extract, fir extract, and mulberry extract.

Mulberry (Broussonetia kazinoki) belongs to the Moraceae family and has been traditionally used for the production of Hanji (Korean paper) and for alleviating and treating inflammatory/infectious diseases (Korean Patent Publication No. 10-2012-0003603). Recently, it has also been used as a whitening material.

Psoriasis is a deciduous shrub of the legume family that commonly grows to a height of 2 to 3 m in mountains and fields and blooms in July to August. It is widely used for medicinal purposes due to its unique medicinal effects. It is known that fir tree contains flavonoids, pestidine, protein, fat, calcium, vitamin B1, amino acids, carbohydrates, iron, vitamins B, C, and K, and tannin chlorophyll.

Morus alba for pendula is a deciduous tree belonging to the Morus family of the nettle order and belonging to the dicotyledonous plant family. The scientific name is Morus alba for. It is pendula Dippel, and the leaves are ovate-circular or long oval-ovate, divided into 3-5 pieces, blunt or acuminate, have a deep heart base, are 10 cm long, have dull sawtooth edges, have a pointed tip, and have a rough or smooth surface, with veins on the back. There is fine hair. The petioles are also 2-2.5cm long and have fine hairs. The flower is a dioecious flower that blooms in June. The male flower is borne on a caudal inflorescence that droops down from the leaf axil at the bottom of the new branch where the male flower has fallen. The female flower spike is 5-10 mm long, has a wide oval shape, has 4 flowers, and has a flower stalk. short. The ovary is hairless. Compared to mountain mulberry, the flower stalk is shorter. The fruit is liquid and ripens black in June. The fruit spike is spherical or oval and is 1-2.5cm long. The bark is gray-brown. The branches are gray-brown or gray-white and have fine hairs, but they gradually disappear and the branches droop downward. It is distributed vertically at an altitude of 100 to 1,100 m, and horizontally almost throughout the country.

The PVC antibacterial masterbatch can exhibit excellent antibacterial functionality by including the plant extract.

The plant extract includes the steps of washing, freeze-drying, and pulverizing mulberry trees, fir trees, and mulberry trees to produce mulberry tree powder, fir tree powder, and mulberry tree powder; 20 g of the mixed powder made by mixing the prepared mulberry powder, fir tree powder and drooping mulberry powder in a weight ratio of 1:1:1 was mixed with 200 ml of water and subjected to primary hot water extraction at a temperature of 80°C for 8 hours while stirring. performing steps; After the first hot water extraction, filtering with filter paper and then freeze-drying the filtrate to prepare a first mixed extract; After the first hot water extraction, filter through filter paper and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and perform the second hot water extraction at a temperature of 120°C for 12 hours while stirring. steps; After secondary hot water extraction, filtering through filter paper and then freeze-drying the filtrate to prepare a secondary mixed extract; After secondary hot water extraction, filter through filter paper, and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and then add [BMIm][TFSI] (1-Butyl-3-methylimidazolium Adding 1-2 g of bis(trifluoromethylsulfonyl)imide) and performing third hot water extraction at a temperature of 100°C for 8 hours while stirring; After the third hot water extraction, filtering through filter paper and then freeze-drying the filtrate to prepare a third mixed extract; and mixing the first mixed extract, second mixed extract, and third mixed extract.

In addition, by using a mixture of OBPA and Zn PTO, the physical properties such as impact resistance and thermal stability of the PVC polymer resin itself are not reduced, and there is an effect of improving antibacterial and antibacterial durability against not only bacteria but also mold. It is more preferable to mix 0.8-1.2 parts by weight of OBPA. It is more preferable to mix 0.8-1.2 parts by weight of the Zn PTO.

Mechanical/thermal stabilizers are used to prevent PVC polymer resin from being damaged by mechanical processing or applied heat, and UV stabilizers are used to prevent decomposition of the polymer due to ultraviolet rays. In the present invention, it is preferable to use sodium chloride (NaCl) as a mechanical/thermal stabilizer and hindered amine as an ultraviolet stabilizer. It is more preferable to mix 0.4-0.6 parts by weight of sodium chloride. It is more preferable to mix 0.4-0.6 parts by weight of the hindered amine.

