KR20240001834A - Resin Composition - Google Patents

Abstract

This application can provide polymers and their uses. In this application, it is possible to provide a polymer that has excellent antibacterial properties and excellent durability of the antibacterial properties. In the present application, it is also possible to provide a polymer in which physical properties other than the antibacterial property desired to be obtained from the polymer are not damaged or damaged by the introduction of the antibacterial property, and are stably secured or improved. The present application may also provide uses of the polymer.

Description

Polymer{Resin Composition}

This application relates to polymers.

There are several approaches to preparing polymers with antibacterial properties.

The most representative method is to use a material that combines an antibacterial agent with a polymer, and inorganic antibacterial agents and organic antibacterial agents are typically used as antibacterial agents.

Inorganic antibacterial agents have superior stability to the human body and thermal stability compared to organic antibacterial agents. However, the inorganic antibacterial agent is expensive, easily discolors the material, and can deteriorate the physical properties of the polymer during processing such as extrusion or injection. Additionally, inorganic antibacterial agents have low immediate antibacterial effectiveness.

Organic antibacterial agents are relatively inexpensive compared to inorganic antibacterial agents and have excellent immediate antibacterial effectiveness. However, organic antibacterial agents have poor stability to the human body and poor thermal stability, resulting in poor antibacterial persistence.

Another method for producing a polymer with antibacterial properties is to introduce the antibacterial agent into the polymer chain by applying an antibacterial agent with a polymerizable functional group rather than simply mixing the antibacterial agent with the polymer.

However, in this method, since a separate monomer is applied during the polymerization process, the polymerization does not proceed as designed, and the properties such as molecular weight of the polymer are not secured as desired, or depending on the polymer, the properties that the polymer should exhibit are not guaranteed. Its unique advantages may be damaged.

In addition, depending on the type of polymer, the polymerization efficiency of the antibacterial agent having the polymerizable functional group is low, so the introduction efficiency of the antibacterial agent during the polymerization process is low, and as a result, the desired antibacterial property is often not obtained.

Polyvinyl chloride (poly(vinyl chloride), hereinafter referred to as “PVC”) is a polymer material widely used in a variety of products. For example, PVC is used in the manufacture of building materials such as windows and doors, wallpaper and flooring, pipes, automobile parts, hoses, agricultural films used for house cultivation of vegetables and fruits, and construction sheets.

The reason why PVC is widely used in various fields is because PVC has the property of mixing well with various materials such as plasticizers, heat stabilizers, or fillers.

It is not an easy task to provide appropriate antibacterial properties to such PVC while maintaining its advantages.

This application relates to polymers and their uses. One purpose of this application is to provide a polymer that has excellent antibacterial properties and excellent durability of the antibacterial properties. The present application also aims to provide a polymer in which physical properties other than the antibacterial property desired to be obtained from the polymer are not damaged or damaged by the introduction of the antibacterial property, and are stably secured or improved. The present application also aims to provide uses for the polymer.

Among the physical properties mentioned in this specification, the physical properties where the measurement temperature affects the physical properties are those measured at room temperature, unless otherwise specified.

The term room temperature refers to a natural temperature that is not heated or reduced, for example, any temperature in the range of about 10°C to 30°C, for example, about 15°C, about 18°C, about 20°C, about 23°C. Or it means a temperature of about 25℃. Additionally, unless otherwise specified in the specification, the unit of temperature is ℃.

Among the physical properties mentioned in this specification, in cases where the measurement pressure affects the results, unless otherwise specified, the physical properties are those measured at normal pressure. The term normal pressure refers to natural pressure that is not pressurized or decompressed, and is usually referred to as atmospheric pressure of about 1 atmosphere (about 700 to 800 mmHg).

In cases where humidity affects the results of the physical properties mentioned in this specification, unless otherwise specified, the physical properties are those measured at room temperature and pressure and with humidity not specifically adjusted.

