Antimicrobial additive based on non-crosslinked antimicrobial polymer and method for producing the same, vinyl chloride resin composition and molded product

Abstract

The present invention relates to an antibacterial additive based on a non-crosslinked antibacterial polymer and a method for producing the same, a vinyl chloride resin composition and a molded product. The antibacterial additive of the present invention comprises: a non-crosslinked antibacterial polymer comprising at least one unit selected from unit A and unit B and a unit based on vinyl chloride, wherein unit A is selected from at least one of the units represented by the following formula (A1) and the units represented by the following formula (A2); unit B is selected from at least one of the units represented by the following formula (B1), the units represented by the following formula (B2) and the units represented by the following formula (B3): wherein R1 to R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, X is independently selected from at least one of -O-, -S-, and -NR5-, R5 is hydrogen, Y, an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Y is a group having an antibacterial group.

Description

Technical Field

[0001] The present invention relates to an antimicrobial additive containing a non-crosslinked antimicrobial polymer and a method for producing the same, and a vinyl chloride resin composition and a molded product using the antimicrobial additive. Background Art

[0002] Polyvinyl chloride (PVC) is one of the most widely used general thermoplastics. Due to its good biocompatibility, transparency, excellent toughness and resilience, and low cost, it is widely used in the medical and health field to make various medical device products, and its usage accounts for about 25% of medical polymer materials. However, as a major medical polymer material, PVC itself does not have antibacterial properties. Medical devices made of it, such as infusion tubes and blood transfusion tubes, are easy to breed bacteria when in contact with biological fluids. At the same time, due to the hydrophobicity of PVC, it is easy for bacteria to attach to form biofilms during use, and it is easy to cause infection by pathogenic microorganisms through contact with human tissues or through intravenous infusion, blood transfusion, etc. Research results show that about a quarter of deaths from infection worldwide each year are caused by infection. This means that the issue of how to reduce bacterial infections will continue to receive attention. Therefore, it is of great significance to effectively modify PVC materials with antibacterial properties to improve the performance of medical PVC products to reduce bacterial infections.

[0003] It is a common technical means to add antibacterial agents to PVC substrates and obtain antibacterial polyPVC molded products through blending and modification. Antibacterial agents are mainly divided into inorganic antibacterial agents and organic antibacterial agents. Among them, inorganic antibacterial agents include Ag, Zn-zeolite, etc., which have disadvantages such as high prices and delayed antibacterial effects. Organic antibacterial agents such as small molecule antibacterial agents such as quaternary ammonium salts or quaternary phosphonium salts have poor compatibility with the matrix, low charge density, short duration of volatile antibacterial effects, and migration during use, resulting in antibacterial failure and other applicability problems. It is reported that the migration of low molecular weight quaternary ammonium salts can cause hemolysis and cytotoxicity, which will greatly limit its application in the field of medical devices.

[0004] In this regard, some high molecular polymers having antibacterial properties obtained by modifying maleic anhydride units have been proposed in the prior art.

[0005] In Patent Document 1, dimethylaminoethyl methacrylate or benzyl halide is used as an antibacterial functional monomer to be copolymerized with maleic anhydride in a binary or ternary manner, and the functional groups of maleic anhydride are used to react with the reactive groups on the surface of the substrate, and quaternary ammonium salt groups are introduced into the substrate through covalent bonding to prepare an antibacterial material. However, there are no groups that react with anhydride in the PVC substrate, and the structural characteristics of PVC itself make it incompatible with positively charged polymers, which easily leads to phase separation.

[0006] In Non-Patent Document 1, amide side chains were introduced into poly(isobutylene-alt-propylene-alt-maleic anhydride) by post-functionalization to synthesize a novel cationic polymer having good antibacterial activity.

[0007] However, although the above-mentioned high molecular polymers with antibacterial properties take into account the migration of antibacterial agents, when applied to a PVC matrix, this degree of migration resistance is still insufficient.

[0008] Patent document 1: Reactive polymer antibacterial agent and its preparation method and application. CN100554296C.

[0009] Non-patent literature 1: Uppu, DSS M., Samaddar, S., Ghosh, C., aramanandham, K., Shome, B R., Haldar, J. Amide side chain amphiphilic polymers disrupt surface established bacterial bio-films and protect mice from chronic acinetobacterbaumannii infection. Biomaterials, 2016, 74, 131-143. Summary of the invention

[0010] Problem that the invention aims to solve

[0011] In view of the above-mentioned defects in the art, the technical problem to be solved by the present invention is to provide an antimicrobial additive that can be obtained in a simple manner and can impart excellent antimicrobial properties to vinyl chloride resin molded products and show excellent migration resistance therein. In addition, the technical problem to be solved by the present invention is also to provide a method for obtaining the above-mentioned antimicrobial additive in a simple manner. In addition, the technical problem to be solved by the present invention is also to provide a vinyl chloride resin composition and a molded product obtained therefrom, which enables the molded product prepared therefrom to have excellent antimicrobial properties and excellent antimicrobial durability (this is due to the excellent migration resistance of the antimicrobial additive).

[0012] Solutions for solving problems

[0013] According to the inventor's intensive research, it is found that the above technical problems can be solved by implementing the following technical solutions:

[0014] [1] An antimicrobial additive, comprising: a non-crosslinked antimicrobial polymer comprising at least one unit selected from unit A and unit B and a unit based on vinyl chloride,

[0015] The unit A is selected from at least one of the unit represented by the following formula (A1) and the unit represented by the following formula (A2):

[0016]

[0017] The unit B is selected from at least one of the unit represented by the following formula (B1), the unit represented by the following formula (B2), and the unit represented by the following formula (B3):

[0018]

[0019] Among them, R1~R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, X is independently at least one selected from -O-, -S-, and -NR5-, R5 is hydrogen, Y, an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Y is a group having an antibacterial group.

[0020] [2] The antimicrobial additive according to [1], wherein the content of the Y group is 5 to 2000 mg / g relative to the total amount of the antimicrobial polymer.

