Copolymer, antibacterial agent, bactericide, antibacterial material, bactericidal material, antibacterial method, sterilization method, and method for producing copolymer

Abstract

Provided is a novel compound having an excellent antibacterial or bactericidal effect.　This copolymer includes a structural unit represented by formula (1) and a structural unit represented by formula (2). [In formula (1), R1 represents an (un)substituted C1-C20 alkanediyl group and R2 represents -N+R3R4R5Y- or -NR6R7 (wherein R3, R4, R5, R6, and R7 each independently represent a hydrogen atom or an (un)substituted C1-C20 hydrocarbon group and Y- represents a counter anion).] [In formula (2), R8 represents a hydrogen atom or an (un)substituted C1-C20 hydrocarbon group.]

Description

Copolymer, antibacterial agent, disinfectant, antibacterial material, disinfectant material, antibacterial method, disinfectant method, and method for producing copolymer

[0001] The present invention relates to a copolymer, an antibacterial agent, a disinfectant, an antibacterial material, a disinfectant material, an antibacterial method, a disinfection method, and a method for producing a copolymer.

[0002] Conventionally, in various fields such as paints, marine, architecture, sanitation, food, cosmetics, machinery, medicine, daily necessities, various appliances, etc., it has been widely practiced to impart antibacterial or bactericidal properties by applying or blending antibacterial agents or bactericides, or to mold articles using antibacterial or bactericidal materials to make them have antibacterial or bactericidal properties. For example, it has been reported that a copolymer of aminopropyl vinyl ether and methyl methacrylate, butyl methacrylate, or diethylaminoethyl methacrylate has an antibacterial effect against Staphylococcus aureus and Pseudomonas aeruginosa (Patent Document 1).

[0003] Special Publication No. 2003-507542

[0004] An object of the present invention is to provide a novel compound having excellent antibacterial or bactericidal effects.

[0005] As a result of intensive research, the present inventors have found that a copolymer having a specific maleimide structural unit in addition to a specific vinyl ether structural unit containing a nitrogen atom in the molecule has excellent antibacterial or bactericidal effects, and have completed the present invention.

[0006] That is, the present invention provides the following items <1> to <21>: <1> A copolymer having a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (1)") and a structural unit represented by the following formula (2) (hereinafter also referred to as "structural unit (2)") (hereinafter also referred to as "copolymer of the present invention").

[0007]

[0008] [In formula (1), R 1 represents a substituted or unsubstituted alkanediyl group having 1 to 20 carbon atoms, R 2 is -N + R 3 R 4 R 5 Y - or -NR6 R 7 (R 3 , R 4 , R 5 , R 6 and R 7 each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; Y - indicates a counter anion).

[0009]

[0010] [In formula (2), R 8 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.

[0011] <2> R 1 <3> The copolymer according to <1>, wherein R is a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms. 3 , R 4 and R 5 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and R 6 and R 7 <4> The copolymer according to <1> or <2>, wherein R are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms. 8 <5> The copolymer according to any one of <1> to <3>, wherein R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 8 <6> The copolymer according to any one of <1> to <5>, which is an alternating copolymer.

[0012] <7> An antibacterial agent, a disinfectant, or an antibacterial and disinfectant agent, containing the copolymer according to any one of <1> to <6> as an active ingredient (hereinafter, these are also collectively referred to as "the antibacterial and / or disinfectant of the present invention"). <8> The agent according to <7>, which is for bacteria selected from gram-positive bacteria and gram-negative bacteria. <9> The agent according to <7> or <8>, which is used for antibacterial, disinfecting, or antibacterial and disinfecting an article.

[0013] <10> An antibacterial material, a germicidal material, or an antibacterial and germicidal material, containing the copolymer according to any one of <1> to <6> (hereinafter, these are also collectively referred to as the "antibacterial and / or germicidal material of the present invention"). <11> The material according to <10>, which is for bacteria selected from gram-positive bacteria and gram-negative bacteria. <12> The material according to <10> or <11>, which is used for antibacterial, germicidal, or antibacterial and germicidal purposes on an article.

[0014] <13> An antibacterial method, a sterilization method, or an antibacterial and sterilization method, which uses the copolymer according to any one of <1> to <6> (hereinafter, these are also collectively referred to as the "antibacterial and / or sterilization method of the present invention"). <14> The method according to <13>, which is an antibacterial method for bacteria selected from gram-positive bacteria and gram-negative bacteria, a sterilization method for bacteria selected from gram-positive bacteria and gram-negative bacteria, or an antibacterial and sterilization method for bacteria selected from gram-positive bacteria and gram-negative bacteria. <15> The method according to <13> or <14>, which is a method for antibacterial, sterilization, or antibacterial and sterilization of an article.

[0015] <16> A method for producing the copolymer according to any one of <1> to <6>, comprising a polymerization step of polymerizing a monomer represented by the following formula (M1) (hereinafter also referred to as “monomer (M1)”) and a monomer represented by the following formula (M2) (hereinafter also referred to as “monomer (M2)”) (hereinafter also referred to as “method for producing the copolymer of the present invention”):

[0016]

[0017] [In formula (M1), X 1 represents a protected amino group, a halogen atom, -N + R 3 R 4 R 5 Y - or -NR 6 R 7 (R 3 , R 4 , R 5 , R 6 , R 7 and Y - has the same meaning as above), R 1 has the same meaning as above.]

[0018]

[0019] [In formula (M2), R 8 has the same meaning as above.]

[0020] <17> X 1 <18> The production method according to <16>, wherein X is a halogen atom, and the method further comprises an amination or quaternary ammonium conversion step of amminating or quaternizing the polymer obtained in the polymerization step. 1 is a protected amino group, and the method further comprises a deprotection step of deprotecting the polymer obtained in the polymerization step.

[0021] <19> The copolymer according to any one of <1> to <6>, used for antibacterial, sterilizing, or antibacterial and sterilizing (hereinafter, these are also collectively referred to as "antibacterial and / or sterilizing"). <20> Use of the copolymer according to any one of <1> to <6> for producing an antibacterial agent, a sterilizing agent, or an antibacterial and sterilizing agent. <21> Use of the copolymer according to any one of <1> to <6> for producing an antibacterial material, a sterilizing material, or an antibacterial and sterilizing material.

[0022] The copolymer of the present invention has excellent antibacterial or bactericidal effects. Therefore, according to the method for producing a copolymer of the present invention, a copolymer having excellent antibacterial or bactericidal effects can be produced simply and efficiently.

