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

Abstract

The present invention relates to an antibacterial additive based on cross-linked antibacterial polymer particles and a method for producing the same, a vinyl chloride resin composition and a molded product. The antibacterial additive of the present invention includes cross-linked antibacterial polymer particles, which contain at least one unit selected from unit A and unit B, a unit based on vinyl chloride and a unit based on a cross-linking monomer, unit A is selected from at least one of the units shown in the following formula (A1) and the units shown in the following formula (A2): unit B is selected from at least one of the units shown in the following formula (B1), the units shown in the following formula (B2) and the units shown in 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 an 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-purpose thermoplastics. In particular, PVC materials are widely used in the medical and health field to make various medical device products due to their good transparency, excellent toughness and resilience, low adsorption characteristics to hemoglobin, and low cost. Its usage accounts for about 25% of medical polymer materials. However, polyvinyl chloride materials themselves have no antibacterial properties. Once the manufactured medical devices such as infusion tubes and blood transfusion tubes come into contact with biological fluids, it is easy for bacteria to breed. At the same time, during use, it is easy for bacteria to attach to form biofilms, which can easily cause infection by pathogenic microorganisms through contact with human tissues or through intravenous infusion, blood transfusion, etc. Therefore, effective antibacterial modification of PVC materials is of great significance to improving the performance of medical PVC products.

[0003] It is a common technical means to add small molecule antibacterial agents such as quaternary ammonium salts or quaternary phosphonium salts to the PVC matrix and obtain antibacterial polyvinyl chloride through blending modification. However, these small molecule antibacterial agents have poor compatibility with the matrix, low charge density, volatility, and applicability problems such as migration during use leading to antibacterial failure. Organic polymer compounds with antibacterial groups can overcome some of the shortcomings of the above-mentioned small molecule antibacterial agents and have more efficient antibacterial properties than small molecule antibacterial agents. However, when these polymer antibacterial compounds are added to the PVC matrix as additives, there is a lack of consideration of compatibility with the matrix, processing matching, etc. Therefore, for PVC products, there is still room for improvement in the research and development of antibacterial compounds with high antibacterial efficiency and resistance to migration. Summary of the invention

[0004] Problem that the invention aims to solve

[0005] 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).

[0006] Solutions for solving problems

[0007] According to the inventor's intensive research, it is found that the above technical problems can be solved by implementing the following technical solutions:

[0008] [1] An antimicrobial additive, comprising cross-linked antimicrobial polymer particles, the antimicrobial polymer particles comprising at least one unit selected from unit A and unit B, a unit based on vinyl chloride and a unit based on a cross-linking monomer,

[0009] 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):

[0010]

[0011] 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):

[0012]

[0013] 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.

[0014] [2] The antimicrobial additive according to [1], wherein the content of the Y group is 5 to 1500 mg / g relative to the total amount of the antimicrobial polymer particles; and the antimicrobial polymer particles contain at least one unit selected from unit A and unit B on at least the surface thereof.

[0015] [3] The antimicrobial additive according to [1] or [2], wherein the unit based on the crosslinkable monomer is at least one selected from difunctional or higher-functional allyl esters, difunctional or higher-functional allyl ethers and difunctional or higher-functional (meth)acrylates.

[0016] [4] The antimicrobial additive according to any one of [1] to [3], wherein, relative to all units of the antimicrobial polymer particles, the proportion of at least one unit selected from unit A and unit B is 5 to 50 mol%, the proportion of the unit based on vinyl chloride is 40 to 95 mol%, and the proportion of the unit based on the cross-linking monomer is 2 to 30 mol%.

[0017] [5]. The antimicrobial additive according to any one of [1] to [4], wherein the antimicrobial polymer particles further include 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.

[0018] [6] The antimicrobial additive according to [5], wherein, in the antimicrobial polymer particles, the ratio of the other units is less than the total ratio of the vinyl chloride-based units and the crosslinking monomer-based units on a mol basis.