[0021] [3] The antimicrobial additive according to [1] or [2], wherein the proportion of at least one unit selected from unit A and unit B is 5 to 50 mol% and the proportion of the vinyl chloride-based unit is 40 to 95 mol% relative to all units of the antimicrobial polymer.

[0022] [4] The antimicrobial additive according to any one of [1] to [3], wherein the antimicrobial polymer further comprises other units, and the other units are at least one selected from the group consisting of units based on monofunctional (meth)acrylate monomers, units based on monofunctional vinyl ester monomers, units based on monofunctional vinyl ether monomers, and units based on monofunctional styrene monomers.

[0023] [5] The antimicrobial additive according to [4], wherein in the antimicrobial polymer, the proportion of the other units is smaller than the proportion of the units based on vinyl chloride on a mol basis.

[0024] [6] The antimicrobial additive according to any one of [1] to [5], wherein the number average molecular weight of the antimicrobial polymer is 1,000 to 20,000.

[0025] [7] A method for producing an antimicrobial additive according to any one of [1] to [6], comprising:

[0026] A polymer F comprising at least one unit selected from the group consisting of the unit represented by the following formula (Af) and the unit represented by the following formula (Bf) and a unit based on vinyl chloride is reacted with a compound having at least one group selected from the group consisting of -OH, -SH, and -NHR5 and an antimicrobial group to form the antimicrobial polymer,

[0027]

[0028] Wherein, R1 to R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms.

[0029] [8]. A method for producing an antimicrobial additive according to [7], wherein, in the polymer F, the ratio of at least one unit selected from the unit represented by the formula (Af) and the unit represented by the formula (Bf) that reacts with a compound having at least one group selected from -OH, -SH, and -NHR5 and an antimicrobial group is 10 mol% or more relative to the total amount of at least one unit selected from the unit represented by the formula (Af) and the unit represented by the formula (Bf); and at least one unit selected from the unit represented by the formula (Af) and the unit represented by the formula (Bf) is at least one unit selected from the unit based on maleic anhydride, the unit based on citraconic anhydride, and the unit based on itaconic anhydride.

[0030] [9]. A vinyl chloride resin composition, comprising: a vinyl chloride resin and the antimicrobial additive according to any one of [1] to [6].

[0031]

[10] . A vinyl chloride resin molded product, wherein the molded product is produced by using the vinyl chloride resin composition according to [9].

[0032]

[11] . Use of a non-crosslinked polymer comprising at least one unit selected from unit A and unit B and a unit based on vinyl chloride as an antimicrobial additive in a vinyl chloride resin composition,

[0033] The unit A is selected from at least one of the unit represented by the following formula (A1) and the unit represented by the following formula (A2):

[0034]

[0035] The unit B is selected from at least one of the unit represented by the following formula (B1), the unit represented by the following formula (B2), and the unit represented by the following formula (B3):

[0036]

[0037] Among them, R1~R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, X is independently at least one selected from -O-, -S-, and -NR5-, R5 is hydrogen, Y, an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Y is a group having an antibacterial group.

[0038] Effects of the Invention

[0039] Through the implementation of the above technical solutions, the present invention can achieve the following technical effects:

[0040] (1) The antibacterial additive has a high density of antibacterial groups and high antibacterial efficiency;

[0041] (2) The introduction of the vinyl chloride component in the antibacterial additive improves the processing compatibility with the polyvinyl chloride matrix and the dispersibility in the matrix;

[0042] (3) The vinyl chloride resin composition made of the antibacterial additive and the polyvinyl chloride matrix has excellent antibacterial effect, excellent migration resistance and long-lasting antibacterial property. The antibacterial additive does not migrate to the surface of the product, which gives the vinyl chloride resin composition good antibacterial property even when the surface is damaged. DETAILED DESCRIPTION

[0043] The following is a detailed description of the present invention. The following description of the technical features is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:

[0044] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints numerical values ​​A and B.

[0045] In the present specification, the numerical range expressed using "above" and "below" means a range including the endpoint numerical values.

[0046] In the present specification, a numerical range expressed using "greater than" and "less than" means a range excluding the numerical endpoints.

[0047] In this specification, unless otherwise specified, "%" means percentage by weight.

[0048] In this specification, the word "may" means both performing a certain process and not performing a certain process.

[0049] In the present specification, "optional" or "optionally" means that the event or situation described below may or may not occur, and the description includes cases where the event occurs and cases where it does not occur.

[0050] In the present specification, "(meth)acrylate" encompasses both "methacrylate" and "acrylate".

[0051] In the present specification, "alkyl" or "alkylene" means a linear, branched or cyclic unsubstituted "alkyl" or "alkylene"; "hydroxyalkyl" means a linear, branched or cyclic "alkyl" or "alkylene" substituted by any number of hydroxyl groups.

[0052] In this specification, the references to "some specific / preferred embodiments", "other specific / preferred embodiments", "embodiments", etc., mean that the specific elements (e.g., features, structures, properties and / or characteristics) described in connection with the embodiments are included in at least one embodiment described herein, and may or may not exist in other embodiments. In addition, it should be understood that the elements may be combined in various embodiments in any suitable manner.

[0053] <<Antibacterial Additives>>

[0054] The antimicrobial additive of the present invention includes a non-crosslinked antimicrobial polymer (hereinafter referred to as an antimicrobial polymer) comprising at least one unit selected from the unit A and the unit B and a vinyl chloride-based unit.

[0055] The unit A is selected from at least one of the unit represented by the following formula (A1) and the unit represented by the following formula (A2):

[0056]

[0057] The unit B is selected from at least one of the unit represented by the following formula (B1), the unit represented by the following formula (B2), and the unit represented by the following formula (B3):

[0058]

[0059] Among them, R1~R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, X is independently at least one selected from -O-, -S-, and -NR5-, R5 is hydrogen, Y, an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Y is a group having an antibacterial group.