[0023] The alternating copolymer obtained in Synthesis Example 1 1 1H-NMR spectrum of the alternating copolymer obtained in Synthesis Example 2. 1 1H-NMR spectrum of the alternating copolymer obtained in Synthesis Example 3. 1 1H-NMR spectrum of the alternating copolymer obtained in Synthesis Example 4. 1 1H-NMR spectrum of the alternating copolymer obtained in Synthesis Example 5. 1 1H-NMR spectrum of the alternating copolymer obtained in Synthesis Example 6. 11H-NMR spectrum. A diagram showing the antibacterial and bactericidal effects of the alternating copolymers obtained in Synthesis Examples 1 and 2 against Bacillus subtilis. A diagram showing the antibacterial and bactericidal activity of the alternating copolymers obtained in Synthesis Examples 2, 5, and 6 against Bacillus subtilis. A diagram showing the antibacterial and bactericidal activity of the alternating copolymers obtained in Synthesis Examples 5 and 6 against Escherichia coli.

[0024] <Copolymer> The copolymer of the present invention has the structural unit (1) and the structural unit (2).

[0025] (Structural Unit (1)) The copolymer of the present invention has the structural unit (1). In formula (1), R 1 represents a substituted or unsubstituted alkanediyl group having 1 to 20 carbon atoms. 1 The alkanediyl group represented by the formula (I) may be linear or branched. 1 The number of carbon atoms in the alkanediyl group represented by the formula (R) is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. 1 Examples of the alkanediyl group represented by the formula (I) include a methane-1,1-diyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a propane-2,2-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. Among these, a methane-1,1-diyl group, an ethane-1,2-diyl group, and a propane-1,3-diyl group are preferred, and an ethane-1,2-diyl group is more preferred. R 1 The alkanediyl group represented by the following formula may or may not have a substituent. Examples of the substituent include halogen atoms such as chlorine atoms, bromine atoms, and fluorine atoms. The substitution position and the number of the substituents are optional, and when two or more substituents are present, the substituents may be the same or different.

[0026] In formula (1), R 2 is -N + R 3 R 4 R 5 Y - or -NR6 R 7 (R 3 , R 4 , R 5 , R 6 and R 7 each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12, more preferably 1 to 7), and Y - indicates a counter anion). 3 , R 4 and R 5 From the viewpoint of antibacterial and bactericidal effects, each of the groups is preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12, more preferably 1 to 7).

[0027] Y - The counter anion may be a monovalent anion or a polyvalent anion derived from citric acid or the like. The counter anion may be a monoatomic anion or a polyatomic anion. Examples of the monovalent counter anion include Cl. - ,Br - , I - halogen ions such as ClO - , BF4 - , CH3(C=O)O - , PF6 - and the like.

[0028] R 3 ~R 7The hydrocarbon group represented by the formula (I) is a concept that encompasses aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, and may be linear, branched, or cyclic, and may be either saturated or unsaturated. Among these, aliphatic hydrocarbon groups are preferred. The aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 3. As the aliphatic hydrocarbon group, an alkyl group is preferred. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms, more preferably 3 to 7. As the alicyclic hydrocarbon group, a cycloalkyl group is preferred. Specific examples include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 12. As the aromatic hydrocarbon group, an aryl group or an aralkyl group is preferred. Examples of the aryl group include a phenyl group, etc. Examples of the aralkyl group include a benzyl group and a phenethyl group, etc. R 3 ~R 7 The hydrocarbon group represented by the formula (I) may or may not have a substituent. Examples of the substituent include halogen atoms such as chlorine atoms, bromine atoms, and fluorine atoms. The substitution position and the number of the substituents are optional, and when two or more substituents are present, the substituents may be the same or different.

[0029] The total content of the structural unit (1) is preferably 25 mol% or more, more preferably 30 mol% or more, even more preferably 32.5 mol% or more, particularly preferably 35 mol% or more, based on the total structural units of the copolymer, from the viewpoint of the alternation of the structural units, antibacterial effect, bactericidal effect, etc., and is preferably 70 mol% or less, more preferably 67.5 mol% or less, even more preferably 65 mol% or less, particularly preferably 60 mol% or less, based on the total structural units of the copolymer, from the viewpoint of the alternation of the structural units, antibacterial effect, bactericidal effect, etc. As a specific range, based on the total structural units of the copolymer, 25 mol% or more and 70 mol% or less is preferred, 30 mol% or more and 67.5 mol% or less is more preferred, 32.5 mol% or more and 65 mol% or less is even more preferred, and 35 mol% or more and 60 mol% or less is particularly preferred.

[0030] (Structural unit (2)) In formula (2), R 8 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and from the viewpoint of antibacterial and bactericidal effects, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms is preferred.

[0031] R 8 The number of carbon atoms in the hydrocarbon group represented by R is preferably 2 to 20, more preferably 4 to 20, even more preferably 4 to 16, still more preferably 4 to 12, and particularly preferably 6 to 10. 8 When the number of carbon atoms in the hydrocarbon group represented by the formula (R) is 4 or more or 6 or more, the compound has an excellent antibacterial or bactericidal effect against both gram-positive and gram-negative bacteria. 8 The hydrocarbon group represented by R is a concept that encompasses aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, and may be linear, branched, or cyclic, and may be a saturated or unsaturated hydrocarbon group. Among these, from the viewpoint of antibacterial and bactericidal effects, etc., aliphatic hydrocarbon groups and aromatic hydrocarbon groups are preferred, and aromatic hydrocarbon groups are more preferred. 8 When is an aromatic hydrocarbon group, the antibacterial and bactericidal effects are particularly excellent.

[0032] The number of carbon atoms in the aliphatic hydrocarbon group is preferably 2 to 20, more preferably 4 to 20, even more preferably 4 to 16, still more preferably 4 to 12, and particularly preferably 6 to 10. 8 When the number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is 4 or more or 6 or more, the compound has an excellent antibacterial or bactericidal effect against both gram-positive and gram-negative bacteria. The aliphatic hydrocarbon group is preferably an alkyl group. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. Of these, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group are preferred. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 12, and more preferably 4 to 8. The alicyclic hydrocarbon is preferably a cycloalkyl group. Specific examples include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 12. The aromatic hydrocarbon group is preferably an aryl group or an aralkyl group. Examples of the aryl group include a phenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. R 8 The hydrocarbon group represented by the formula (I) may or may not have a substituent. Examples of the substituent include halogen atoms such as chlorine atoms, bromine atoms, and fluorine atoms; alkoxy groups such as methoxy groups and ethoxy groups; and hydroxy groups. The substitution positions and number of the substituents are optional, and when two or more substituents are present, the substituents may be the same or different.