[0019] [7] The antimicrobial additive according to any one of [1] to [6], wherein the gel content of the antimicrobial polymer particles is 20% to 100%.

[0020] [8] A method for producing an antimicrobial additive according to any one of [1] to [7], comprising:

[0021] The antimicrobial polymer particles are formed by reacting crosslinked polymer particles 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), units based on vinyl chloride and units based on a crosslinking monomer with a compound having at least one group selected from the group consisting of -OH, -SH, and -NHR5 and an antimicrobial group,

[0022]

[0023] Wherein, R1 to R4 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms.

[0024] [9]. A method for producing an antimicrobial additive according to [8], wherein 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 group consisting of a maleic anhydride-based unit, a citraconic anhydride-based unit and an itaconic anhydride-based unit.

[0025]

[10] . A vinyl chloride resin composition, comprising: a vinyl chloride resin and the antimicrobial additive according to any one of [1] to [7].

[0026]

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

[0027] 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):

[0028]

[0029] 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):

[0030]

[0031] 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.

[0032] Effects of the Invention

[0033] Through the implementation of the above technical solutions, the present invention can achieve the following technical effects:

[0034] (1) The antibacterial additive has a high density of antibacterial groups and high antibacterial efficiency;

[0035] (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;

[0036] (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

[0037] 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:

[0038] 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.

[0039] In the present specification, the numerical range expressed using "above" and "below" means a range including the endpoint numerical values.

[0040] In the present specification, a numerical range expressed using "greater than" and "less than" means a range excluding the numerical endpoints.

[0041] In this specification, unless otherwise specified, "%" means percentage by weight.

[0042] In this specification, the word "may" means both performing a certain process and not performing a certain process.

[0043] 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.

[0044] In the present specification, "(meth)acrylate" encompasses both "methacrylate" and "acrylate".

[0045] 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.

[0046] 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.

[0047] <<Antibacterial Additives>>

[0048] The antimicrobial additive of the present invention comprises cross-linked antimicrobial polymer particles, wherein the antimicrobial polymer particles comprise at least one unit selected from the group consisting of units A and B, units based on vinyl chloride, and units based on a cross-linking monomer.

[0049] 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):

[0050]

[0051] 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):

[0052]

[0053] 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.

[0054] In some preferred embodiments, from the viewpoint of better exerting antibacterial properties, the content of the antibacterial polymer particles 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 costs, the antibacterial additive particles of the present invention are formed only by antibacterial polymer particles.

[0055] In the present invention, there is no particular limitation on the form in which the antimicrobial additive comprises antimicrobial polymer particles. For example, the antimicrobial additive may be in the form of antimicrobial polymer particles themselves, a mixture of antimicrobial polymer particles and other antimicrobial substances, or a form in which the antimicrobial polymer particles (or a mixture of antimicrobial polymer particles and other antimicrobial substances) are encapsulated with inorganic particles such as silicon dioxide or titanium dioxide or a polymer film.

[0056] The details of each component forming the antimicrobial additive of the present invention will be described in more detail below.

[0057] <Crosslinked Antimicrobial Polymer Particles>

[0058] The antimicrobial polymer particles of the present invention comprise at least one unit selected from the group consisting of unit A and unit B, a unit based on vinyl chloride, and a unit based on a crosslinking monomer.

[0059] 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):

[0060]

[0061] 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):

[0062]

[0063] 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-.

[0064] 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.

[0065] 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.

[0066] In the present invention, the Y group is a residue derived from the following antibacterial compound.

[0067] 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 particles. In some preferred embodiments, from the viewpoint of further improving the antibacterial property, the content of the Y group is preferably 5 to 1500 mg / g, more preferably 5 to 1300 mg / g, and even more preferably 10 to 1000 mg / g relative to the total mass of the antibacterial polymer particles. 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.