[0060] In some preferred embodiments, from the viewpoint of better exerting antibacterial property, the content of the antibacterial polymer of the present invention in the antibacterial additive of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. In some more preferred embodiments, from the viewpoint of reducing cost, the antibacterial additive of the present invention is formed only by the antibacterial polymer.

[0061] In the present invention, there is no particular restriction on the form in which the antimicrobial additive comprises the antimicrobial polymer. For example, the antimicrobial additive may be in the form of the antimicrobial polymer itself, in the form of a mixture of the antimicrobial polymer and other antimicrobial substances, in the form of encapsulating the antimicrobial polymer (or its mixture with other antimicrobial substances) with inorganic particles such as silicon dioxide or titanium dioxide or a polymer film, or in the form of coating the antimicrobial polymer (or its mixture with other antimicrobial substances) on an inorganic particle core such as silicon dioxide or titanium dioxide or a polymer core.

[0062] The details of each component forming the antimicrobial additive of the present invention will be described in more detail below.

[0063] <Antibacterial polymer>

[0064] The antimicrobial polymer of the present invention comprises at least one unit selected from unit A and unit B and a unit based on vinyl chloride,

[0065] The unit A is selected from at least one of a unit represented by the following formula (A1) (hereinafter also referred to as unit A1) and a unit represented by the following formula (A2) (hereinafter also referred to as unit A2):

[0066]

[0067] The unit B is selected from at least one of a unit represented by the following formula (B1) (hereinafter also referred to as unit B1), a unit represented by the following formula (B2) (hereinafter also referred to as unit B2), and a unit represented by the following formula (B3) (hereinafter also referred to as unit B3):

[0068]

[0069] In the formulas of the present invention, R1 to R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, preferably each independently hydrogen, methyl, ethyl, n-propyl or isopropyl. More preferably, R1 and R2 are each independently hydrogen or methyl, and R3 and R4 are both hydrogen. X is independently at least one selected from -O-, -S-, -NR5-, preferably independently -O- or -NR5-.

[0070] Among them, R5 is hydrogen, Y, an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, preferably hydrogen, Y, an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and from the viewpoint of reducing costs, more preferably hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0071] In the formulas of the present invention, the Y group is a group having an antibacterial group. In the present invention, there is no particular limitation on the type of the antibacterial group, which may be those known in the art, such as a guanidine group or a salt thereof, a quaternary ammonium salt group, a quaternary phosphonium salt group, a polypeptide group, a chitosan group, and the like. In the present invention, in some preferred embodiments, the antibacterial group is preferably a quaternary ammonium salt group or a quaternary phosphonium salt group from the viewpoint of more easily exerting antibacterial properties and reducing costs.

[0072] In the present invention, the Y group is a residue derived from the following antibacterial compound.

[0073] In the present invention, as long as the antibacterial property can be achieved, there is no particular restriction on the content of the Y group contained in the antibacterial polymer. In some preferred embodiments, from the viewpoint of further improving the antibacterial property, the content of the Y group is preferably 5 to 2000 mg / g, more preferably 10 to 1500 mg / g, and even more preferably 30 to 1300 mg / g relative to the total mass of the antibacterial polymer. In the present invention, there is no particular restriction on the method for measuring the content of the Y group, and various known methods used in the art can be used, and specific means can be selected according to the specific type of the Y group.

[0074] In the present invention, there is no particular limitation on the proportion of at least one unit selected from unit A and unit B in the antimicrobial polymer. In some preferred embodiments, from the viewpoint of further improving the antimicrobial property and ensuring the affinity between the antimicrobial polymer and the vinyl chloride resin matrix, the proportion of at least one unit selected from unit A and unit B is preferably 5 to 50 mol%, more preferably 8 to 45 mol%, and even more preferably 10 to 40 mol% relative to all units of the antimicrobial polymer.

[0075] In some preferred embodiments, from the viewpoint of further improving antibacterial properties, facilitating production and reducing costs, as unit A, unit A1 is preferably selected; as unit B, at least one selected from unit B1 and unit B2 is preferably selected.

[0076] In the present invention, the ratio of the units based on vinyl chloride to the total units of the antimicrobial polymer is preferably 40 to 95 mol %, more preferably 50 to 90 mol %, and even more preferably 60 to 80 mol %.

[0077] In addition, the antibacterial polymer of the present invention may optionally contain at least one unit selected from the unit represented by the following formula (Af) and the unit represented by the following formula (Bf) (the details of the unit represented by the following formula (Af) and the unit represented by the following formula (Bf) are described below). There is no particular restriction on the proportion of at least one unit selected from the unit represented by the following formula (Af) and the unit represented by the following formula (Bf) in the polymer. In some preferred embodiments, the proportion of at least one unit selected from the unit represented by the following formula (Af) and the unit represented by the following formula (Bf) relative to all the units of the antibacterial polymer is preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 10 mol% or less.

[0078] In addition to at least one unit selected from unit A and unit B, a unit based on vinyl chloride, and at least one unit selected from the unit represented by the following formula (Af) and the unit represented by the following formula (Bf), the antimicrobial polymer may further include other units. In some preferred embodiments, the other units are at least one unit selected from a unit based on a monofunctional (meth)acrylate monomer, a unit based on a monofunctional vinyl ester monomer, a unit based on a monofunctional vinyl ether monomer, and a unit based on a monofunctional styrene monomer.

[0079] There is no particular limitation on the monofunctional (meth)acrylate monomer, examples of which include, but are not limited to: alkyl (meth)acrylates (preferably, alkyl (meth)acrylates having an alkyl group with 1 to 8 carbon atoms), such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, and the like; hydroxyalkyl (meth)acrylates (preferably, hydroxyalkyl (meth)acrylates having an alkyl group with 1 to 8 carbon atoms), such as hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate; glycidyl (meth)acrylate, and the like. These monofunctional (meth)acrylate monomers may be used alone or in combination of any two or more.