[0033] The total content of the structural unit (2) is preferably 30 mol% or more, more preferably 32.5 mol% or more, even more preferably 35 mol% or more, particularly preferably 40 mol% or more, based on the total structural units of the copolymer, from the viewpoint of the alternation of the structural units, antibacterial effect, bactericidal effect, etc.; and from the viewpoint of the alternation of the structural units, antibacterial effect, bactericidal effect, etc., it is preferably 75 mol% or less, more preferably 70 mol% or less, even more preferably 67.5 mol% or less, particularly preferably 65 mol% or less, based on the total structural units of the copolymer. As a specific range, it is preferably 30 mol% or more and 75 mol% or less, more preferably 32.5 mol% or more and 70 mol% or less, even more preferably 35 mol% or more and 67.5 mol% or less, and particularly preferably 40 mol% or more and 65 mol% or less, based on the total structural units of the copolymer. The content of each structural unit in the copolymer of the present invention is 1 It can be measured by H-NMR or the like.

[0034] The molar ratio of the content of the structural unit (2) to the structural unit (1) [(2) / (1)] is preferably 0.4 or more, more preferably 0.45 or more, even more preferably 0.5 or more, and particularly preferably 0.65 or more, from the viewpoints of the alternation of the structural units, antibacterial effect, bactericidal effect, etc., and is preferably 3 or less, more preferably 2.5 or less, even more preferably 2.25 or less, and particularly preferably 2 or less, from the viewpoints of the alternation of the structural units, antibacterial effect, bactericidal effect, etc. Specifically, the molar ratio is preferably 0.4 or more and 3 or less, more preferably 0.45 or more and 2.5 or less, even more preferably 0.5 or more and 2.25 or less, and particularly preferably 0.65 or more and 2 or less.

[0035] The total content of the segments formed by bonding the structural unit (1) and the structural unit (2) is preferably 80 mol% or more and 100 mol% or less, more preferably 90 mol% or more and 100 mol% or less, and particularly preferably 95 mol% or more and 100 mol% or less, based on the total structural units of the copolymer.

[0036] The copolymer of the present invention is preferably an alternating copolymer. Furthermore, the copolymer of the present invention is preferably a non-crosslinked polymer. Examples of the terminals of the copolymer of the present invention include hydrogen atoms, halogen atoms, chain transfer agent residues, and polymerization initiator residues.

[0037] The number average molecular weight (Mn) of the copolymer of the present invention is preferably 1,000 to 100,000, and more preferably 1,500 to 50,000. The weight average molecular weight (Mw) of the copolymer of the present invention is preferably 1,000 to 200,000, and more preferably 1,500 to 100,000. The molecular weight distribution (Mw / Mn) is preferably 1 to 3, and more preferably 1 to 2. The number average molecular weight, weight average molecular weight, and molecular weight distribution refer to values ​​measured by gel permeation chromatography (GPC).

[0038] <Method for Producing Copolymer> The method for producing a copolymer of the present invention is a method for producing the copolymer of the present invention, and includes a polymerization step of polymerizing a monomer represented by the following formula (M1) and a monomer represented by the following formula (M2). According to the method for producing a copolymer of the present invention, the copolymer of the present invention can be produced simply and efficiently.

[0039]

[0040] [In formula (M1), X 1 represents a protected amino group, a halogen atom, -N + R 3 R 4 R 5 Y - or -NR 6 R 7 (R 3 , R 4 , R 5 , R 6 , R 7 and Y - has the same meaning as above), R 1 has the same meaning as above.]

[0041]

[0042] [In formula (M2), R 8 has the same meaning as above.]

[0043] (Polymerization step) X in formula (M1) 1 -N + R 3 R 4 R 5 Y - or -NR6 R 7 is R in formula (1). 2 -N + R 3 R 4 R 5 Y - or -NR 6 R 7 It is synonymous with X. 1 The protected amino group represented by the formula (1) is an amino group protected with a protecting group, which is deprotected by, for example, an acid, a base, or heat. Examples of the protecting group include imide-based protecting groups, amide-based protecting groups, carbamate-based protecting groups (e.g., tert-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, etc.), and sulfonamide-based protecting groups (e.g., tosyl group, etc.). Among these, R 2 When preparing a compound in which X is —NH2, an imide-based protecting group is preferred. An example of an amino group protected with an imide-based protecting group is a phthalimide residue. 1 Examples of the halogen atom represented by the formula (I) include a chlorine atom, a bromine atom, and a fluorine atom.

[0044] Examples of the monomer (M1) include vinyl 2-phthalimidyl methyl ether, vinyl 2-phthalimidyl ethyl ether (2-vinyloxyethylphthalimide), vinyl 2-phthalimidyl propyl ether, 2-chloromethyl vinyl ether, 2-bromomethyl vinyl ether, 2-iodomethyl vinyl ether, 2-chloroethyl vinyl ether, 2-bromoethyl vinyl ether, 2-iodoethyl vinyl ether, 2-chloropropyl vinyl ether, 2-bromopropyl vinyl ether, 2-iodopropyl vinyl ether, 2-(vinyloxy)-N,N,N-trimethylmethanaminium chloride, 2-(vinyloxy)-N,N,N-trimethylmethanaminium bromide, 2-(vinyloxy)-N,N,N-trimethylmethanaminium iodide, 2-(vinyloxy)-N,N,N-trimethylethanaminium chloride, and 2-(vinyloxy)-N,N,N-trimethylethanaminium. bromide, 2-(vinyloxy)-N,N,N-trimethylethanaminium iodide, 2-(vinyloxy)-N,N,N-trimethylpropanaminium chloride, 2-(vinyloxy)-N,N,N-trimethylpropanaminium bromide, 2-(vinyloxy)-N,N,N-trimethylpropanaminium iodide, etc. Furthermore, as the monomer (M1), a commercially available product or one synthesized according to a conventional method may be used.

[0045] The amount of monomer (M1) used is, from the viewpoint of alternation of structural units, antibacterial effect, bactericidal effect, etc., preferably 35 mol% or more, more preferably 37.5 mol% or more, even more preferably 40 mol% or more, particularly preferably 45 mol% or more, relative to the total amount of monomers used in the polymerization step 100 mol%, and from the viewpoint of alternation of structural units, antibacterial effect, bactericidal effect, etc., preferably 65 mol% or less, more preferably 62.5 mol% or less, even more preferably 60 mol% or less, particularly preferably 55 mol% or less. As a specific range, relative to the total amount of monomers used in the polymerization step 100 mol%, preferably 35 mol% or more and 65 mol% or less, more preferably 37.5 mol% or more and 62.5 mol% or less, more preferably 40 mol% or more and 60 mol% or less, even more preferably 45 mol% or more and 55 mol% or less.