[0068] 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 relative to all units of the antimicrobial polymer particles is preferably 5 to 50 mol%, more preferably 8 to 45 mol%, and even more preferably 10 to 40 mol%.

[0069] In some preferred embodiments, the antimicrobial polymer particles contain at least one unit selected from the unit A and the unit B on at least the surface thereof. In some specific embodiments, from the viewpoint of saving production costs, at least one unit selected from the unit A and the unit B is preferably present only on the surface of the antimicrobial polymer particles. In other specific embodiments, from the viewpoint of further improving antimicrobial properties, at least one unit selected from the unit A and the unit B is preferably also present in the particle main body of the antimicrobial polymer particles other than the surface, for example, in the entire antimicrobial polymer particles.

[0070] 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.

[0071] In the present invention, the ratio of the units based on vinyl chloride to the total units of the antimicrobial polymer particles is preferably 40 to 95 mol%, more preferably 50 to 90 mol%, and even more preferably 60 to 80 mol%.

[0072] In the present invention, from the viewpoint of the antibacterial polymer particles of the present invention, the unit based on the crosslinkable monomer is preferably at least one selected from the group consisting of a unit based on a difunctional or higher allyl ester, a unit based on a difunctional or higher allyl ether, and a unit based on a difunctional or higher (meth)acrylate.

[0073] There is no particular limitation on the specific type of difunctional or higher allyl esters, but preferably difunctional to trifunctional allyl esters, for example, difunctional allyl esters such as diallyl phthalate, diallyl maleate, diallyl itaconate, etc., trifunctional allyl esters such as triallyl trimellitate, etc.

[0074] There is no particular limitation on the specific type of the difunctional or higher allyl ether, but preferably a difunctional allyl ether, for example, polyethylene glycol diallyl ether, triethylene glycol diallyl ether, diethylene glycol diallyl ether, ethylene glycol diallyl ether, polypropylene diallyl ether, tripropylene diallyl ether, dipropylene diallyl ether, propylene diallyl ether and the like.

[0075] There is no particular limitation on the specific type of the difunctional or higher (meth)acrylate, but it is preferably a di- to hexafunctional (meth)acrylate, for example, a difunctional (meth)acrylate such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, Ester, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, etc.; trifunctional (meth)acrylate, such as pentaerythritol tri(meth)acrylate, trihydroxymethane tri(meth)acrylate and glycerol tri(meth)acrylate, etc.; tetrafunctional (meth)acrylate, such as pentaerythritol tetra(meth)acrylate; pentafunctional (meth)acrylate, such as dipentaerythritol penta(meth)acrylate; hexafunctional (meth)acrylate, such as dipentaerythritol hexa(meth)acrylate, etc.

[0076] In the present invention, the ratio of the units based on the crosslinkable monomer to the total units of the antibacterial polymer particles is preferably 2 to 30 mol %, more preferably 5 to 25 mol %, and even more preferably 10 to 20 mol %.

[0077] In addition, the antibacterial polymer particles 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 particles 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, a unit represented by the following formula (Af) and a unit represented by the following formula (Bf), the antimicrobial polymer particles may optionally further include other units to adjust the mechanical properties of the antimicrobial polymer particles. In some preferred embodiments, from the viewpoint of easier polymerization, the other units are at least one 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, 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 particles, the proportion of other units is smaller than the total proportion of units based on vinyl chloride and units based on crosslinking monomers on a mol basis.

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

[0085] In some more preferred embodiments, relative to all units of the antibacterial polymer particles, the ratio of at least one unit selected from units A and units B / units based on vinyl chloride / at least one unit selected from the units represented by the following formula (Af) and the units represented by the following formula (Bf) / units based on other monomers 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 limitation on the gel content of the antimicrobial polymer particles. In some preferred embodiments, the gel content of the antimicrobial polymer particles is preferably 20% to 100%, more preferably 30% to 100%, and even more preferably 40% to 100%, from the viewpoint of being more conducive to improving the migration resistance and improving the processability when preparing the vinyl chloride resin molded product.