The colorant is also called a pigment, and the colorant is applied to color PVC plastic products. The colorant may be a copper phthalocyanine pigment. It is more preferable to mix 7-9 parts by weight of the colorant.

In addition, the step of preparing the second mixture is,

In the first mixture, 4-8 parts by weight of dioctyl phthalate, 1-5 parts by weight of methylcellulose, 25-29 parts by weight of zinc oxide particles with a particle size of 20-30 nm, 15-19 parts by weight of cuprous oxide particles, and 5 parts by weight of plant extract. -9 parts by weight, 10,10'-oxybisphenoxarsine (OBPA) 0.5-2 parts by weight, Zinc 2-pyridinethiol-1-oxide (Zn PTO) 0.5- It is more preferable to mix 2 parts by weight, 0.3-0.7 parts by weight of sodium chloride, 0.3-0.5 parts by weight of hindered amine, 6-10 parts by weight of colorant, and 3-7 parts by weight of nano silica sol surface-modified with siloxane. It is most preferable to mix 4-6 parts by weight of surface-modified nano silica sol.

By including nano silica sol surface-modified with the siloxane, physical properties such as tensile strength can be further improved.

The nano silica sol is formed by adding trivalent alkoxy silane or tetravalent alkoxy silane to an alcohol-based solvent that is miscible with water to form a silane mixture, and then adding the trivalent alkoxy silane or the tetravalent alkoxy silane to the alcohol-based solvent in a fixed amount. It means that it is obtained by stirring so that it is well dispersed.

The nano silica sol may have a particle size of 5-100 nm, and it is preferable to use 5-20 nm.

The trivalent alkoxy silane refers to a silane containing three hydroxy groups (-OH), and includes trimethoxysilane, triethoxysilane, and tri-n-propoxysilane (Tri-n- propoxysilane), Triisopropoxysilane, Methyltrimethoxysilane, Methyltriethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane (3-Glycidoxypropyltrimethoxysilane), etc.

The tetravalent alkoxy silane is a silane containing four hydroxy groups (-OH), and includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane. (Tetraisopropoxysilane), Tetrabutoxysilane, Tetraphenoxysilane, Tetraacethoxysilane, etc.

The alcohol-based solvent includes methanol, ethanol, propanol, isopropanol, butanol, etc.

The nano silica sol and siloxane are preferably mixed at a weight ratio of 1:2-5, more preferably at a weight ratio of 1:3-5, and most preferably at a weight ratio of 1:4.5.

The nano silica sol can be surface modified using 10-30% by weight of siloxane-type material after adjusting the pH to acidic.

The siloxanes are alkyl siloxanes, and the alkyl siloxanes may be hexaalkylsiloxane or tetraalkylsiloxane, and hexaalkylsiloxane is preferably used.

Next, the method for producing the PVC antibacterial masterbatch according to the present invention includes the steps of stirring the second mixture and melting and extruding it at a temperature range of 220-250°C.

In this step, the second mixture prepared in the previous step is stirred and melted and extruded at a temperature of 220-250°C to produce an extrudate.

The melting and extruding temperature range is preferably 220-250°C, and more preferably 230-240°C. We intend to manufacture a masterbatch by melting and extruding within the above range.

Next, the method for producing the PVC antibacterial masterbatch according to the present invention includes the step of cooling and cutting the extrudate formed by performing the melting and extrusion to produce the masterbatch.

Finally, the extrudate is cooled and cut to produce the PVC antibacterial masterbatch.

Additionally, the present invention provides a PVC antibacterial window sash containing the above PVC antibacterial masterbatch.

In addition, the present invention provides a photocatalytic non-polluting PVC antibacterial window sash containing the above PVC antibacterial masterbatch.

The PVC antibacterial window sash containing the PVC antibacterial masterbatch according to the present invention does not deteriorate even in a high temperature and high humidity environment, has excellent wear resistance, scratch resistance, and durability, and exhibits excellent antibacterial properties while maintaining excellent antibacterial properties. In addition, it is not polluted by solar ultraviolet rays and can decompose pollutants using a photocatalyst, showing even better performance.