[0046] Examples of the monomer (M2) include maleimide, N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-tert-butylmaleimide, N-n-pentylmaleimide, N-n-hexylmaleimide, N-cyclohexylmaleimide, N-4-chlorocyclohexylmaleimide, N-phenylmaleimide, N-o-methoxyphenylmaleimide, and N-m-methoxyphenylmaleimide. Examples of the monomer (M2) include N-o-hydroxybenzylmaleimide, N-m-hydroxybenzylmaleimide, N-p-hydroxybenzylmaleimide, N-o-methoxybenzylmaleimide, N-m-methoxybenzylmaleimide, N-p-methoxybenzylmaleimide, and N-p-chlorobenzylmaleimide. These may be used singly or in combination of two or more. Monomer (M2) may be a commercially available product or one synthesized according to a conventional method.

[0047] The amount of monomer (M2) used is, from the viewpoint of alternation of structural units, antibacterial effect, bactericidal effect, etc., preferably 35 mol% or more, more preferably 37.5 mol% or more, even more preferably 40 mol% or more, particularly preferably 45 mol% or more, relative to the total amount of monomers used in the polymerization step 100 mol%, and from the viewpoint of alternation of structural units, antibacterial effect, bactericidal effect, etc., preferably 65 mol% or less, more preferably 62.5 mol% or less, even more preferably 60 mol% or less, particularly preferably 55 mol% or less. As a specific range, relative to the total amount of monomers used in the polymerization step 100 mol%, preferably 35 mol% or more and 65 mol% or less, more preferably 37.5 mol% or more and 62.5 mol% or less, more preferably 40 mol% or more and 60 mol% or less, even more preferably 45 mol% or more and 55 mol% or less.

[0048] The method for producing the copolymer of the present invention can be carried out with reference to known techniques described in Soft Matter, 2008, 4, 1066-1071, Polymers, 2020, 12, 2255, etc., except for polymerizing the monomer (M1) and the monomer (M2).

[0049] As the polymerization method in the polymerization step, radical polymerization is preferred from the viewpoint of alternation of structural units. From the viewpoint of narrow dispersion, living radical polymerization is more preferred, reversible addition-fragmentation chain transfer polymerization (RAFT polymerization), atom transfer radical polymerization (ATRP polymerization), and nitroxide-mediated radical polymerization (NMP polymerization) are further preferred, and RAFT polymerization is particularly preferred.

[0050] From the viewpoint of reaction efficiency, the polymerization step is preferably carried out in the presence of a radical polymerization initiator and / or a chain transfer agent, and also from the viewpoint of reaction efficiency, the polymerization step is preferably carried out in the presence of a solvent.

[0051] Examples of the radical polymerization initiator include azo-based polymerization initiators such as 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] disulfate dihydrate, azobisisobutyronitrile, methyl azobisisobutyrate, azobisdimethylvaleronitrile, and azobiscyanovaleric acid; and peroxide-based polymerization initiators such as benzoyl peroxide and tert-butyl hydroperoxide. These may be used alone or in combination of two or more.

[0052] The molar ratio of the amount of radical polymerization initiator used to the total amount of monomers (M1) and (M2) [(radical polymerization initiator) / ((M1)+(M2))] is preferably 0.0001 to 0.02, more preferably 0.0002 to 0.01, from the viewpoint of controlling the polymerization reaction.

[0053] The chain transfer agent is preferably a chain transfer agent used in RAFT polymerization (hereinafter also referred to as "RAFT agent"). The RAFT agent is not particularly limited as long as it is used in RAFT polymerization, and examples thereof include dithiobenzoate-type RAFT agents such as 2-cyanopropan-2-yl benzodithioate and 4-cyano-4-[(thiobenzoyl)sulfanyl]pentanoic acid; 2-hydroxyethyl benzyl trithiocarbonate, 4-[(2-carboxyethylsulfanylthiocarbonyl)sulfanyl]-4-cyanopentanoic acid, 2-{[(2-carboxyethyl)sulfanylthiocarbonyl]sulfanyl}propanoic acid, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, and 2-cyano-2-[(dodecylsulfanylthiocarbonyl)sulfanyl] trithiocarbonate-type RAFT agents such as 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propane, S,S-dibenzyltrithiocarbonate, 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, and methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate; and dithiocarbamate-type RAFT agents such as 2'-cyanonobutan-2'-yl 4-chloro-3,5-dimethylpyrazole-1-carbodithioate, 2'-cyanonobutan-2'-yl 3,5-dimethylpyrazole-1-carbodithioate, cyanomethyl 3,5-dimethylpyrazole-1-carbodithioate, and cyanomethyl N-methyl-N-phenyldithiocarbamate. In addition to these, examples of xanthate-type RAFT agents include O-phenyl-S-benzyl xanthate, O-ethyl-S-(1-phenylethyl)xanthate, O-ethyl-S-[2-(ethoxycarbonyl)prop-2-yl]xanthate, O-ethyl-S-(2-cyanoprop-2-yl)xanthate, O-ethyl-S-cyanomethyl xanthate, and O-pentafluorophenyl-S-benzyl xanthate. These may be used alone or in combination of two or more.

[0054] When a chain transfer agent is used, the molar ratio of the amount of the chain transfer agent to the radical polymerization initiator [(chain transfer agent) / (radical polymerization initiator)] is preferably 1 to 50, more preferably 2 to 25, from the viewpoint of controlling the polymerization reaction.

[0055] The solvent is preferably water, an organic solvent, or a mixture thereof. Examples of the organic solvent include ether solvents such as diethyl ether, dibutyl ether, tert-butyl methyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; amide solvents such as N,N-dimethylformamide; halogenated hydrocarbon solvents such as methylene chloride (dichloromethane), chloroform, and 1,2-dichloroethane (ethylene chloride); aromatic hydrocarbon solvents such as benzene, toluene, xylene, and anisole; aliphatic hydrocarbon solvents such as n-hexane, n-heptane, n-octane, and isooctane; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene (decalin); nitrile solvents such as acetonitrile; ketone solvents such as acetone; monohydric lower alcohol solvents such as methanol, ethanol, and isopropanol; and polyhydric lower alcohol solvents such as ethylene glycol and glycerin. The solvents may be used alone or in combination of two or more. When a mixture of water and an organic solvent is used, the mass ratio of the amounts of water and organic solvent used is preferably 30:70 to 70:30.