[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 particles of the present invention), inorganic particles such as silicon dioxide and titanium dioxide, etc. The content of each of them 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 crosslinked polymer particles F (hereinafter sometimes referred to as particles F) containing 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), units based on vinyl chloride, and units based on a crosslinking monomer with a compound having at least one group selected from -OH, -SH, -NHR1 and an antimicrobial group to form the antimicrobial polymer particles (hereinafter sometimes referred to as the antimicrobial polymer particle formation 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 cost saving and easy to obtain particles 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 particles are as described above and will not be repeated here.

[0097] In the present invention, the details of the crosslinking monomer-based units in the particle F are as described above, and will not be described in detail here. In the present invention, the particle F comprising at least one unit selected from the unit Af and the unit Bf, the unit based on vinyl chloride and the unit based on the crosslinking monomer may further optionally include other units. The details of the other units are as described above, and will not be described in detail here.

[0098] Particularly preferably, from the viewpoint of more easily obtaining the antibacterial polymer particles of the present invention, the proportion of at least one unit selected from unit Af and unit Bf relative to all units of particle F is preferably greater than 0 and less than 50 mol%, more preferably 20-40 mol%, and more preferably 30-40 mol%; the proportion of units based on vinyl chloride is preferably 40-95 mol%, more preferably 50-90 mol%, and more preferably 60-80 mol%; the proportion based on crosslinking units is preferably 2-30 mol%, more preferably 5-25 mol%, and more preferably 10-20 mol%; the proportion of other units is preferably less than 40 mol%, more preferably less than 20 mol%, more preferably less than 10 mol%, and even more preferably less than 5 mol%.

[0099] In some preferred embodiments, the gel content of the particles F is preferably 20% to 100%, more preferably 30% to 100%, and even more preferably 40% to 100%.

[0100] In the present invention, there is no particular limitation on the source of the particles F, which may be a commercially available 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 particles, there is no particular limitation on the method for reacting the particles F with the antimicrobial compound, and the methods that may be used include but are not limited to: reacting the particles F after dispersing them in any suitable solvent in which the antimicrobial compound is dissolved; reacting a solution of the antimicrobial compound with the particles F in a solid state; and the like.

[0114] In the step of forming the antimicrobial polymer particles, there is no particular limitation on the reaction conditions between the particles 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 30 to 480 minutes, preferably 60 to 360 minutes.

[0115] In the antimicrobial polymer particle formation step, in some preferred embodiments, from the viewpoint of more easily obtaining the antimicrobial polymer particles of the present invention, at least one unit selected from unit Af and unit Bf on at least the surface of particle F reacts with a compound having at least one group selected from -OH, -SH, -NHR5 and an antimicrobial group.

[0116] In addition to the above-mentioned antibacterial polymer particle formation step, the manufacturing method of the present invention may optionally include other steps, such as a step of preparing particles F, a step of preparing antibacterial compounds, a step of mixing antibacterial compounds with other antibacterial substances, a step of encapsulating antibacterial polymer particles, a step of loading the antibacterial polymer particles on a core, a step of washing the antibacterial polymer particles or antibacterial additives using any solvent, and a step of drying the antibacterial polymer particles or antibacterial additives.

[0117] The particles F can be obtained by polymerization methods known in the art, such as 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 antibacterial polymer particles that can achieve better technical effects. In some particularly preferred embodiments, the particles F can be prepared by the following method: vinyl chloride, at least one monomer selected from maleic anhydride, citraconic anhydride, and itaconic anhydride, a crosslinking monomer, 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 the vinyl chloride resin particles.

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

[0119] 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.

[0120] 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 30 minutes to 4 days, more preferably 60 minutes to 2 days.

[0121] In addition, the washing and drying steps may each be performed once or a plurality of times as desired.