In addition, the present invention

After melting 100 parts by weight of PVC polymer resin, 13-17 parts by weight of polymer resin represented by Chemical Formula 1, 4-8 parts by weight of dioctyl phthalate, and silane surface-treated antimony trioxide (Sb) are added to 100 parts by weight of PVC polymer resin. ₂ O ₃ ) Preparing a first mixture by mixing 5-9 parts by weight, 3-7 parts by weight of chlorosulfonated polyethylene rubber, and 1-5 parts by weight of copper fiber;

In the first mixture, 4-8 parts by weight of dioctyl phthalate, 1-5 parts by weight of methylcellulose, 25-29 parts by weight of zinc oxide particles with a particle size of 20-30 nm, 15-19 parts by weight of cuprous oxide particles, and 5 parts by weight of plant extract. -9 parts by weight, 10,10'-oxybisphenoxarsine (OBPA) 0.5-2 parts by weight, Zinc 2-pyridinethiol-1-oxide (Zn PTO) 0.5- Preparing a second mixture by mixing 2 parts by weight, 0.3-0.7 parts by weight of sodium chloride, 0.3-0.5 parts by weight of hindered amine, and 6-10 parts by weight of a colorant;

Melting and extruding the second mixture at a temperature range of 220-250° C. while stirring;

Cooling and cutting the extrudate formed by performing the melting and extrusion to produce a masterbatch; and

After making the masterbatch into a gel form, injecting it into an extrusion molding machine with air suction, extruding it into a mold at a constant pressure and speed to produce a PVC window profile through cooling using water cooling. A method of manufacturing a PVC window profile including a step. provides.

Hereinafter, the method for manufacturing a PVC window profile according to the present invention will be described in detail at each step.

Up to the step of manufacturing the masterbatch, it can be manufactured by performing the same method as the above-described PVC antibacterial masterbatch manufacturing method.

The PVC window profile manufacturing method according to the present invention uses the PVC antibacterial masterbatch produced in this way, and after making the masterbatch into a gel form, it is injected into an extrusion molding machine (or extrusion molding device) with air suction to maintain a certain pressure in the mold. It includes producing PVC window profiles by extruding at high speed and cooling using water cooling.

In this step, the finished masterbatch is stirred and co-extruded to produce the PVC window profile. As an example, it can be performed using an extrusion molding device as shown in Figure 1. The extrusion molding device includes a hopper into which the PVC antibacterial masterbatch, which is a molding material, is injected, the PVC antibacterial masterbatch is injected in gel form and moved to the mold, a main body including a heater, a heating cylinder, and a screw, and a hopper located between the main body and the mold. It includes a mold to extrude the shape of the blocking plate and PVC window profile.

In addition, the present invention

After melting 100 parts by weight of PVC polymer resin, 13-17 parts by weight of polymer resin represented by the following formula 1, 4-8 parts by weight of dioctyl phthalate, and silane surface-treated antimony trioxide (Sb) are added to 100 parts by weight of PVC polymer resin. ₂ O ₃ ) Preparing a first mixture by mixing 5-9 parts by weight, 3-7 parts by weight of chlorosulfonated polyethylene rubber, and 1-5 parts by weight of copper fiber;

In the first mixture, 4-8 parts by weight of dioctyl phthalate, 1-5 parts by weight of methylcellulose, 25-29 parts by weight of zinc oxide particles with a particle size of 20-30 nm, 15-19 parts by weight of cuprous oxide particles, and 5 parts by weight of plant extract. -9 parts by weight, 10,10'-oxybisphenoxarsine (OBPA) 0.5-2 parts by weight, Zinc 2-pyridinethiol-1-oxide (Zn PTO) 0.5- Preparing a second mixture by mixing 2 parts by weight, 0.3-0.7 parts by weight of sodium chloride, 0.3-0.5 parts by weight of hindered amine, and 6-10 parts by weight of a colorant;

Melting and extruding the second mixture at a temperature range of 220-250° C. while stirring;

Cooling and cutting the extrudate formed by performing the melting and extrusion to produce a masterbatch;

After making the masterbatch into a gel form, injecting it into an extrusion molding machine with air suction and extruding it into a mold at a constant pressure and speed to produce a PVC window profile through cooling using water cooling; and

A step of forming a surface coating layer by applying a composition for forming a surface coating layer to the PVC window profile,