[0056] The mass ratio of the amount of the solvent to the total amount of the monomers (M1) and (M2) [(solvent) / ((M1)+(M2))] is preferably from 0.1 to 50, and more preferably from 1 to 25, from the viewpoints of reaction efficiency, polymerization reaction control, and the like.

[0057] The polymerization temperature in the polymerization step may be appropriately selected as long as it is equal to or lower than the boiling point of the solvent, and is usually 20 to 120° C. The polymerization time is usually 0.5 to 120 hours, and from the viewpoint of reaction efficiency, 1 to 24 hours is preferred.

[0058] The method for producing a copolymer of the present invention may be any method as long as it includes the polymerization step as described above, and specific examples of the method include the following methods A to C. <Method A> In the monomer (M1), X 1<Method B> A method comprising a polymerization step of polymerizing a monomer (M1) in which X is a protected amino group with a monomer (M2), and a deprotection step of deprotecting the polymer obtained in the polymerization step. 1 wherein X is a halogen atom, is polymerized with a monomer (M2), and the polymer obtained in the polymerization step is aminated or quaternized. 1 Ga-N + R 3 R 4 R 5 Y - or -NR 6 R 7 and a monomer (M2).

[0059] Among these methods A to C, methods A and B are preferred from the viewpoint of production efficiency, and method B is preferred because it allows the desired copolymer to be produced simply and efficiently. By producing by method B, it is easy to selectively produce the desired copolymer from primary to tertiary amines and quaternary ammonium. On the other hand, method A is suitable for producing the copolymer of the present invention by using the R 2 is suitable for producing -NH2.

[0060] (Deprotection Step) The deprotection step of Method A is a deprotection step of deprotecting the polymer obtained in the polymerization step. By this step, the monomer (M1) (where X 1 = protected amino group) is deprotected. The deprotection step in Method A may be carried out appropriately by a known method depending on the type of protecting group. For example, when the protecting group is an imide-based protecting group, examples of the deprotection method include hydrolysis using an acid or a base, or contact with hydrazine or methylamine. When the protecting group is a carbamate-based protecting group, examples of the deprotection method include strong acidic conditions, Birch reduction, or contact with an amine such as piperidine.

[0061] (Amination or quaternary ammonium conversion step) The amination or quaternary ammonium conversion step of method B is a step of aminating or quaternary ammonium converting the polymer obtained in the polymerization step. By this step, the monomer (M1) (where X 1 The halogen atom at the end of the side chain in the structural unit derived from R = halogen atom is aminated or quaternized. 3 R 4 R 5 A compound represented by N (e.g., trimethylamine) and R 6 R 7 It is preferable to carry out the quaternary ammonium conversion using a compound (nucleophile) selected from compounds represented by R NH (e.g., dimethylamine). 2 Ga-N + R 3 R 4 R 5 Y - In the case where the polymer obtained in the polymerization step is 3 R 4 R 5 In the case of aminating the copolymer of the present invention (the copolymer of the present invention, R 2 Ga-NR 6 R 7 In the case where the polymer obtained in the polymerization step is 6 R 7 It is preferred to react a compound represented by NH.

[0062] R 3 R 4 R 5 Compounds represented by N and R 6 R 7 The amount of the compound selected from the compounds represented by NH is usually 0.01 to 5 molar equivalents per mole of the structural unit derived from the monomer (M1).

[0063] From the viewpoint of reaction efficiency, the amination or quaternary ammonium conversion step is preferably carried out in the presence of a solvent. Examples of the solvent include the same solvents as those used in the polymerization step. The amount of the solvent used is about 1 to 10,000 parts by mass per 100 parts by mass of the polymer obtained in the polymerization step.

[0064] The reaction temperature for the amination or quaternary ammonium conversion step may be appropriately selected as long as it is equal to or lower than the boiling point of the solvent, but is usually 20 to 120° C. The reaction time is usually 0.5 to 150 hours, but from the viewpoint of reaction efficiency, 1 to 100 hours is preferred.

[0065] In addition, the monomer (M1) of the polymer obtained in the polymerization step (wherein X 1 When the halogen atom at the end of the side chain in the structural unit derived from R = halogen atom is a chlorine atom, a halogen exchange reaction may be carried out prior to the amination or quaternary ammonium formation step. For example, a halogen exchange reaction is carried out using sodium iodide to obtain R 3 R 4 R 5 When the compound represented by N is used as a nucleophilic agent to form a quaternary ammonium compound, R 2 Ga-N + R 3 R 4 R 5 I - The reaction product of each step may be isolated and purified as necessary.

[0066] The copolymer of the present invention produced in this manner has excellent antibacterial or bactericidal effects. Fungi are broadly classified as bacteria and fungi, and the copolymer of the present invention is particularly useful for inhibiting bacterial growth. While the reason why the copolymer of the present invention has excellent antibacterial or bactericidal effects is not entirely clear, the inventors speculate that this is because the antibacterial and bactericidal effects are significantly enhanced by combining the structural unit (1) with the structural unit (2) to form a copolymer. Therefore, the copolymer of the present invention can be used as an antibacterial and / or bactericidal agent or an antibacterial and / or bactericidal material, either directly or in combination with other components as needed. The copolymer of the present invention can be used for antibacterial and / or bactericidal purposes and can also be used to produce antibacterial and / or bactericidal agents. The above-mentioned "use" can be applied to articles, as well as humans, non-human animals, and specimens derived from humans or non-human animals. Among these, the copolymer of the present invention is suitable for antibacterial and / or bactericidal purposes for articles. When used in humans or non-human animals, non-therapeutic use (non-medical procedures) is preferred.

[0067] Examples of the above-mentioned articles include daily necessities (e.g., toothbrushes, combs, cosmetics, diapers, etc.), clothing, automobiles (particularly seats, steering wheels, door handles), bathrooms, bathroom supplies (e.g., shower curtains, bathtubs, etc.), toilets, toilet supplies, kitchens, kitchen supplies (e.g., sponges, etc.), toys, food and beverages, medical supplies, hospital equipment, home appliances and electrical products (e.g., telephones, air conditioners, cash registers, etc.), building materials (e.g., handrails, flooring, roofs, toilet bowls (e.g., toilet seats), walls, wallpaper, etc.), paints, protective coatings, manufacturing equipment (e.g., food processing machines, etc.), packaging (e.g., food packaging, etc.), animal cages, animal sheds, contact lenses, operating parts of equipment (e.g., touch panels, etc.), public transportation (e.g., train handrails, straps, etc.), ship hulls, buoys, ballast tanks, etc. It should be noted that the term "non-therapeutic" does not include medical procedures, i.e., methods of operating, treating, or diagnosing humans, and more specifically, does not include methods of operating, treating, or diagnosing humans by a physician, medical professional, or a person under the direction of a physician.