[0122] <<Vinyl chloride resin composition>>

[0123] The vinyl chloride resin composition of the present invention comprises a vinyl chloride resin and the above-mentioned antimicrobial additive of the present invention.

[0124] In addition, by using polymer particles containing at least one unit selected from unit A and unit B, units based on vinyl chloride and units based on cross-linking monomers as an antibacterial additive in a vinyl chloride resin composition, excellent effects 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] <<Example>>

[0131] 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.

[0132] <Gel content measurement>

[0133] In the present invention, the method for measuring the gel content is as follows: accurately weigh a certain mass m0 of dry resin and load it into a filter cartridge, extract it with THF in a Soxhlet extractor for more than 24 hours, and weigh the insoluble matter after drying to obtain a mass m1. The ratio of the mass of the insoluble matter to the mass of the resin, i.e. (m1 / m0)×100%, is the gel content.

[0134] <Determination of Antibacterial Group Y Content>

[0135] The weight gain of the cross-linked polymer particles F after the reaction with the antibacterial compound is obtained by the weight method, and then converted into the mass ratio of the Y group in the entire antibacterial additive by the number average molecular weight of the Y group. <Antibacterial Test>

[0136] This part was evaluated using Escherichia coli and Staphylococcus aureus.

[0137] a). Culture medium preparation

[0138] 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.

[0139] b). Preparation of bacterial suspension

[0140] Take three 12mL bacterial culture tubes, add 3mL LB liquid culture medium to each, pick single colonies from Escherichia coli and Staphylococcus aureus solid culture medium 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) for shaking culture overnight (15h), and adjust the bacterial solution concentration to 108CFU / mL by comparing with the bacterial turbidity tube.

[0141] c). Sample processing

[0142] 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.

[0143] d). Co-culture + plate spread count test

[0144] 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.

[0145] 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.

[0146] Bactericidal efficiency = (1-test group bacterial solution concentration / control group bacterial solution concentration) × 100%

[0147] <Migration resistance>

[0148] 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.

[0149] Synthesis example 1

[0150] (1) Synthesis of particles F: 9.45 g of maleic anhydride (MAH), 14.7 g of diethylene glycol diacrylate as a cross-linking agent, 0.5 g of di-(4-tert-butylcyclohexyl peroxydicarbonate), and 300 g of a mixed solvent of n-hexane and ethyl acetate (v:v=1:1) were added to a 500 ml reactor. After evacuation, 75.85 g of vinyl chloride (VCM) was added. After reacting at 45°C for 18 h, the sample was washed by centrifugation and dried in a vacuum oven at 30°C to obtain particles F1.

[0151] (2) Synthesis of antimicrobial polymer particles: Particles F1 and dodecyl dimethyl hydroxypropyl sulfobetaine were subjected to a ring-opening reaction in a mixed solvent of tetrahydrofuran / n-hexane at 50°C for 6 h. After the reaction, unreacted dodecyl dimethyl hydroxypropyl sulfobetaine was removed and the product was dried in a vacuum oven at 40°C to constant weight to obtain antimicrobial polymer particles P1.

[0152] Synthesis example 2

[0153] (1) Synthesis of particles F: 42.2 g of MAH, 14.7 g of diethylene glycol diacrylate as a cross-linking agent, 0.5 g of di-(4-tert-butylcyclohexyl peroxydicarbonate), and 300 g of a mixed solvent of n-hexane and ethyl acetate (v:v=1:1) were added to a 500 ml reactor. After evacuation, 45.0 g of VCM was added. After reacting at 45° C. for 18 h, the sample was washed by centrifugation and dried in a vacuum oven at 30° C. to obtain particles F2.

[0154] (2) Synthesis of antimicrobial polymer particles: Particles F2 and dodecyl dimethyl hydroxypropyl sulfobetaine were subjected to a ring-opening reaction in a mixed solvent of tetrahydrofuran / n-hexane 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 antimicrobial polymer particles P2.