The plant extract is,

Washing, freeze-drying, and pulverizing mulberry trees, fir trees, and drooping mulberry trees to produce mulberry tree powder, fir tree powder, and drooping mulberry tree powder; 20 g of the mixed powder made by mixing the prepared mulberry powder, fir tree powder and drooping mulberry powder in a weight ratio of 1:1:1 was mixed with 200 ml of water and subjected to primary hot water extraction at a temperature of 80°C for 8 hours while stirring. performing steps; After the first hot water extraction, filtering with filter paper and then freeze-drying the filtrate to prepare a first mixed extract; After the first hot water extraction, filter through filter paper and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and perform the second hot water extraction at a temperature of 120°C for 12 hours while stirring. steps; After secondary hot water extraction, filtering through filter paper and then freeze-drying the filtrate to prepare a secondary mixed extract; After secondary hot water extraction and filtering with filter paper, the remaining solids are mixed with water again so that the mixing ratio of solids and water is 0.1 g/ml, and then [BMIm][TFSI] (1-Butyl-3-methylimidazolium Adding 1-2 g of bis(trifluoromethylsulfonyl)imide) and performing third hot water extraction at a temperature of 100°C for 8 hours while stirring; After the third hot water extraction, filtering through filter paper and then freeze-drying the filtrate to prepare a third mixed extract; and mixing the first mixed extract, second mixed extract, and third mixed extract;

The composition for forming the surface coating layer includes 45-49 parts by weight of a polymer resin represented by the following formula (2), 18-22 parts by weight of an acrylic modified polyurethane resin, 5-9 parts by weight of copper powder, 5-9 parts by weight of calcium carbonate, and sodium dodecyl. 3-7 parts by weight of benzene sulfonate, 2-6 parts by weight of activated carbon powder, 0.5-4 parts by weight of cellulose thickener, 0.5-4 parts by weight of rosin ester-based adhesion enhancer, 2.2-methylenebis(6-tert-butyl-4) -Methylphenol) 0.3-2 parts by weight, 0.1-1 parts by weight of sodium chloride, and 0.1-1 parts by weight of hindered amine. A method of manufacturing a PVC window profile with a surface coating layer is provided.

<Formula 1>

(In Formula 1, n is 20-30, m is 20-30, a is 20-30, b is 20-30, and x is 5-50.)

<Formula 2>

(In Formula 2, o is 20-30, p is 20-30, q is 20-30, and r is 20-30.)

Hereinafter, the manufacturing method of the PVC window profile with the surface coating layer according to the present invention will be described in detail at each step.

Up to the step of producing the PVC window profile, it can be manufactured by performing the same method as the above-described PVC window profile manufacturing method.

The method of manufacturing a PVC window profile with a surface coating layer according to the present invention uses the PVC window profile produced in this way, and includes the step of forming a surface coating layer by applying a composition for forming a surface coating layer to the surface of the PVC window profile.

The composition for forming the surface coating layer includes 45-49 parts by weight of a polymer resin represented by Formula 2, 18-22 parts by weight of an acrylic modified polyurethane resin, 5-9 parts by weight of copper powder, 5-9 parts by weight of calcium carbonate, and sodium dodecyl. 3-7 parts by weight of benzene sulfonate, 2-6 parts by weight of activated carbon powder, 0.5-4 parts by weight of cellulose thickener, 0.5-4 parts by weight of rosin ester-based adhesion enhancer, 2.2-methylenebis(6-tert-butyl-4) -methylphenol) 0.3-2 parts by weight, 0.1-1 parts by weight of sodium chloride, and 0.1-1 parts by weight of hindered amine, and 46-48 parts by weight of the polymer resin represented by Formula 2, acrylic 19-21 parts by weight of modified polyurethane resin, 6-8 parts by weight of silicone compound represented by the following formula (4), 6-8 parts by weight of copper powder, 6-8 parts by weight of calcium carbonate, 4-6 parts by weight of sodium dodecyl benzene sulfonate parts, 3-5 parts by weight of activated carbon powder, 1-3 parts by weight of cellulose-based thickener, 1-3 parts by weight of rosin ester-based adhesion enhancer, 0.5-1.5 parts by weight of 2.2-methylenebis (6-tert-butyl-4-methylphenol) It is more preferable to include 0.3-0.7 parts by weight of sodium chloride and 0.3-0.7 parts by weight of hindered amine.