[0068] The bacteria include gram-positive bacteria and gram-negative bacteria. 8 When the number of carbon atoms in the hydrocarbon group represented by the formula (I) is 4 or more or 6 or more, the compound has an excellent antibacterial or bactericidal effect against both Gram-positive and Gram-negative bacteria. Examples of Gram-positive bacteria include bacteria of the genus Propionibacterium or Cutibacterium; bacteria of the genus Corynebacterium such as Corynebacterium xerosis; Staphylococcus such as Staphylococcus aureus; bacteria of the genus Listeria; bacteria of the genus Bacillus such as Bacillus subtilis; and bacteria of the genus Alicyclobacillus. Examples of Gram-negative bacteria include bacteria of the genus Escherichia, such as Escherichia coli; bacteria of the genus Salmonella; bacteria of the genus Vibrio; bacteria of the genus Pseudomonas, such as Pseudomonas aeruginosa; bacteria of the genus Acinetobacter, such as Acinetobacter baumannii; and bacteria of the genus Klebsiella, such as Klebsiella pneumoniae. The bacteria may be resistant bacteria.

[0069] <Antibacterial and / or bactericidal agent, antibacterial and / or bactericidal material> The antibacterial and / or bactericidal agent of the present invention contains the copolymer of the present invention as an active ingredient. The antibacterial and / or bactericidal material of the present invention contains the copolymer of the present invention. The content of the copolymer of the present invention relative to the total mass of the antibacterial and / or bactericidal agent is 10 -5 Preferably, the content is up to 10% by mass. The antibacterial and / or bactericidal agent and antibacterial and / or bactericidal material of the present invention can be in any form such as a liquid, spray, sheet, capsule, etc. When the antibacterial and / or bactericidal agent and antibacterial and / or bactericidal material of the present invention is in the form of a liquid, for example, it may contain a solvent, a surfactant, etc. in addition to the copolymer of the present invention.

[0070] Specific examples of using the copolymer of the present invention as an antibacterial and / or bactericidal material include a molded article formed by combining the copolymer of the present invention with other polymeric materials, organic materials, or inorganic materials to obtain a molded article having antibacterial and / or bactericidal properties. Examples of molding methods for the molded article include a method of mixing the copolymer of the present invention with a curing agent or the like and curing the mixture, and a method of chemically reacting the copolymer of the present invention with another compound. Examples of such molded articles include touch panels, handrails, and everyday items.

[0071] <Antibacterial and / or Sterilizing Method> The antibacterial and / or sterilizing method of the present invention uses the copolymer of the present invention. Examples include a method comprising a coating step of coating the surface of an object with a liquid containing the copolymer of the present invention and, if necessary, a solvent; a method comprising a molded body formation step of combining the copolymer of the present invention with other polymeric materials, organic materials, or inorganic materials to form a molded body (e.g., a method of mixing the copolymer of the present invention with a curing agent or the like and curing it, or a method of chemically reacting the copolymer of the present invention with another compound); and a method of carrying out the copolymer production method of the present invention on an object to form a copolymer layer on the surface of the object. Examples of the object include the articles listed above. The material of the object is not particularly limited, and examples include plastic, rubber, metal, glass, and wood. In addition, examples of coating methods in the coating step include spray coating, coater coating, dipping, brush coating, and roll coating.

[0072] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The analytical conditions in the examples are as follows.

[0073] [ 1H-NMR] Apparatus: Bruker AC-500, internal standard: non-deuterated solvent, solvent: deuterated chloroform, heavy water, deuterated dimethyl sulfoxide [Molecular weight measurement] Measurement method: GPC method, apparatus: TOSOH EcoSEC HLC-8320GPC, column: TOSOH TSK-GEL H (2 columns), elution solvent: tetrahydrofuran, standard: polystyrene (Scientific Polymer Products, Inc.; Mn = 580-670,000 g mol -1 , Mw / Mn = 1.01-1.07)

[0074] Synthesis Example 1: Synthesis of Alternating Copolymer (1) An alternating copolymer was synthesized according to the following synthesis route.

[0075]

[0076] (1) That is, 1.2 g of 1,2-dichloroethane was added to 110 mg of 2-chloroethyl vinyl ether, and then 125 mg of N-ethylmaleimide, 5.0 mg of 2-hydroxyethyl benzyl trithiocarbonate, 0.7 mg of azobisisobutyronitrile, and 41 mg of decahydronaphthalene as an internal standard substance were added. The mixture was immediately connected to a vacuum line, and degassed by repeating the freeze-degassing method three times. The tube was sealed under reduced pressure and reacted at 60°C for 2.5 hours. The product was then purified by reprecipitation (good solvent: dichloromethane, poor solvent: hexane) to obtain a copolymer. (2) Next, 110 mg of the product obtained above was diluted with 4.3 mol L -1 0.28 mL of an aqueous trimethylamine solution and 2.0 mL of acetonitrile were added, and the mixture was reacted for 48 hours at 60° C. The product was purified by dialysis (MWCO: 2000) to obtain the target quaternary ammonium copolymer.

[0077] Synthesis Example 2: Synthesis of Alternating Copolymer (2) An alternating copolymer was synthesized according to the following synthesis route.

[0078]

[0079] (1) Specifically, 10 g of 1,2-dichloroethane was added to 705 mg of 2-vinyloxyethylphthalimide, followed by the addition of 410 mg of N-ethylmaleimide, 16 mg of 2-hydroxyethyl benzyl trithiocarbonate, and 2.1 mg of azobisisobutyronitrile. The mixture was immediately connected to a vacuum line and degassed by repeating the freeze-degassing method three times. The tube was sealed under reduced pressure and allowed to react at 60°C for 16 hours. The product was then purified by reprecipitation (good solvent: dichloromethane, poor solvent: methanol) to obtain a copolymer. (2) Next, 30 mL of ethanol, 15 mL of dioxane, and 1.0 mL of hydrazine monohydrate were added to 100 mg of the product obtained above, and the mixture was allowed to react at 80°C for 2 hours. The reaction mixture was concentrated, and then water was added to precipitate the by-products. The supernatant solution was purified by dialysis (MWCO: 2000), and the solution was diluted with 0.6 mol L to bring the pH to around 4. -1 After adding an aqueous solution of hydrochloric acid, the mixture was freeze-dried to obtain the desired aminated copolymer.