[0080] There is no particular limitation on the monofunctional vinyl ester monomer, and examples thereof include, but are not limited to, vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, etc. These monofunctional vinyl ester monomers may be used alone or in combination of any two or more.

[0081] There is no particular limitation on the monofunctional vinyl ether monomers, and examples thereof include, but are not limited to, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, etc. These monofunctional vinyl ether monomers may be used alone or in combination of any two or more.

[0082] There is no particular limitation on the monofunctional styrene-based monomer, and examples thereof include, but are not limited to, styrene, α-methylstyrene, o-methylstyrene, etc. These monofunctional styrene-based monomers may be used alone or in combination of any two or more.

[0083] In some preferred embodiments, in the antimicrobial polymer, the proportion of other units is smaller than the proportion of vinyl chloride-based units on a mol basis.

[0084] In other preferred embodiments, the proportion of other units relative to all units of the antibacterial polymer is preferably 40 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and even more preferably 5 mol% or less.

[0085] In some more preferred embodiments, the ratio of unit A / unit based on vinyl chloride / at least one unit selected from the unit represented by the following formula (Af) and the unit represented by the following formula (Bf) / unit based on other monomers, relative to all units of the antibacterial polymer, is preferably 5-50 mol% / 40-95 mol% / 0-45 mol% / 0-40 mol%, more preferably 8-40 mol% / 50-90 mol% / 0-42 mol% / 0-20 mol%.

[0086] In addition, in the present invention, there is no particular restriction on the molecular weight of the antimicrobial polymer. In some preferred embodiments, from the viewpoint of being more conducive to improving antimicrobial properties and migration resistance and improving processability when preparing vinyl chloride resin molded products, the number average molecular weight of the antimicrobial polymer is preferably 1000 to 20000, more preferably 1500 to 18000, and even more preferably 2000 to 15000.

[0087] <Other components>

[0088] As mentioned above, the antimicrobial additive of the present invention may contain other components.

[0089] Examples of other components include, but are not limited to, other antimicrobial substances, other cross-linked or non-cross-linked polymers (e.g., polymers encapsulating the antimicrobial polymer of the present invention, polymers serving as the core), inorganic particles such as silicon dioxide and titanium dioxide, etc. The content of each of these components can be appropriately adjusted according to actual needs.

[0090] Examples of other cross-linked or non-cross-linked polymers include, without limitation, vinyl chloride-based resins, polylactic acid-based resins, styrene-based resins, other (meth)acrylate-based resins, thermoplastic elastomers, silicone resins, and the like.

[0091] <<Method for producing antimicrobial additive>>

[0092] The method for producing an antimicrobial additive of the present invention comprises: reacting a polymer F comprising at least one unit selected from the unit represented by the following formula (Af) (hereinafter also referred to as unit Af) and the unit represented by the following formula (Bf) (hereinafter also referred to as unit Bf) and a unit based on vinyl chloride with a compound having at least one group selected from -OH, -SH, -NHR5 and an antimicrobial group to form the antimicrobial polymer (hereinafter sometimes referred to as the antimicrobial polymer forming step).

[0093]

[0094] Wherein, R1 to R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, preferably each independently hydrogen, methyl, ethyl, n-propyl or isopropyl.

[0095] In some preferred embodiments of the present invention, from the viewpoint of further saving costs and facilitating the acquisition of polymer F, at least one unit selected from units Af and Bf is preferably at least one unit selected from maleic anhydride-based units, citraconic anhydride-based units and itaconic anhydride-based units.

[0096] The details of the antimicrobial additive and the antimicrobial polymer are as described above and will not be repeated here.

[0097] In the present invention, the polymer F comprising at least one unit selected from the group consisting of units Af and Bf and units based on vinyl chloride may optionally further comprise other units. The details of the other units are as described above and will not be repeated here.

[0098] Particularly preferably, from the viewpoint of more easily obtaining the antibacterial polymer of the present invention, the proportion of at least one unit selected from unit Af and unit Bf relative to all units of polymer F is preferably greater than 0 and 50 mol% or less, more preferably 20 to 40 mol%, and more preferably 30 to 40 mol%; the proportion of units based on vinyl chloride is preferably 40 to 95 mol%, more preferably 50 to 90 mol%, and more preferably 60 to 80 mol%; the proportion of other units is preferably 40 mol% or less, more preferably 20 mol% or less, more preferably 10 mol% or less, and even more preferably 5 mol% or less.

[0099] In some preferred embodiments, the number average molecular weight of polymer F is preferably 1,000 to 20,000, more preferably 1,500 to 18,000, and even more preferably 2,000 to 15,000.

[0100] In the present invention, there is no particular limitation on the source of polymer F, which can be a commercial product or homemade.

[0101] In the present invention, there is no particular restriction on the specific structure of the compound having at least one group selected from -OH, -SH, -NHR5 (hereinafter also referred to as a connecting group) and an antibacterial group (hereinafter sometimes referred to as an antibacterial compound), which may be a small molecule compound, an oligomer, a polymer, etc.

[0102] In addition, there is no particular restriction on the source of the compound having at least one group selected from -OH, -SH, -NHR5 and the antibacterial group, and the compound may be homemade or commercially available. In the case of homemade, the structure including at least one group selected from -OH, -SH, -NHR5 may be combined with a commercially available antibacterial agent by methods known in the art, or the structure including the antibacterial group and / or the commercially available antibacterial agent may be chemically combined with a compound, oligomer or polymer having at least one group selected from -OH, -SH, -NHR5 by methods known in the art, or the structure including at least one group selected from -OH, -SH, -NHR5 and the structure including the antibacterial group may be chemically combined with various available compounds, oligomers or polymers by methods known in the art.

[0103] In some preferred embodiments, the compound having at least one group selected from -OH, -SH, and -NHR5 and an antibacterial group of the present invention is preferably a compound having at least one group selected from -OH and -NHR5 and an antibacterial group.