As used herein, the term alkyl group or alkoxy group refers to an alkyl group or alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkyl group or alkoxy group may be a straight-chain, branched, or cyclic alkyl group or alkoxy group, and may be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, the term alkenyl group or alkynyl group refers to an alkenyl group or alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. do. The alkenyl group or alkynyl group may be straight-chain, branched, or cyclic, and may be optionally substituted with one or more substituents.

As used herein, the term alkylene group may refer to an alkylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless otherwise specified. The alkylene group may be a straight-chain, branched, or cyclic alkylene group, and may be optionally substituted with one or more substituents.

As used herein, the term alkylidene group may mean an alkylidene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkylidene group may be a straight-chain, branched, or cyclic alkylidene group, and may be optionally substituted with one or more substituents.

In this specification, both an alkylene group and an alkylidene group refer to a substituent formed by removing two hydrogen atoms from an alkane. The alkylene group is a substituent formed by removing a hydrogen atom from another carbon atom in an alkane, and an alkylidene group refers to a substituent formed by removing two hydrogen atoms from an alkane. It is a substituent formed by removing two hydrogen atoms from a carbon atom.

In this specification, the term alkenylene group or alkynylene group refers to an alkenylene group or alkynylene having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless otherwise specified. It means energy. The alkenylene group or alkynylene group may be straight-chain, branched, or cyclic, and may be optionally substituted with one or more substituents.

In this specification, the term aryl group or arylene group, unless specifically defined otherwise, is a structure in which one benzene, two or more benzene are connected while sharing one or two carbon atoms, or are connected by an arbitrary linker. It may refer to a monovalent or divalent residue derived from a compound containing or a derivative thereof. Unless otherwise specified, the aryl group or arylene group is, for example, an aryl group or arylene group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms. You can.

In this application, the term aromatic structure refers to the aryl group or arylene group.

In this application, the term single bond may mean a case where no separate atom exists at the corresponding site. For example, in a structure indicated by A-B-C, if B is a single bond, there is no separate atom at the site indicated by B, and A and C are directly connected to form a structure indicated by A-C.

In the present application, substituents that may be optionally substituted such as an alkyl group, alkoxy group, alkenyl group, alkynyl group, alkylene group, alkylidene group, alkenylene group, alkynylene group, aryl group, or arylene group include hydroxy group, halogen, and carboxyl. Group, glycidyl group, acryloyl group, methacryloyl group, acryloyl group oxy group, methacryloyl group oxy group, thiol group, alkyl group, alkenyl group, alkynyl group, alkoxy group or aryl group, etc. may be exemplified. It is not limited to this.

This application relates to polymers.

The polymer of the present application may be a polymer that contains vinyl chloride-based monomer units and has antibacterial properties.

As used herein, having antibacterial properties means that the bacteriostatic reduction rate measured according to ASTM E2149 or JIS Z2801 is 50% or more. The specific measurement method of the bacteriostatic reduction rate is described in the Examples. In other examples, the bacteriostatic reduction rate is 55% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 91% or more, 92% or more. , may be 93% or more, 94% or more, 95% or more, or 95.3% or more. The upper limit of the bacteriostatic reduction rate is not particularly limited, and for example, the bacteriostatic reduction rate may be 100% or less or less than 100%.

In this application, the antibacterial properties of the polymer are derived from the cationic functional group contained in the polymer. In general, cell walls such as bacteria are often negatively charged, and the cationic functional group can destroy the cell wall.

The antibacterial properties of the present application are based on the antibacterial properties of organic antibacterial agents. Organic antibacterial agents are less expensive than inorganic antibacterial agents and have excellent immediate antibacterial effect, but are known to have poor thermal stability and thus low antibacterial persistence. In addition, even if organic antibacterial agents are polymerizable, polymerization efficiency is low during the polymer manufacturing process, so they are not properly incorporated into the polymer chain, and as a result, the polymer often does not exhibit the desired antibacterial properties. In addition, the polymerizable organic antibacterial agent often affects the physical properties of the polymer, thereby damaging the inherent advantages of the polymer.