[0080] Synthesis Example 3: Synthesis of Alternating Copolymer (3) An alternating copolymer was synthesized according to the following synthesis route.

[0081]

[0082] That is, an alternating copolymer of 2-chloroethyl vinyl ether and N-ethylmaleimide was obtained by the same procedure as in Synthesis Example 1(1). 0.15 mL of a 50% aqueous dimethylamine solution and 20 mL of acetonitrile were added to 110 mg of the obtained alternating copolymer, and the mixture was reacted at 25°C for 72 hours. The product was purified by reprecipitation (good solvent: methanol, poor solvent: ethyl acetate) to obtain the desired aminated copolymer.

[0083] Synthesis Example 4: Synthesis of Alternating Copolymer (4) An alternating copolymer was synthesized according to the following synthesis route.

[0084]

[0085] (1) That is, 3.0 g of 2-chloroethyl vinyl ether was mixed with 4.3 mol L -119 mL of aqueous trimethylamine solution and 35 mL of acetone were added, and the reaction was carried out at 50°C for 24 hours. The reaction mixture was concentrated, and then dichloromethane was added to precipitate the by-products. The supernatant solution was then concentrated to obtain a quaternary ammonium vinyl ether monomer. (2) Next, 1.1 g of a water / acetonitrile mixed solvent (1 / 1 (v / v)) was added to 170 mg of the vinyl ether monomer obtained above, and 84 mg of N-ethylmaleimide and 4.3 mg of VA-044 (2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride) were further added. The mixture was immediately connected to a vacuum line, and degassed by repeating the freeze-degassing method three times. The tube was sealed under reduced pressure, and the reaction was carried out at 60°C for 4.5 hours. The product was purified by dialysis (MWCO: 2000), to obtain the desired quaternary ammonium copolymer.

[0086] Synthesis Example 5: Synthesis of Alternating Copolymer (5) An alternating copolymer was synthesized according to the following synthesis route.

[0087]

[0088] (1) Specifically, 10 g of 1,2-dichloroethane was added to 607 mg of 2-vinyloxyethylphthalimide, followed by the addition of 506 mg of N-hexylmaleimide, 14 mg of 2-hydroxyethyl benzyl trithiocarbonate, and 1.8 mg of azobisisobutyronitrile. The mixture was immediately connected to a vacuum line and degassed by repeating the freeze-degassing method three times. The tube was sealed under reduced pressure and allowed to react at 60°C for 16 hours. The product was then purified by reprecipitation (good solvent: dichloromethane, poor solvent: methanol) to obtain a copolymer. (2) Next, 30 mL of ethanol, 15 mL of dioxane, and 1.0 mL of hydrazine monohydrate were added to 100 mg of the product obtained above, and the mixture was allowed to react at 80°C for 2 hours. The reaction mixture was concentrated, and then methanol was added to precipitate the by-products. The supernatant solution was purified by dialysis (MWCO: 2000), and the solution was diluted with 0.6 mol L to bring the pH to around 4. -1 After adding an aqueous solution of hydrochloric acid, the mixture was freeze-dried to obtain the desired aminated copolymer.

[0089] Synthesis Example 6: Synthesis of Alternating Copolymer (6) An alternating copolymer was synthesized according to the following synthesis route.

[0090]

[0091] (1) Specifically, 10 g of 1,2-dichloroethane was added to 598 mg of 2-vinyloxyethylphthalimide, followed by the addition of 515 mg of N-benzylmaleimide, 13 mg of 2-hydroxyethyl benzyl trithiocarbonate, and 1.8 mg of azobisisobutyronitrile. The mixture was immediately connected to a vacuum line and degassed by repeating the freeze-degassing method three times. The tube was sealed under reduced pressure and allowed to react at 60°C for 16 hours. The product was then purified by reprecipitation (good solvent: dichloromethane, poor solvent: methanol) to obtain a copolymer. (2) Next, 30 mL of ethanol, 15 mL of dioxane, and 1.0 mL of hydrazine monohydrate were added to 100 mg of the product obtained above, and the mixture was allowed to react at 80°C for 2 hours. The reaction mixture was concentrated, and then a methanol / acetone mixed solvent (1 / 1 (v / v)) was added to precipitate the by-products. The supernatant solution was purified by dialysis (MWCO: 2000) and diluted with 0.6 mol L to bring the pH of the solution to around 4. -1 After adding an aqueous solution of hydrochloric acid, the mixture was freeze-dried to obtain the desired aminated copolymer.

[0092] Test Example 1 The molecular weight and composition ratio (mol %) of the alternating copolymers obtained in Synthesis Examples 1 to 6 were measured. The molecular weight was determined by GPC measurement of the precursor copolymer before amination. The composition ratio was: 1 The results are shown in Table 1. The alternating copolymers obtained in Synthesis Examples 1 to 6 were 1 When the H-NMR spectrum was measured, it was found that the alternation of the structural unit (1) and the structural unit (2) was high. 1 The H-NMR spectra are shown in Figures 1 to 6, respectively.

[0093]

[0094] The results of Test Example 1 revealed that the products obtained in Synthesis Examples 1 to 6 were alternating copolymers.

[0095] Comparative Synthesis Example 1 The same procedure as in Synthesis Example 4(1) was carried out to obtain 2-(vinyloxy)-N,N,N-trimethylethanaminium chloride.

[0096] Comparative Synthesis Example 2 Poly(2-(vinyloxy)-N,N,N-trimethylethanaminium chloride) was synthesized according to the following synthesis route.

[0097]

[0098] That is, 660 mg of water was added to 660 mg of 2-(vinyloxy)-N,N,N-trimethylethanaminium chloride obtained in Comparative Synthesis Example 1, and 6.6 mg of VA-044 (2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride) was further added. The mixture was immediately connected to a vacuum line, and degassed by repeating the freeze-degassing method three times. The tube was sealed under reduced pressure, and the reaction was carried out at 60°C for 8 hours. The product was purified by reprecipitation (good solvent: water, poor solvent: acetone) to obtain the target homopolymer.