[0104] As mentioned above, there is no particular limitation on the antimicrobial group, which may be those known in the art, such as a guanidine group or a salt thereof (e.g., hydrochloride, sulfate, etc.), a quaternary ammonium salt group, a quaternary phosphonium salt group, a polypeptide group, a chitosan group, etc. In some preferred embodiments, the antimicrobial group is preferably a quaternary ammonium salt group or a quaternary phosphonium salt group.

[0105] In some more preferred embodiments, the antibacterial compound is preferably at least one selected from guanidines or their salts (such as hydrochlorides), chitosans, polypeptides, quaternary ammonium salts, and quaternary phosphonium salts. From the viewpoint of further ensuring the antibacterial properties in the vinyl chloride resin matrix, it is more preferably at least one selected from quaternary ammonium salts and quaternary phosphonium salts.

[0106] Examples of guanidines include, but are not limited to, biguanides such as biguanides, bis(substituted or unsubstituted biguanide)alkanes (e.g., chlorhexidine, etc.), polyalkylene biguanides (e.g., polytetramethylene biguanide, polypentamethylene biguanide, polyhexamethylene biguanide, polyheptamethylene biguanide, polyoctamethylene biguanide, etc.); monoguanidines such as guanidine, alkylguanidine, polyalkyleneguanidine (e.g., polytetramethyleneguanidine, polypentamethyleneguanidine, polyhexamethyleneguanidine, polyheptamethyleneguanidine, polyoctamethyleneguanidine, etc.).

[0107] Examples of chitosans include, but are not limited to, chitosan and the like.

[0108] Examples of polypeptides include, but are not limited to, antimicrobial peptide LL37, antimicrobial peptide E6, antimicrobial peptide DP7, and the like.

[0109] There is no particular limitation on the specific structure of the quaternary ammonium salts, as long as they have at least one connecting group and at least one quaternary ammonium salt group. In some preferred embodiments, the quaternary ammonium salts are preferably composed of R((A)3N + B - ) m represents, wherein R is a hydrocarbon chain of C1 to 22, m represents an integer greater than 1, -((A)3N + B - ) is arbitrarily present at the end and / or in the chain of R; each A is independently a C1-22 hydrocarbon group, B represents a counter anion, which can be optionally connected to at least one of A and R; in addition, at least one of each A, R and B has at least one connecting group. In some more preferred embodiments, when m represents 1, R is a hydrocarbon group, -((A)3N + B - ) is arbitrarily present at the end or in the chain of R; when m represents 2 or more, at least one end of R has (-((A)3N + B - )(More preferably, at least two ends of R have (-((A)3N + B -)). In some more preferred embodiments, the hydrocarbon group mentioned about the quaternary ammonium salts is an alkyl group having 1 to 20 carbon atoms, which is optionally substituted with a halogen group, an aryl group having 6 to 20 carbon atoms, which is optionally substituted with a halogen group, or an aralkyl group having 7 to 20 carbon atoms, which is optionally substituted with a halogen group. In some other more preferred embodiments, m represents an integer of 1 to 6. In some other more preferred embodiments, B is preferably a halogen ion, an organic acid ion optionally connected to at least one of A and R, or an inorganic acid ion optionally connected to at least one of A and R.

[0110] In some particularly preferred embodiments, quaternary ammonium salts are particularly preferably composed of R((A)3N + B - ) represents, wherein each A and R is independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and at least one of each A and R further has at least one connecting group, wherein the connecting group is at least one group selected from -OH and -NHR5, and B is a halogen ion, a carboxylate ion optionally connected to at least one of A and R, or a sulfonate ion optionally connected to at least one of A and R.

[0111] There is no particular limitation on the specific structure of the quaternary phosphonium salts, as long as they have at least one connecting group and at least one quaternary phosphonium salt group. In some preferred embodiments, the phosphonium salts are preferably composed of R((A)3P + B - ) m Here, R, A, and B have the same meanings as those mentioned above for quaternary ammonium salts.

[0112] In some particularly preferred embodiments, the quaternary phosphonium salts are particularly preferably composed of R((A)3P + B - ) represents that each A and R is independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and at least one of each A and R also has at least one connecting group, which is at least one group selected from -OH and -NHR5, and B is a halogen ion.

[0113] In the step of forming the antimicrobial polymer, there is no particular restriction on the reaction method between polymer F and the antimicrobial compound, and the methods that can be used include but are not limited to: reacting after dissolving both in any suitable solvent, and reacting a solution of the antimicrobial compound with polymer F in a solid state.

[0114] In the step of forming the antimicrobial polymer, there is no particular limitation on the reaction conditions of the polymer F and the antimicrobial compound. In some specific embodiments, the reaction temperature may be 20 to 85° C., preferably 25 to 50° C. In other specific embodiments, the reaction time may be 1 to 120 minutes, preferably 2 to 60 minutes.

[0115] In the antimicrobial polymer formation step, in some preferred embodiments, from the viewpoint of more easily obtaining the antimicrobial polymer of the present invention, in polymer F, the proportion of at least one unit selected from unit Af and unit Bf that reacts with a compound having at least one group selected from -OH, -SH, -NHR5 and an antimicrobial group, relative to the total amount of at least one unit selected from unit Af and unit Bf, is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more.

[0116] In addition to the above-mentioned antimicrobial polymer formation step, the manufacturing method of the present invention may optionally include other steps, such as a step of preparing polymer F, a step of preparing an antimicrobial compound, a step of mixing the antimicrobial compound with other antimicrobial substances, a step of encapsulating the antimicrobial polymer, a step of coating the antimicrobial polymer on a core, a step of washing the antimicrobial polymer or the antimicrobial additive using any solvent, and a step of drying the antimicrobial polymer or the antimicrobial additive.