[0155] Synthesis example 3

[0156] Antimicrobial polymer particles P3 were obtained in the same manner as in Synthesis Example 2 except that the ratio of the particles F2 obtained in Synthesis Example 2 and dodecyldimethylhydroxypropylsulfobetaine was adjusted.

[0157] Synthesis example 4

[0158] Antimicrobial polymer particles P4 were obtained in the same manner as in Synthesis Example 2 except that the ratio of the particles F2 obtained in Synthesis Example 2 and dodecyldimethylhydroxypropylsulfobetaine was adjusted.

[0159] Synthesis example 5

[0160] (1) Synthesis of particles F: 46 g of MAH, 1.5 g of diethylene glycol diacrylate as a cross-linking agent, 0.5 g of di-(4-tert-butylcyclohexyl peroxydicarbonate), and 300 g of a mixed solvent of n-hexane and ethyl acetate (v:v=1:1) were added to a 500 ml reactor. After evacuation, 57.0 g of VCM was added. After reacting at 45° C. for 18 h, the sample was washed by centrifugation and dried in a vacuum oven at 30° C. to obtain particles F3.

[0161] (2) Synthesis of antimicrobial polymer particles: Particles F3 and dodecyl dimethyl hydroxypropyl sulfobetaine were subjected to a ring-opening reaction in a mixed solvent of tetrahydrofuran / n-hexane at 50°C for 6 h at a molar ratio of anhydride to hydroxyl of 1:1. 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 antimicrobial polymer particles P3.

[0162] Table 1

[0163]

[0164] Examples 1 to 6 and Comparative Examples

[0165] The antibacterial polymer particles obtained in the synthesis examples (Examples 1 to 6) 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 polymer particles 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.

[0166] Table 2

[0167]

Claims

1. An antimicrobial additive, characterized in that: The invention comprises cross-linked antimicrobial polymer particles, wherein the antimicrobial polymer particles comprise at least one unit selected from the group consisting of unit A and unit B, a unit based on vinyl chloride, and a unit based on a cross-linking monomer. 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 45 to 1000 mg / g relative to the total amount of the antibacterial polymer particles.

2. The antimicrobial additive according to claim 1, characterized in that: The antimicrobial polymer particles include at least one unit selected from the group consisting of unit A and unit B at least on the surface thereof.

3. The antimicrobial additive according to claim 1 or 2, characterized in that: The unit based on the crosslinkable monomer is at least one selected from difunctional or higher-functional allyl esters, difunctional or higher-functional allyl ethers, and difunctional or higher-functional (meth)acrylates.

4. The antimicrobial additive according to claim 1 or 2, characterized in that: With respect to all units of the antimicrobial polymer particles, the at least one unit selected from unit A and unit B accounts for 5 to 50 mol%, the unit based on vinyl chloride accounts for 40 to 95 mol%, and the unit based on the crosslinking monomer accounts for 2 to 30 mol%.

5. The antimicrobial additive according to claim 1 or 2, characterized in that: The antibacterial polymer particles further include other units, which 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.

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

7. The antimicrobial additive according to claim 1 or 2, characterized in that: The gel content of the antibacterial polymer particles is 20% to 100%.

8. A method for producing an antimicrobial additive according to any one of claims 1 to 7, characterized in that: include: The crosslinked polymer particles 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), units based on vinyl chloride and units based on a crosslinking monomer are reacted with a compound having at least one group selected from -OH, -SH, and -NHR5 and an antibacterial group to form the antibacterial polymer particles, wherein the antibacterial 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.

9. The method for producing an antimicrobial additive according to claim 8, characterized in that: 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.

10. 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 7.

11. Use of polymer particles comprising at least one unit selected from unit A and unit B, units based on vinyl chloride and units based on a crosslinking monomer 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 45 to 1000 mg / g relative to the total amount of the polymer particles.

Images