However, in the present application, by combining a unit having an organic antibacterial functional group of a specific structure with a vinyl chloride monomer unit through copolymerization, the organic antibacterial agent can be efficiently incorporated into the polymer chain, and thus the antibacterial agent's advantage, immediate antibacterial effect, can be achieved. While maintaining or improving, the advantages derived from the vinyl chloride monomer unit can also be stably maintained.

The polymer of the present application has the above-mentioned excellent antibacterial properties and antibacterial persistence, while also maintaining or improving the inherent physical properties desired from the polymer.

As will be described later, the polymer may be a so-called PVC (poly(vinyl chloride))-based polymer containing the vinyl chloride-based monomer unit as a main component. The advantages of the PVC-based polymer include easy processing, plasticizer, and heat stabilizer. It has the property of mixing well with various materials such as fillers.

The polymer of the present application exhibits appropriate and excellent antibacterial properties while stably maintaining the advantages of the PVC-based polymer as described above.

For example, the polymer may exhibit a CPA (cold plasticizer absorption) of 20% by weight or more. In other examples, the CPA of the polymer is about 22% by weight or more, 24% by weight or more, 26% by weight or more, 28% by weight or more, 30% by weight or more, or 32% by weight or more, or 60% by weight or less, 58% by weight or less, 56% by weight or less, 54% by weight or less, 52% by weight or less, 50% by weight or less, 48% by weight or less, 46% by weight or less, 44% by weight or less, 42% by weight or less, 40% by weight or less, 38% by weight or less, It may be about 36% by weight or less, 34% by weight or less, or 32% by weight or less. The CPA can be confirmed by the general method of measuring CPA for PVC, and specifically can be confirmed by the ASTM D3367 standard.

For example, the polymer may exhibit a BD (Bulk Density) in the range of 0.2 to 0.8. In other examples, the BD of the polymer may be 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, or 0.5 or more, or 0.75 or less, 0.7 or less, 0.65 or less, 0.6 or less, 0.55 or less, or 0.5 or less. The BD can be confirmed by the general method of measuring BD for PVC, and specifically can be confirmed by the ASTM D1895 standard.

For example, the polymer may be in the form of particles and may have an average particle diameter in the range of about 50 μm to 300 μm. In other examples, the average particle diameter of the polymer in the form of particles is about 60 μm or more, 70 μm or more, 80 μm or more, 90 μm or more, 100 μm or more, 110 μm or more, 120 μm or more, 130 μm or more, or 140 μm or more, 290 μm or less, 280 μm or less, 270 μm or less, 260 μm or less, 250 μm or less, 240 μm or less, 230 μm or less, 220 μm or less, 210 μm or less, 200 μm or less, 190 μm or less, 180 μm or less, 170 μm or less It may be about 160 μm or less or 150 μm or less. The average particle diameter can be confirmed by a general method of measuring the average particle diameter of PVC, and specifically, it can be confirmed by the ASTM D1921 standard.

These polymers may have a weight average molecular weight (Mw) in the range of 70,000 to 200,000. In this application, the weight average molecular weight is measured by GPC (Gel Permeation Chromatography) according to the method of the Examples described later, and the unit is g/mol. In other examples, the weight average molecular weight may be 75,000 or more, 80,000 or more, 85,000 or more, 90,000 or more, or 95,000 or more, or 150,000 or less or 100,000 or less.

As described above, the polymer may include vinyl chloride-based monomer units. In this specification, monomer unit or unit refers to the state in which a certain monomer is included in the polymer after polymerization.

In the above example, the vinyl chloride-based monomer unit may be represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently hydrogen or chlorine, and at least one of R ₁ and R ₂ is chlorine.

The polymer of the present application is a polymer containing the unit of Formula 1 above as a main component, and may be a so-called PVC-based polymer.