The polymer resin represented by Formula 2 is an acrylic copolymer synthesized from zinc-2-ethylhexanoate methacrylate, methacrylic acid, and glycidyl methacrylate monomers, 3- Using an amine compound such as (Dimethylamino)-1-propylamine, it is combined through the epoxy group contained in glycidyl methacrylate to form a hydroxy group (-OH), a secondary amine linker (-NH-), and a tertiary amine group. can do. The polymer resin represented by Formula 2 has the above structure and can be applied as an effective acrylic polymer resin that is not only environmentally friendly but also has high antifouling properties. In Formula 2, o is 23-27, p is 23-27, q is 23-27, r is more preferably 23-27, o is 25, p is 25, and q is 25. , r is most preferably 25.

The acrylic modified polyurethane is prepared by mixing diisocyanate, polyol, and an organic solvent to prepare a mixed solution, reacting the mixed solution to prepare polyurethane having an isocyanate end group, and polyurethane having an isocyanate end group. It is preferable to prepare a polyurethane having a vinyl end group by reacting urethane with a monomer containing a hydroxy group, and to use a polyurethane prepared by reacting a monomer with the polyurethane having a vinyl end group.

It is preferable to use polyether polyol as the polyol.

The diisocyanate may include hexamethylene diisocyanate, isophorone diisocyanate, and 4,4'-methylenebis(cyclohexyl isocyanate). and preferably hexamethylene diisocyanate.

The organic solvent may be toluene, methyl ethyl ketone, ethyl acetate, acetone, and dimethylformamide, and toluene is preferably used.

Monomers containing the hydroxy group include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-hydroxyethyl acrylate (2-hydroxyethyl methacrylate). hydroxyethyl acrylate) and allyl alcohol, etc., preferably 2-hydroxyethyl acrylate,

It is preferable to use glycidyl methacrylate as the monomer added to the polyurethane having the vinyl end group.

Tensile strength and adhesion can be further improved by applying the acrylic modified polyurethane.

The copper powder is used as a filler to improve the physical properties of the surface coating layer.

The calcium carbonate is used as a filler to improve the physical properties of the surface coating layer.

The sodium dodecyl benzene sulfonate is an anionic surfactant and is applied to disperse the composition for forming a surface coating layer.

The activated carbon powder can improve the dispersibility due to its high porosity and at the same time improve the strength of the surface coating layer by improving the bonding force between components in the composition.

The cellulose-based thickener may have water retention properties.

The rosin ester-based adhesion enhancer is intended to facilitate adhesion to the target surface.

The 2.2-methylenebis(6-tert-butyl-4-methylphenol) is used as an antioxidant.

The sodium chloride is used as a mechanical/thermal stabilizer.

The hindered amine is used as an ultraviolet stabilizer.

In addition, the composition for forming the surface coating layer more preferably contains 3-7 parts by weight, and most preferably 4-6 parts by weight, of the silicone-based compound represented by the following formula (3) based on 100 parts by weight of the total composition.

<Formula 3>

The silicone-based compound represented by Formula 3 is silicon methacrylate, and can increase adhesion to the surface of the PVC window profile applied, including silicon methacrylate, and further increase durability.

Hereinafter, the present invention will be explained in more detail by the following examples.

However, the following examples only illustrate the content of the present invention and the scope of the invention is not limited by the examples and experimental examples.

<Preparation Example 1> Preparation of plant extract

Mulberry tree, Japanese fir tree, and drooping mulberry tree are washed, freeze-dried, and then pulverized to produce mulberry tree powder, fir tree powder, and drooping mulberry tree powder, and the prepared mulberry tree powder, fir tree powder, and drooping mulberry tree powder are mixed in a weight ratio of 1:1:1. 20 g of the mixed powder was mixed with 200 ml of water, and the first hot water extraction was performed at a temperature of 80°C for 8 hours while stirring. After the first hot water extraction, it was filtered through filter paper and the filtrate was freeze-dried to prepare the first mixed extract.

After the first hot water extraction, filter through filter paper and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and perform the second hot water extraction at a temperature of 120°C for 12 hours while stirring. did. After secondary hot water extraction, it was filtered through filter paper and the filtrate was freeze-dried to prepare a secondary mixed extract.