[0117] Polymer F can be obtained by polymerization methods known in the art, such as solution polymerization, emulsion polymerization, suspension polymerization, dispersion polymerization, and precipitation polymerization. In some more preferred embodiments, precipitation polymerization is preferably used from the viewpoint of more easily obtaining an antibacterial polymer that can achieve better technical effects and is more suitable for industrial production. In some particularly preferred embodiments, polymer F can be prepared by the following method: vinyl chloride, at least one monomer selected from maleic anhydride, citraconic anhydride, and itaconic anhydride, a solvent, and a free radical initiator are added to a polymerization reactor, and a polymerization reaction is carried out under dynamic or static conditions without using a dispersing aid and a chain transfer agent; the solvent is a poor solvent for polymer F.

[0118] The method for encapsulating the antimicrobial polymer can be implemented by various methods known in the art, such as physical blending, seed emulsion polymerization, self-assembly reaction, etc.

[0119] The step of coating the core with the antimicrobial polymer can be implemented by various methods known in the art, such as physical blending, seed emulsion polymerization, self-assembly reaction, and the like.

[0120] There is no particular limitation on the washing method, and various methods known in the art such as immersion washing method and rinsing method can be used.

[0121] There is no particular limitation on the drying method, and various methods known in the art may be used, such as oven drying, hot air drying, cold air drying, natural air drying, etc. Although there are no particular limitations, generally, the drying temperature is preferably 10 to 60° C., more preferably 20 to 40° C.; the drying time is preferably 2 minutes to 4 days, more preferably 10 minutes to 2 days.

[0122] In addition, the washing and drying steps may each be performed once or a plurality of times as desired.

[0123] <<Vinyl chloride resin composition>>

[0124] The vinyl chloride resin composition of the present invention comprises a vinyl chloride resin and the antimicrobial additive of the present invention or the antimicrobial additive obtained by the production method of the present invention.

[0125] In addition, by using a non-crosslinked polymer containing at least one unit selected from unit A and unit B and a unit based on vinyl chloride as an antibacterial additive in a vinyl chloride resin composition, an excellent antibacterial effect can be obtained: while obtaining excellent antibacterial properties, it has good compatibility with vinyl chloride resins and has excellent resistance to solvent migration, thereby giving the vinyl chloride resin composition long-lasting antibacterial properties.

[0126] In the present invention, the content of the antimicrobial additive of the present invention is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 0.5 to 10% by mass, relative to the total mass of the vinyl chloride resin.

[0127] In addition to the vinyl chloride resin and the above-mentioned specific antimicrobial additive, the vinyl chloride resin composition of the present invention may also optionally include other polymer components, examples of which include other resins, such as other vinyl chloride resins, propylene resins, ethylene resins, polyester resins such as polyethylene terephthalate, styrene resins, fluororesins, silicone resins, polyamide resins, polyimide resins, etc.; rubbers, such as styrene-butadiene rubber, nitrile rubber, butyl rubber, chloroprene rubber, isoprene rubber, butadiene rubber, ethylene propylene rubber, ethylene propylene diene rubber, silicone rubber; thermoplastic elastomers, such as olefin thermoplastic elastomers, styrene thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, polyvinyl chloride thermoplastic elastomers, polyurethane thermoplastic elastomers, fluoropolymer thermoplastic elastomers, etc. They can be used alone or in combination of two or more.

[0128] The vinyl chloride resin composition of the present invention may also optionally include various other additives generally known in the art in any content, such as fillers, pigments, plasticizers, ultraviolet absorbers, light stabilizers, matting agents, surfactants, leveling agents, surface conditioners, degassing agents, heat stabilizers, antistatic agents, rust inhibitors, silane coupling agents, antifouling agents, other antibacterial agents, foaming agents, crosslinking agents, lubricants, etc. These may be used alone or in combination of two or more.

[0129] The vinyl chloride resin composition of the present invention can be prepared by methods generally known in the art. For example, all components constituting the vinyl chloride resin composition of the present invention are mixed using standard mixing equipment such as a blender, a Banbury or Brabender mixer, an extruder, a kneader, and a two-roll mixer. There is no particular restriction on the preparation method of the composition, and the above-mentioned mixing can be carried out in a single stage or a multi-stage manner according to the desired composition of the composition. There is no particular restriction on the mixing temperature and mixing speed of the above-mentioned mixing, and they can be appropriately selected according to the desired composition of the composition.

[0130] Examples of compositions of the present invention include, but are not limited to, solid blends and liquid mixtures (including solutions, emulsions, and dispersions), and the like.

[0131] <<Vinyl chloride resin molded products>>

[0132] The vinyl chloride resin of the present invention is produced by using the above-mentioned vinyl chloride resin composition of the present invention.

[0133] In the present invention, examples of the vinyl chloride resin molded product include, but are not limited to, various vinyl chloride resin shaped materials (such as sheets or profiles), indwelling needles, hoses, films, and the like.

[0134] <<Example>>

[0135] The present invention is described in more detail below with reference to the following examples, but the scope of the present invention is not limited by these examples. Unless otherwise specified, the following percentages are based on mass conversion.

[0136] <Number average molecular weight and distribution>

[0137] The number average molecular weight and molecular weight distribution of the resulting polymer F were measured using gel permeation chromatography (GPC) with polystyrene as a standard.

[0138] In the present invention, the measured number average molecular weight and molecular weight distribution of polymer F are generally regarded as the number average molecular weight and molecular weight distribution of the antimicrobial polymer.

[0139] <Determination of Antibacterial Group Y Content>

[0140] The antibacterial group Y on the non-cross-linked antibacterial polymer was characterized by nuclear magnetic hydrogen spectroscopy (Bruker Avance 400) to obtain the molar ratio of the Y group in the entire antibacterial polymer, which was then converted into the mass ratio of the Y group in the entire antibacterial polymer based on the number average molecular weight of the antibacterial compound used and the Y group.

[0141] <Antibacterial Test>

[0142] This part was evaluated using Escherichia coli and Staphylococcus aureus.