In this case, the PVC-based polymer may contain more than 60 mol% of the polymerized unit of Formula 1. In other examples, the ratio of the polymerized units may be 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 85 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more. there is. In this application, through the application of a specific antibacterial monomer unit described later, excellent antibacterial properties can be imparted to the polymer even when the antibacterial monomer unit is applied in a very small amount. Therefore, in the present application, a relatively large number of polymerized units of Formula 1 can be included, and as a result, the inherent advantages of the polymer can be maintained or improved while exhibiting appropriate antibacterial properties. There is no particular limitation on the upper limit of the ratio of the polymerized units of Formula 1 in the polymer, for example, the ratio may be less than 100 mol%.

In this application, a cationic functional group can be introduced to impart antibacterial properties to the polymer. Various types may be applied as the cationic functional group, but in an appropriate example of the present application, a quaternary ammonium-based substituent is used as the cationic functional group.

The polymer is a unit containing the quaternary ammonium-based substituent and may further include a unit of the following formula (2).

[Formula 2]

In Formula 2, L ₁ is an alkylene group having 2 to 20 carbon atoms or an alkylidene group having 1 to 20 carbon atoms, R ₃ is an alkyl group having 6 to 20 carbon atoms, and R ₄ and R ₅ are each independently a group having 1 to 5 carbon atoms. It may be an alkyl group.

In Formula 2, L ₁ is, in other examples, an alkylene group having 2 to 10 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms, or an alkylene group having 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. It may be an alkylidene group. At this time, the alkylene group or alkylidene group may be linear.

In Formula 2, R ₃ may be an alkyl group having 6 to 15 carbon atoms, and the carbon number of the alkyl group may be 7 or more, 8 or more, 9 or more, or 10 or more, or 14 or less, 13 or less, 12 or less, 11 or less, or 10 or less. there is. These alkyl groups may be straight-chain.

In Formula 2, R ₄ and R ₅ may each independently be an alkyl group having 1 to 3 carbon atoms, and specifically, may each independently be a methyl group, an ethyl group, or a propyl group.

In Formula 2, R may be hydrogen or an alkyl group, where the alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, or a methyl or ethyl group. . The alkyl group may be straight-chain or branched.

The unit of Formula 2 as described above can be copolymerized with the unit of Formula 1 with appropriate efficiency, and can impart excellent antibacterial properties to the polymer even when applied in a small amount.

The unit of Formula 2 may be included in the polymer at a ratio of 0.1 to 10 parts by weight based on 100 parts by weight of the polymerized unit of Formula 1. In other examples, the ratio is 0.15 parts by weight or more, 0.2 parts by weight or more, 0.25 parts by weight or more, 0.3 parts by weight or more, 0.35 parts by weight or more, 0.4 parts by weight or more, 0.45 parts by weight or more, 0.5 parts by weight or more, 0.55 parts by weight or more. , 0.6 parts by weight or more, 0.65 parts by weight or more, 0.7 parts by weight or more, or 0.75 parts by weight or more, or about 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, 4 Part by weight or less, 3 parts by weight or less, 2 parts by weight or less, 1 part by weight or less, 0.95 parts by weight or less, 0.9 parts by weight or less, 0.85 parts by weight or less, 0.8 parts by weight or less, 0.75 parts by weight or less, 0.7 parts by weight or less, 0.65 parts by weight or less It may be 0.6 parts by weight or less, 0.55 parts by weight or less, or 0.5 parts by weight or less.

In a polymer, the ratio (M1/M2) of the number of moles (M1) of the polymerized units of Formula 1 to the number of moles (M2) of the units of Formula 2 (M1/M2) may be in the range of about 600 to 1500. In other examples, the ratio (M1/M2) is about 650 or more, 700 or more, 750 or more, 800 or more, 850 or more, 900 or more, 950 or more, 1000 or more, 1050 or more, 1100 or more, 1150 or more, or 1200 or more, or 1450 or more. It may be 1400 or less, 1350 or less, 1300 or less, 1250 or less, 1200 or less, 1150 or less, 1100 or less, 1050 or less, 1000 or less, 950 or less, 900 or less, or 850 or less.