After secondary hot water extraction, filter through filter paper, and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and then add [BMIm][TFSI] (1-Butyl-3-methylimidazolium After adding 2 g of bis(trifluoromethylsulfonyl)imide), the third hot water extraction was performed at a temperature of 100°C for 8 hours while stirring. After the third hot water extraction, it was filtered through filter paper and the filtrate was freeze-dried to prepare a third mixed extract.

A plant extract was prepared by mixing the first mixed extract, second mixed extract, and third mixed extract.

<Example 1> Preparation of PVC antibacterial masterbatch-1

100 parts by weight of p-1000 as a PVC polymer resin was placed in a stirrer and melted at a temperature of 180°C, and 15 parts by weight of the polymer resin represented by Chemical Formula 1, 6 parts by weight of dioctyl phthalate, and silane surface-treated antimony trioxide ( A first mixture was prepared by adding 7 parts by weight of Sb ₂ O ₃ ), 5 parts by weight of chlorosulfonated polyethylene rubber, and 3 parts by weight of copper fiber and stirring at 2500 rpm. At this time, the polymer resin represented by Formula 1 was used in which n, m, a, and b were 25, and x was 15.

Subsequently, in the first mixture, 6 parts by weight of dioctyl phthalate, 3 parts by weight of methylcellulose, 27 parts by weight of zinc oxide particles with a particle size of 24-26 nm, and 17 parts by weight of cuprous oxide particles with a particle size of 94-96 nm, prepared as above. 7 parts by weight of the plant extract prepared in Example 1, 1 part by weight of 10,10'-oxybisphenoxarsine (OBPA), Zinc 2-pyridinethiol-1-oxide, Zn PTO) 1 part by weight, 0.5 parts by weight of sodium chloride, 0.5 parts by weight of hindered amine, and 8 parts by weight of copper phthalocyanine pigment as a colorant were added and stirred at 3500 rpm to prepare a second mixture.

The second mixture was put into a melt extruder, the internal temperature was set to 235°C, melted and extruded, and the extrudate was cooled and cut to prepare a masterbatch.

<Example 2> Preparation of PVC antibacterial masterbatch-2

A masterbatch was prepared in the same manner as in Example 1, except that 5 parts by weight of nano-silica sol surface-modified with siloxane was added when preparing the second mixture in Example 1.

<Comparative Example 1>

A masterbatch was prepared in the same manner as Example 1, except that PVC resin was used instead of the polymer resin represented by Chemical Formula 1.

<Comparative Example 2>

In Example 1, 7 parts by weight of silane surface-treated antimony trioxide (Sb ₂ O ₃ ), 5 parts by weight of chlorosulfonated polyethylene rubber, and 3 parts by weight of copper fiber were not applied, but 42 parts by weight of zinc oxide particles were added to the second mixture. A masterbatch was prepared in the same manner as in Example 1 except that a sub-process was applied.

<Example 3> Preparation of composition for forming surface coating layer-1

47 parts by weight of polymer resin represented by Formula 2, 20 parts by weight of acrylic modified polyurethane resin, 7 parts by weight of copper powder, 7 parts by weight of calcium carbonate, 5 parts by weight of sodium dodecyl benzene sulfonate, 4 parts by weight of activated carbon powder, cellulose-based Mix 2 parts by weight of thickener, 2 parts by weight of rosin ester adhesion enhancer, 1 part by weight of 2.2-methylenebis (6-tert-butyl-4-methylphenol), 0.5 part by weight of sodium chloride, and 0.5 part by weight of hindered amine. A composition for forming a surface coating layer was prepared. At this time, in the polymer resin represented by Formula 2, o was 25, p was 25, q was 25, and r was 25.

<Example 4> Preparation of composition for forming surface coating layer-2

47 parts by weight of polymer resin represented by Chemical Formula 2, 20 parts by weight of acrylic modified polyurethane resin, 5 parts by weight of silicone compound represented by Chemical Formula 3, 7 parts by weight of copper powder, 7 parts by weight of calcium carbonate, 5 parts by weight of sodium dodecyl benzene sulfonate parts by weight, 4 parts by weight of activated carbon powder, 2 parts by weight of cellulose-based thickener, 2 parts by weight of rosin ester-based adhesion enhancer, 1 part by weight of 2.2-methylenebis (6-tert-butyl-4-methylphenol), 0.5 parts by weight of sodium chloride, and A composition for forming a surface coating layer was prepared by mixing 0.5 parts by weight of hindered amine. At this time, in the polymer resin represented by Formula 2, o was 25, p was 25, q was 25, and r was 25.