[0143] a). Culture medium preparation

[0144] LB liquid culture medium - use a measuring cylinder to measure 100mL of distilled water and pour it into a 250mL reagent bottle. Use an analytical electronic balance to weigh 2.5g of LB broth culture medium and add it to mix well. Sterilize it in a high-temperature and high-pressure steam sterilizer at 121℃ for 15min and set aside. LB solid culture medium - use a measuring cylinder to measure 100mL of distilled water and pour it into a 250mL reagent bottle. Use an analytical electronic balance to weigh 2.5g of LB broth culture medium and 1.5g of agar powder. Add the above weighed reagents and mix well. Sterilize it in a high-temperature and high-pressure steam sterilizer at 121℃ for 15min. When the culture medium cools to about 40-50℃, use an electric pipette to draw 15mL of culture medium and pour it into a disposable sterile plate for use. 1 / 500 nutrient broth culture medium - use a measuring cylinder to measure 100mL of distilled water and pour it into a 250mL reagent bottle. Use an analytical electronic balance to weigh 1.8g of nutrient broth culture medium and add it to mix well and dissolve. Dilute the nutrient broth 500 times with deionized water and place it in a high-temperature and high-pressure steam sterilizer at 115°C for 30 minutes for later use.

[0145] b). Preparation of bacterial suspension

[0146] Take three 12mL bacterial culture tubes, add 3mL LB liquid culture medium to each, pick single colonies from the solid culture medium of Escherichia coli and Staphylococcus aureus and add them to the liquid culture medium, and use the other tube as a blank control. Place in a constant temperature oscillator (37℃, 200rpm) and shake culture overnight (15h), and adjust the bacterial solution concentration to 10 by comparing with the bacterial turbidity tube. 8 CFU / mL.

[0147] c). Sample processing

[0148] Place the samples in disposable culture dishes according to the groups, sterilize them on both sides under ultraviolet light for 30 minutes, and set aside.

[0149] d). Co-culture + plate spread count test

[0150] Escherichia coli and Staphylococcus aureus were diluted to 10 6 CFU / mL, place the sterilized sample in a disposable culture dish, draw 100μL of diluted bacterial solution and drop it on the sample surface. Then gently cover the surface of the sample inoculated with bacterial solution with the sterilized covering film, press gently to spread the bacterial solution as much as possible, and pay attention that the bacterial solution should not overflow the edge of the sample. Take another 100μL of diluted bacterial solution and drop it into the culture dish, then use sterile tweezers to grab the covering film and cover it on the bacterial solution as a blank control. Then place it in a constant temperature incubator at 37℃ and culture it for 24h. After the culture is completed, first use 10mL of sterile PBS solution to ultrasonically wash out the bacterial solution, then use PBS solution to dilute the washed bacterial solution 10 times continuously, and take 100μL of the dilution solution and evenly apply it on the LB solid culture medium. Place it in a 37℃ constant temperature incubator for 24h, take it out, take pictures and record the number of colonies.

[0151] The counting principle is based on the national standard GB4789.2-2016. The colony count is between 30 CFU and 300 CFU. The calculation method of the bacterial solution concentration (CFU / mL) is: colony count × dilution factor × 100 (100 μL bacterial solution is rinsed with 10 mL PBS) × 10 (0.1 mL coating). Furthermore, the bactericidal efficiency is calculated based on the following formula as the initial bactericidal efficiency.

[0152] Bactericidal efficiency = (1-test group bacterial solution concentration / control group bacterial solution concentration) × 100%

[0153] <Migration resistance>

[0154] The sample formed by the vinyl chloride resin composition with various antibacterial additives added is soaked in water, taken out after every 24 hours, and its surface is wiped back and forth 100 times with cotton, and then soaked in water for three cycles, that is, after 72 hours, the sample is tested with Staphylococcus aureus in the antibacterial test, and the bactericidal efficiency is calculated again as the post-treatment bactericidal efficiency. The post-treatment bactericidal efficiency is compared with the initial bactericidal efficiency, and it is believed that the smaller the difference between the two, the better.

[0155] Synthesis example 1

[0156] (1) Synthesis of polymer F1: 6.8 g of MAH, 0.5 g of di-(4-tert-butylcyclohexyl peroxydicarbonate), and 300 g of a mixed solvent of n-hexane and ethyl acetate (v:v=3:7) were added to a 500 ml reactor. After evacuation, 68.2.0 g of vinyl chloride VCM was added. After reacting at 45° C. for 8 h, the sample was washed by centrifugation and dried in a vacuum oven at 30° C. to obtain polymer F1.

[0157] (2) Synthesis of antimicrobial polymer: Polymer F1 and dodecyl dimethyl hydroxypropyl sulfobetaine were subjected to a ring-opening reaction in tetrahydrofuran (THF) at 50°C for 6 h. After the reaction, the unreacted dodecyl dimethyl hydroxypropyl sulfobetaine was removed and the product was dried in a vacuum oven at 40°C to constant weight to obtain an antimicrobial polymer P1.

[0158] Table 1 shows the details of the polymer F1 and the antimicrobial polymer P1.

[0159] Synthesis example 2

[0160] (1) Synthesis of polymer F2: 25.75 g of MAH, 0.5 g of di-(4-tert-butylcyclohexyl peroxydicarbonate), and 300 g of a mixed solvent of n-hexane and ethyl acetate (v:v=3:7) were added to a 500 ml reactor. After evacuation, 50.0 g of VCM was added. After reacting at 45° C. for 8 h, the sample was washed by centrifugation and dried in a vacuum oven at 30° C. to obtain polymer F2.

[0161] (2) Synthesis of antimicrobial polymer: Polymer F1 and dodecyl dimethyl hydroxypropyl sulfobetaine were subjected to a ring-opening reaction in tetrahydrofuran (THF) at 50°C for 6 h. After the reaction, the unreacted dodecyl dimethyl hydroxypropyl sulfobetaine was removed and the product was dried in a vacuum oven at 40°C to constant weight to obtain an antimicrobial polymer P2.

[0162] Table 1 shows the details of the polymer F2 and the antimicrobial polymer P2.