In the above case, the ratio of the total number of moles of the polymerized unit of Formula 1 and the unit of Formula 2 in the polymer is 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, It may be 85 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and the upper limit may be 100 mol% or less or less than 100 mol%.

Within the range of the above weight ratio or mole ratio, the polymer can exhibit excellent antibacterial properties and the inherent advantages of the polymer can be stably maintained.

The polymer may further include other monomer units in addition to the units described above. At this time, there is no particular limitation on the type of unit that can be added, and for example, a unit of a monomer applied to the production of PVC-based polymer may be used. Examples of such units may include one or more units selected from the group consisting of vinyl acetate units, olefin units, styrene units, isobutylene units, acrylonitrile units, and isoprene units, and the ratio may be appropriately adjusted depending on the purpose. It can be.

In the present application, there is no particular limitation on the method of producing the above polymer, and for example, a conventional method of producing a PVC-based polymer may be applied. In applying the conventional method, the desired polymer can be manufactured by applying monomers capable of forming the unit of Formula 2. Additionally, the monomer forming the unit of Formula 2 can be synthesized based on known material synthesis methods.

The present application also relates to compositions comprising the above polymers. The composition basically includes the polymer, and may include other polymers or components other than the polymer.

This composition can also exhibit excellent antibacterial properties and antibacterial persistence by containing the polymer as described above, and can additionally exhibit excellent properties resulting from the polymer.

There is no particular limitation on the types of other additives that can be included with the polymer, and for example, additives that are usually mixed with PVC can be used. Such additives may include one or more selected from the group consisting of plasticizers, impact modifiers, stabilizers, fillers, and pigments, but are not limited thereto.

These polymers and compositions of the present application can be applied to various uses. For example, the polymer exhibits excellent antibacterial properties and antibacterial persistence as described above, and also has the advantages of PVC-based polymers, so it can be applied to a variety of applications.

There is no particular limitation on the specific use to which it can be applied, and for example, it can be applied without limitation to the use to which conventional PVC has been applied.

This application can provide polymers and their uses. In this application, it is possible to provide a polymer that has excellent antibacterial properties and excellent durability of the antibacterial properties. In the present application, it is also possible to provide a polymer in which physical properties other than the antibacterial property desired to be obtained from the polymer are not damaged or damaged by the introduction of the antibacterial property, and are stably secured or improved. The present application may also provide uses of the polymer.

The present application will be described in detail through examples below, but the scope of the present application is not limited by the examples below.

1. GPC(Gel Permeation Chromatograph)

Molecular weight was measured using GPC (Gel permeation chromatography). Approximately 4.32 g of LiBr was dissolved in 1L of dimethylform amide (DMF) and filtered using a solvent clarification system to prepare a mobile phase. The material to be analyzed (polymer) was diluted in DMF (Dimethylformamide) to a concentration of about 2 mg/mL, dissolved at 50°C for about 6 hours, and filtered through a PVDF (polyvinylidene fluoride) filter (pore size: 0.45μm) to obtain the sample. After preparing, the molecular weight characteristics were evaluated in the following manner. The analysis program used was ChemStation from Agilent technologies, and the elution time of the sample was compared with the calibration curve to obtain the weight average molecular weight (Mw) or number average molecular weight (Mn), respectively. The measurement conditions of GPC are as follows.

<GPC measurement conditions>

Instrument: 1200 series from Agilent technologies

Stationary phase: 3x Agilent PLgel MIXED-C, 7.5 × 300 mm, 5 μm

Mobile phase A: 0.05M LiBr in DMF

Flow rate: 1.0 mL/min

Stationary bed temperature: 40℃

Injection volume: 100μL (0.45 μm filter)

Standard samples: polystyrene (6570000, 2328000, 696000, 238300, 135700, 67600, 29460, 9820, 3050, 580

2. NMR analysis

NMR analysis can be performed at room temperature (about 23 ± 2°C) using a 500 MHz or 700 MHz NMR from Bruker. The analyte was diluted in a solvent for NMR measurement (DMSO-d ₆ or TCE-d ₂ ) to a concentration of approximately 10 mg/ml and applied for analysis, and the chemical shift was expressed in ppm.