<Experimental Example 1> Physical property analysis of PVC antibacterial masterbatch

Wear resistance, tensile strength, tear strength, and elongation tests were performed using the masterbatches prepared in Example 1, Example 2, Comparative Example 1, and Comparative Example 2, and the results are shown in Table 1 below.

Abrasion resistance was measured by the ASTM D 1630 method, tensile strength was measured by the ASTM D412 method, tear strength was measured by the ASTM D624 method, and elongation was measured by the ASTM D412 method (specimen size: horizontal and 15 cm each, test site temperature: 19℃, humidity: 60%).

Wear resistance rate
(%) tensile strength
(kg/ ^cm2 ) Tear strength
(kg/cm) elongation rate
(%) Example 1 976 91 75 412 Example 2 980 94 77 390 Comparative Example 1 972 91 75 325 Comparative Example 2 893 77 58 348

As shown in Table 1 above, it was confirmed that the PVC antibacterial masterbatch according to the present invention had excellent physical properties. In particular, it was confirmed that Example 1 maintained or slightly improved the wear resistance, tensile strength, and tear strength compared to Comparative Example 1, and that the elongation rate was very excellent. In addition, in the case of Example 2, it was confirmed that although the elongation rate was insufficient compared to Example 1, the tensile strength was superior.

<Experimental Example 2> Analysis of antibacterial activity of PVC antibacterial masterbatch

Antibacterial performance was measured using the masterbatch prepared in Example 1, and the results are shown in Table 2 below.

Antibacterial performance was performed according to KS J 4206, and the test strains were Staphylococcus aureus ATCC 6538 (hereinafter strain 1), Escherichia coli ATCC 25922 (hereinafter strain 2), and Pischeudomonas. Aruginosa (Pseudomonas aeruginosa ATCC 27853; hereinafter strain 3) and Escherichia coli (E.Coli ATCC 25922; hereinafter strain 4) were used. The test conditions were to culture the test bacterial solution at 37 ± 1°C with shaking for 24 hours and then measure the number of bacteria (120 shaking times/min). The test sample weight was 2.0 g, phosphate buffer solution (pH 7.0±2) was used as the neutralization solution, the reduction rate (%) was [(Mb-Mc)/Ma] (Ma: initial number of bacteria in the control sample, Mb: number of bacteria in the control sample after incubation for 24 hours, Mc: number of bacteria in the test sample after incubation for 24 hours).

for strain 1
Antibacterial activity (%) for strain 2
Antibacterial activity (%) for strain 3
Antibacterial activity (%) for strain 4
Antibacterial activity (%) Example 1 99 98 99 99

As shown in Table 2 above, it was confirmed that the PVC antibacterial masterbatch according to the present invention had very excellent antibacterial activity.

<Experimental Example 3> Physical property analysis of surface coating layer

A surface coating layer was formed by applying the composition for forming a surface coating layer of Examples 3 and 4, dried at room temperature for 20 minutes, and then cured at 60°C for 4 hours to prepare a specimen coating film. Afterwards, the physical properties of the composition and specimen coating were measured in the following manner, and the results are shown in Table 3.

(1) Appearance

The appearance characteristics of the specimen coating were evaluated. Excellent (◎) if there were no pinholes or cratering on the surface, good (○) if 1 to 5 pinholes or cratering occurred per specimen, and good (○) if more than 5 pinholes or cratering occurred per specimen. It was evaluated as average (△), and if more than 10 occurred, it was evaluated as defective (×).

(2) Hardness

The pencil hardness of the specimen film was measured using a Mitsubishi pencil. Specifically, the maximum hardness without damaging the specimen coating was measured using pencils of 3B, 2B, B, HB, F, H, 2H, and 3H (3B, 2B, B, HB, F, H, 2H). , 3H: inferior⇔excellent).