[0163] Synthesis example 3

[0164] The antimicrobial polymer P3 was obtained in the same manner as in Synthesis Example 2 except that the ratio of the polymer F2 synthesized in Synthesis Example 2 and dodecyldimethylhydroxypropylsulfobetaine was adjusted.

[0165] Table 1 shows the details of the antimicrobial polymer P3.

[0166] Synthesis example 4

[0167] The antimicrobial polymer P4 was obtained in the same manner as in Synthesis Example 2 except that the ratio of the polymer F2 synthesized in Synthesis Example 2 and dodecyldimethylhydroxypropylsulfobetaine was adjusted.

[0168] Table 1 shows the details of the antimicrobial polymer P4.

[0169] Synthesis example 5

[0170] The antimicrobial polymer P5 was obtained in the same manner as in Synthesis Example 2 except that the ratio of the polymer F2 synthesized in Synthesis Example 2 and dodecyldimethylhydroxypropylsulfobetaine was adjusted.

[0171] Table 1 shows the details of the antimicrobial polymer P5.

[0172] Table 1

[0173]

[0174] Examples 1 to 4 and Comparative Examples

[0175] The antibacterial polymers obtained in the above synthesis examples (Examples 1 to 4) and commercially available dodecyl dimethyl benzyl ammonium chloride (D1) (Comparative Example) were used as antibacterial additives to prepare vinyl chloride resin compositions and molded products thereof. Specifically, 100 parts of commercially available S-70PVC, 2 parts of methyl tin mercaptan heat stabilizer, 30 parts of plasticizer DINCH, and 10 parts of antibacterial additives were stirred evenly, and then mixed on an open mill for 5 minutes at a mixing temperature of 160°C; then the mixed sample was hot pressed on a flat vulcanizer at 175°C for 5 minutes, and then cold pressed for 5 minutes at a pressure of 10MPa, and the molded product was obtained by sheeting. Each molded product was tested for antibacterial properties and migration resistance. The test results are shown in Table 2.

[0176] Table 2

[0177]

Claims

1. An antimicrobial additive, characterized in that: It comprises: a non-crosslinked antimicrobial polymer comprising at least one unit selected from unit A and unit B and a vinyl chloride-based unit, The unit A is selected from at least one of the unit represented by the following formula (A1) and the unit represented by the following formula (A2): The unit B is selected from at least one of the unit represented by the following formula (B1), the unit represented by the following formula (B2), and the unit represented by the following formula (B3): wherein R1 to R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, X is independently at least one selected from -O-, -S-, and -NR5-, R5 is hydrogen, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Y is a group having an antibacterial group, wherein the antibacterial group is a quaternary ammonium salt group or a quaternary phosphonium salt group, The content of the Y group is greater than 200 mg / g and less than 1300 mg / g relative to the total amount of the antimicrobial polymer.

2. The antimicrobial additive according to claim 1, characterized in that: The content of the Y group is 500 to 1300 mg / g relative to the total amount of the antimicrobial polymer.

3. The antimicrobial additive according to claim 1 or 2, characterized in that: The proportion of at least one unit selected from the unit A and the unit B is 5 to 50 mol% and the proportion of the vinyl chloride-based unit is 40 to 95 mol% relative to all units of the antimicrobial polymer.

4. The antimicrobial additive according to claim 1 or 2, characterized in that: The antimicrobial polymer further includes other units, which are at least one selected from units based on monofunctional (meth)acrylate monomers, units based on monofunctional vinyl ester monomers, units based on monofunctional vinyl ether monomers, and units based on monofunctional styrene monomers.

5. The antimicrobial additive according to claim 4, characterized in that: In the antimicrobial polymer, the ratio of the other units is smaller than the ratio of the units based on vinyl chloride on a mol basis.

6. The antimicrobial additive according to claim 1 or 2, characterized in that: The number average molecular weight of the antibacterial polymer is 1,000 to 20,000.

7. A method for producing an antimicrobial additive according to any one of claims 1 to 6, characterized in that: include: A polymer F comprising at least one unit selected from the unit represented by the following formula (Af) and the unit represented by the following formula (Bf) and a unit based on vinyl chloride is reacted with a compound having at least one group selected from -OH, -SH, and -NHR5 and an antimicrobial group to form the antimicrobial polymer, wherein the antimicrobial group is a quaternary ammonium salt group or a quaternary phosphonium salt group, Wherein, R1 to R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms.

8. The method for producing an antimicrobial additive according to claim 7, characterized in that: In the polymer F, the proportion of at least one unit selected from the unit represented by the formula (Af) and the unit represented by the formula (Bf) that reacts with a compound having at least one group selected from -OH, -SH, and -NHR5 and an antibacterial group is greater than 10 mol% relative to the total amount of at least one unit selected from the unit represented by the formula (Af) and the unit represented by the formula (Bf); and at least one unit selected from the unit represented by the formula (Af) and the unit represented by the formula (Bf) is at least one unit selected from maleic anhydride-based units, citraconic anhydride-based units, and itaconic anhydride-based units.

9. A vinyl chloride resin composition, characterized in that: The composition comprises a vinyl chloride resin and the antimicrobial additive according to any one of claims 1 to 6.

10. A vinyl chloride resin molded product, characterized in that: The molded article is produced by using the vinyl chloride resin composition according to claim 9.

11. Use of a non-crosslinked polymer comprising at least one unit selected from unit A and unit B and a unit based on vinyl chloride as an antimicrobial additive in a vinyl chloride resin composition, The unit A is selected from at least one of the unit represented by the following formula (A1) and the unit represented by the following formula (A2): The unit B is selected from at least one of the unit represented by the following formula (B1), the unit represented by the following formula (B2), and the unit represented by the following formula (B3): in, R1 to R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, X is independently at least one selected from -O-, -S-, and -NR5-, R5 is hydrogen, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, Y is a group having an antibacterial group, and the antibacterial group is a quaternary ammonium salt group or a quaternary phosphonium salt group, The content of the Y group is greater than 200 mg / g and less than 1300 mg / g relative to the total amount of the polymer.

Images