3. Measurement of average particle size

The average particle diameter of the produced polymer was measured using a particle size analyzer (manufactured by Sympatec) in accordance with ASTM D1921 standard (Test Method A).

4. Measurement of bulk density (BD: Bulk Density)

The bulk density of the produced polymer was measured based on ASTM D1895 standards.

5. Measurement of CPA (cold plasticizer absorption)

CPA (cold plasticizer absorption) of the manufactured polymer was measured based on ASTM D3367-95 standard. Based on the above standards, the amount of DOP (Dioctyl Phthalate) absorbed into the sample was calculated as a weight percent based on the sample before absorption.

6. Evaluation of antibacterial properties

The bacteriostatic reduction rate was measured according to ASTM E2149 (Shake Flask Method) for E. coli (ATCC 25922). After the E. coli was brought into contact with the sample to be tested for a certain period of time, it was recovered and cultured in medium, and the bacteriostatic reduction rate was calculated by comparing CFU (colony forming units) with the control group. In the above, the polymer obtained in Comparative Example 1 of this specification is used as the comparative group. Details such as the medium required for measurement and the test group preparation method are as follows.

[Manufacture of badge]

[Liquid medium]

Place 8 g of NB (Nurtient Broth, Becton, Dickinson and Company) and 1L of distilled water in a 2L container, sufficiently dissolve, and sterilize with a high-temperature and high-pressure sterilizer at a steam pressure of 103kPa and a temperature of approximately 120±2°C for 20 minutes to prepare a liquid medium. was manufactured.

[Solid medium]

Put 8 g of NB (Nurtient Broth, Becton, Dickinson and Company), 25 g of agar powder (Bacto agar, Becton, Dickinson and Company), and 1 L of distilled water into a 2 L container, stir and heat to dissolve, and dissolve at high temperature and high pressure. The medium was prepared by sterilizing the medium in a sterilizer at a steam pressure of 103 kPa and a temperature of approximately 120 ± 2°C for 20 minutes. In the above process, the agar powder stuck on the wall was shaken to prevent it from dissolving. Since the NB begins to solidify at about 40°C, when the temperature drops to about 60°C after sterilization, 25 mL of the solution is poured into Petri dishes with a diameter of 90 mm and solidified.

[Test group culture]

(1) A portion of the strain was transplanted into 10 mL of liquid medium using a loop, and cultured in suspension using a shaking incubator at 35±1°C for 16 to 24 hours.

(2) The bacteria cultured in the liquid phase were centrifuged at 13,000 rpm for about 3 minutes to separate only the bacteria from the medium, and diluted using 1X PBS so that the OD (optical density) value was 0.45 at a wavelength of 600 nm. The CFU (colony forming unit) value at OD 600 nm = 0.45 of E. coli was about 2×10 ⁸ CFU/mL.

[Bacteriostatic reduction rate]

(1) About 0.4 g of sample (solid polymer) and 20 mL of bacterial solution with a concentration of 2 × 10 ⁵ CFU/mL (20 mL of 1X PBS, 200 μL of bacteria with an OD of 600 nm = 0.45) were added to a 50 mL conical tube. .

(2) The bacteria and polymer were brought into contact at 35±1°C for 1 hour using a shaking incubator.

(3) Samples for which bacterial culture was completed were diluted 1-fold, 10-fold, and 100-fold, inoculated into 100 μL each on agar solid medium, and then spread using a spreader or glass beads until absorbed into the medium.

(4) The solid medium was cultured statically at 35 ± 1°C for 16 to 20 hours.