(3) Adhesion

According to the ASTM D3359 tape adhesion test method, 25 squares of 2 mm × 2 mm (width × height) were formed on the surface of the specimen coating using a cutter knife, and then the squares were removed using tape to test the adhesion. was measured. At this time, 5B if the 25 squares are 100% intact, 4B if the remaining squares are between 95% and less than 100%, 3B if the remaining squares are between 85% and less than 95%, 2B if the remaining squares are between 65% and less than 85%, and 2B if the remaining squares are between 35% and less than 65%. In case of less than 35%, it was evaluated as 1B, and if less than 35%, it was evaluated as 0B.

(4) anti-foaming

After applying the composition, the time for bubbles to disappear from the surface of the specimen coating was measured. If the time was less than 5 seconds, it was excellent (◎), if it was 5 to 30 seconds, it was good (○), and if it was more than 30 seconds and less than 60 seconds, it was average (△). , if it was longer than 60 seconds, it was evaluated as defective (×).

(5) Impact resistance

According to ASTM D2794, impact resistance was evaluated by dropping a 500g weight onto the sample coating from a height of 10 inches or more, observing the coating surface, and measuring the maximum height at which uniformity and peeling did not occur in the coating.

Exterior Hardness Adhesion impact resistance
(inch) vesicular Example 3 ◎ H 3B 26 ◎ Example 4 ◎ 2H 5B 35 ◎

As shown in Table 3, it was confirmed that the composition for forming a surface coating layer according to the present invention exhibited excellent performance.

Claims (2)

After melting 100 parts by weight of PVC polymer resin, 13-17 parts by weight of polymer resin represented by the following formula 1, 4-8 parts by weight of dioctyl phthalate, and silane surface-treated antimony trioxide (Sb) are added to 100 parts by weight of PVC polymer resin. ₂ O ₃ ) Preparing a first mixture by mixing 5-9 parts by weight, 3-7 parts by weight of chlorosulfonated polyethylene rubber, and 1-5 parts by weight of copper fiber;
In the first mixture, 4-8 parts by weight of dioctyl phthalate, 1-5 parts by weight of methylcellulose, 25-29 parts by weight of zinc oxide particles with a particle size of 20-30 nm, 15-19 parts by weight of cuprous oxide particles, and 5 parts by weight of plant extract. -9 parts by weight, 10,10'-oxybisphenoxarsine (OBPA) 0.5-2 parts by weight, Zinc 2-pyridinethiol-1-oxide (Zn PTO) 0.5- Preparing a second mixture by mixing 2 parts by weight, 0.3-0.7 parts by weight of sodium chloride, 0.3-0.7 parts by weight of hindered amine, and 6-10 parts by weight of a colorant;
Melting and extruding the second mixture at a temperature range of 220-250° C. while stirring; and
Comprising: manufacturing a masterbatch by cooling and cutting the extrudate formed by performing the melting and extrusion,
The plant extract is,
Washing, freeze-drying, and pulverizing mulberry trees, fir trees, and drooping mulberry trees to produce mulberry tree powder, fir tree powder, and drooping mulberry tree powder; 20 g of the mixed powder made by mixing the prepared mulberry powder, fir tree powder and drooping mulberry powder in a weight ratio of 1:1:1 was mixed with 200 ml of water and subjected to primary hot water extraction at a temperature of 80°C for 8 hours while stirring. performing steps; After the first hot water extraction, filtering with filter paper and then freeze-drying the filtrate to prepare a first mixed extract; After the first hot water extraction, filter through filter paper and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and perform the second hot water extraction at a temperature of 120°C for 12 hours while stirring. steps; After secondary hot water extraction, filtering through filter paper and then freeze-drying the filtrate to prepare a secondary mixed extract; After secondary hot water extraction, filter through filter paper, and mix the remaining solids with water again so that the mixing ratio of solids and water is 0.1 g/ml, and then add [BMIm][TFSI] (1-Butyl-3-methylimidazolium Adding 1-2 g of bis(trifluoromethylsulfonyl)imide) and performing third hot water extraction at a temperature of 100°C for 8 hours while stirring; After the third hot water extraction, filtering through filter paper and then freeze-drying the filtrate to prepare a third mixed extract; A method for producing a PVC antibacterial masterbatch, characterized in that it is manufactured by performing the following steps: mixing the first mixed extract, the second mixed extract, and the third mixed extract:
<Formula 1>

(In Formula 1, n is 20-30, m is 20-30, a is 20-30, b is 20-30, and x is 5-50). delete