(5) Among the 1-, 10-, and 100-fold diluted samples, colonies in Petri dishes containing 30 to 300 colonies were counted and recorded. The bacteriostatic reduction rate (%) was calculated by calculating how much the number of CFU of the sample was reduced compared to the comparison group according to Equation B below, and the average value obtained after three repeated experiments on the same sample was taken as a representative value of the bacteriostatic reduction rate.

[Formula B]

Bacteriostatic reduction rate (%) = 100 × {1-(number of bacteria in test group/number of bacteria in comparison group)}

In the above, the number of bacteria in the test group is the number of bacteria in the antibacterial test in the polymer of each Example and Comparative Example, and the number of bacteria in the control group is the number of bacteria in the antibacterial test in the polymer of Comparative Example 1.

Synthesis Example 1. Antibacterial monomer A

The antibacterial monomer of the following formula (A) was synthesized in the following manner.

[Formula A]

Acetonitrile (30 mL) was added to a two-neck RBF (Round Bottom Flask), and after purging with nitrogen, approximately 7.86 g of 2-(dimethylamino)ethyl methacrylate (0.05 mol) and approximately 11.1 g of bromodecane (0.05 mol) were added to the two-neck RBF (Round Bottom Flask). mol) and 4-methoxyphenol (4 mg) were added and reacted for about 16 hours while stirring at about 45°C. 200 mL of diethyl ether was added and stirred for about 1 hour to produce a solid. The resulting solid was filtered to obtain antibacterial monomer A of the above formula (A). The NMR analysis results for the monomer A are as follows.

<NMR analysis>

1H-NMR (500MHz, DMSO-d ₆ , δ[ppm]): 6.07(1H), 5.76(1H), 4.52(2H), 3.69(2H), 3.35(2H), 3.09(6H), 1.91(3H) ), 1.67(2H), 1.26(14H), 0.86(3H)

Example 1

420 kg (140 parts by weight) of polymerization water was added to a stainless steel polymerization reactor equipped with a reflux condenser and a stirrer and having an internal volume of approximately 1 m ³ . Next, 1428 g (0.476 parts by weight) of polyvinyl alcohol with a degree of hydration of about 88%, 1260 g (0.42 parts by weight) of polyvinyl alcohol with a degree of hydration of about 72%, and polyvinyl alcohol with a degree of hydration of about 55% were added to the polymerizer. 300 g (0.1 part by weight), 942 g (0.314 part by weight) of hydroxypropyl methyl cellulose, 402 g (0.134 part by weight) of t-butyl peroxyneodecanoate and cumyl peroxyneodecano. 102 g (0.034 parts by weight) of cumyl peroxyneodecanoate was additionally added.

After that, 300 kg (100 parts by weight) of vinyl chloride was added to the polymerization reactor, and the interior was degassed with a vacuum pump while stirring. Thereafter, while maintaining the temperature of the polymerization reactor at 57.4°C, the standard polymerization temperature to achieve the target average degree of polymerization of 1000 during the entire reaction process, 15 kg (5 parts by weight) of the antibacterial monomer A of Synthesis Example 1 was added for 2 hours. The reaction proceeded, and the polymerization was stopped when the pressure in the polymerization reactor changed by 0.7 kg/cm ² .

Afterwards, 150 g (0.05 parts by weight) of triethylene glycol bis(3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate was added as an antioxidant, and unreacted monomers were recovered. Afterwards, the polymer was recovered from the polymerization reactor.

The recovered polymer was stirred, filtered, and dried in distilled water at 40°C at a speed of 300 rpm for 24 hours to completely remove residual antibacterial monomers, and an antibacterial evaluation was conducted.

As a result of confirming the amount of the antibacterial monomer introduced in Synthesis Example 1 into the obtained polymer using 1H-NMR, it was confirmed that about 0.5 to 0.75 parts by weight was introduced relative to 100 parts by weight of vinyl chloride.

Comparative Example 1

420 kg (140 parts by weight) of polymerization water was added to a stainless steel polymerization reactor equipped with a reflux condenser and a stirrer and having an internal volume of approximately 1 m ³ . Next, 1428 g (0.476 parts by weight) of polyvinyl alcohol with a degree of hydration of about 88%, 1260 g (0.42 parts by weight) of polyvinyl alcohol with a degree of hydration of about 72%, and polyvinyl alcohol with a degree of hydration of about 55% were added to the polymerizer. 300 g (0.1 part by weight), 942 g (0.314 part by weight) of hydroxypropyl methyl cellulose, 402 g (0.134 part by weight) of t-butyl peroxyneodecanoate and cumyl peroxyneodecano. 102 g (0.034 parts by weight) of cumyl peroxyneodecanoate was additionally added.

After that, 300 kg (100 parts by weight) of vinyl chloride was added to the polymerization reactor, and the interior was degassed with a vacuum pump while stirring. Afterwards, the reaction was carried out while maintaining the temperature of the polymerization reactor at 57.4°C, the standard polymerization temperature to achieve the target average degree of polymerization of 1000 during the entire reaction process, and polymerization was performed at the point when the pressure of the polymerization reactor changed by 0.7 kg/cm ² . stopped.

Afterwards, 150 g (0.05 parts by weight) of triethylene glycol bis(3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate was added as an antioxidant, and unreacted monomers were recovered. Afterwards, the polymer was recovered from the polymerization reactor.

The physical property evaluation results for the polymers of the examples and comparative examples are summarized in Tables 1 and 2 below.

Antibacterial properties against E. coli CFU/mL, SUE Log CFU/mL, SUE Bacteriostatic reduction rate (%) Example 1 5200 3.72 95.3 Comparative Example 1 110000 5.04 -

Weight average molecular weight (unit: g/mol) BD(Bulk Density) CPA (unit: weight%) Average particle size (unit: μm) Example 1 97859 0.5 32 149 Comparative Example 1 98003 0.532 27 148

Claims (12)

It contains a polymerized unit of the following formula (1),
Polymers that exhibit a bacteriostatic reduction rate of 50% or more:
[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently hydrogen or chlorine, and at least one of R ₁ and R ₂ is chlorine. The polymer according to claim 1, comprising at least 60 mol% of polymerized units of formula (1). The polymer according to claim 1, wherein the average particle diameter according to ASTM D1921 is in the range of 50 μm to 300 μm. The polymer according to claim 1, wherein BD (Bulk Density) according to ASTM D1895 is in the range of 0.2 to 0.8. The polymer according to claim 1, wherein the CPA (cold plasticizer absorption) according to ASTM D3367 is 20% by weight or more. The polymer according to claim 1, wherein the weight average molecular weight is in the range of 70,000 g/mol to 200,000 g/mol. 2. The polymer according to claim 1, further comprising units of formula (2):
[Formula 2]

In Formula 2, L ₁ is an alkylene group having 2 to 20 carbon atoms or an alkylidene group having 1 to 20 carbon atoms, R ₃ is an alkyl group having 6 to 20 carbon atoms, and R ₄ and R ₅ are each independently a group having 1 to 5 carbon atoms. It is an alkyl group. The method of claim 7, wherein in Formula 2, L ₁ is an alkylene group having 2 to 10 carbon atoms or an alkylidene group having 1 to 10 carbon atoms, R ₃ is an alkyl group having 6 to 15 carbon atoms, and R ₄ and R ₅ are each independent. A polymer that is an alkyl group having 1 to 3 carbon atoms. The polymer according to claim 7, comprising 0.1 to 10 parts by weight of the polymerized unit of Formula 2 based on 100 parts by weight of the polymerized unit of Formula 1. The polymer according to claim 1, further comprising one or more units selected from the group consisting of vinyl acetate units, olefin units, styrene units, isobutylene units, acrylonitrile units, and isoprene units. A composition comprising the polymer of any one of claims 1 to 10. The composition of claim 11, further comprising at least one selected from the group consisting of plasticizers, impact modifiers, stabilizers, fillers, and pigments.