[0099] Test Example 2: Antibacterial and Bactericidal Effect (1) The alternating copolymers obtained in Synthesis Examples 1 and 2 and the compound obtained in Comparative Synthesis Example 1 were evaluated for antibacterial and bactericidal activity against Bacillus subtilis by the halo method (0.01 mL of a 10 mg / mL alternating copolymer solution, 100 μg compound weight). Culture was performed at 30°C for 16 hours using YPD agar medium (yeast extract: 1%, peptone: 2%, dextrose: 2%). Those with confirmed inhibition zones were evaluated as having antibacterial and bactericidal effects, and those without inhibition zones were evaluated as having no antibacterial and bactericidal effects. The results are shown in Figure 7. As shown in Figure 7, the alternating copolymers obtained in Synthesis Examples 1 and 2 were confirmed to have antibacterial and bactericidal effects against Bacillus subtilis. On the other hand, the compound obtained in Comparative Synthesis Example 1 did not exhibit antibacterial and bactericidal effects against Bacillus subtilis.

[0100] Test Example 3: Antibacterial and Bactericidal Effect (2) The antibacterial and bactericidal activity against Bacillus subtilis was evaluated for each of the alternating copolymers obtained in Synthesis Examples 2, 5, and 6 using the same halo method as in Test Example 2. The weight of the alternating copolymer used was reduced to 100 μg, 50 μg, 25 μg, 13 μg, 6 μg, 3 μg, 2 μg, 0.8 μg, 0.4 μg, 0.2 μg, and 0.1 μg, and the minimum weight of the sample at which an inhibition zone was observed was evaluated as the minimum active amount. The results are shown in Figure 8. As shown in Figure 8, the minimum active amounts against Bacillus subtilis for the alternating copolymers obtained in Synthesis Examples 2, 5, and 6 were 50 μg, 13 μg, and 0.8 μg, respectively. The antibacterial and bactericidal effect against Bacillus subtilis was confirmed for all of the alternating copolymers obtained in Synthesis Examples 2, 5, and 6. However, the R in the structural unit (2) contained in the alternating copolymer was not significantly affected. 8 However, it was found that the minimum activity amount decreased as the hydrophobicity increased, such as with the ethyl group, hexyl group, and benzyl group.

[0101] Test Example 4: Antibacterial and Bactericidal Effect (3) The alternating copolymers obtained in Synthesis Examples 5 and 6 were evaluated for antibacterial and bactericidal activity against E. coli using the same halo method as in Test Example 2. The weight of the alternating copolymer used was reduced to 100 μg, 50 μg, 25 μg, 13 μg, 6 μg, 3 μg, 2 μg, 0.8 μg, 0.4 μg, 0.2 μg, and 0.1 μg, and the minimum weight of the sample at which an inhibition zone was observed was evaluated as the minimum active amount. The results are shown in Figure 9. As shown in Figure 9, the minimum active amounts against E. coli of the alternating copolymers obtained in Synthesis Examples 5 and 6 were 3 μg and 0.2 μg, respectively. The antibacterial and bactericidal effect against E. coli was confirmed for both the alternating copolymers obtained in Synthesis Examples 5 and 6.

[0102] Test Example 5: Antibacterial and Bactericidal Effects (4) The antibacterial and bactericidal effects were evaluated using the change in turbidity associated with the growth of Bacillus subtilis in liquid culture medium. The procedure is as follows. The following Samples A to G were prepared. Note that the kanamycin used in Sample F is a known compound with antibacterial and bactericidal effects. Sample A (Example): Alternating copolymer obtained in Synthesis Example 1 (Concentration in culture medium: 0.52 mg / mL) Sample B (Comparative Example): Polymer obtained in Comparative Synthesis Example 2 (Concentration in culture medium: 2.1 mg / mL) Sample C (Comparative Example): Polymer obtained in Comparative Synthesis Example 2 (Concentration in culture medium: 0.52 mg / mL) Sample D (Comparative Example): Compound obtained in Comparative Synthesis Example 1 (Concentration in culture medium: 2.1 mg / mL) Sample E (Comparative Example): Compound obtained in Comparative Synthesis Example 1 (Concentration in culture medium: 0.52 mg / mL) Sample F (Comparative Example): Kanamycin (Concentration in culture medium: 0.52 mg / mL) Sample G (Comparative Example): Water

[0103] Next, Bacillus subtilis was cultured at 30°C using YPD liquid medium (yeast extract: 1%, peptone: 2%, dextrose: 2%), and 3 hours after the start of culture, a sample was added dropwise so that the final concentration would be the concentration in the medium. Turbidity was calculated using a spectrophotometer (AS ONE ASV11D-H) immediately after the start of culture, 2 hours after the start of culture, 3 hours after the start of culture (immediately after sample addition), 6 hours after the start of culture (3 hours after the end of sample addition), and 24 hours after the start of culture. The results are shown in Table 2.

[0104]

[0105] As shown in Table 2, the alternating copolymer obtained in Synthesis Example 1 (Sample A) had excellent antibacterial and bactericidal effects. Kanamycin (Sample F) showed no reduction in turbidity even three hours after the end of sample dropwise addition, but the alternating copolymer obtained in Synthesis Example 1 showed a reduction in turbidity three hours after the end of sample dropwise addition. It is believed that the alternating copolymer obtained in Synthesis Example 1 exhibits a bactericidal effect due to membrane destruction. Furthermore, when Samples B to C (homopolymers of structural unit (1)) were used, an increase in turbidity was observed, but when Sample A (alternating copolymer of structural unit (1) and structural unit (2)) was used, a reduction in turbidity was confirmed. From these results, it is believed that the antibacterial and bactericidal effects were significantly enhanced by combining structural unit (2) with structural unit (1).

Claims

1. A copolymer having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): [In formula (1), R 1 represents a substituted or unsubstituted alkanediyl group having 1 to 20 carbon atoms, R 2 is -N + R 3 R 4 R 5 Y - or -NR 6 R 7 (R 3 , R 4 , R 5 , R 6 and R 7 each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; Y - indicates a counter anion). [In formula (2), R 8 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.

2. R 1 The copolymer according to claim 1, wherein is a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms.

3. R 3 , R 4 and R 5 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and R 6 and R 7 and each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms.

4. R 8 The copolymer according to any one of claims 1 to 3, wherein is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.

5. R 8 The copolymer according to any one of claims 1 to 3, wherein is a substituted or unsubstituted hydrocarbon group having 4 to 20 carbon atoms.

6. The copolymer according to any one of claims 1 to 5, which is an alternating copolymer.

7. An antibacterial agent, a bactericide, or an antibacterial and bactericide, which contains the copolymer according to any one of claims 1 to 6 as an active ingredient.

8. The agent according to claim 7, which is for bacteria selected from gram-positive bacteria and gram-negative bacteria.

9. An antibacterial material, a bactericidal material, or an antibacterial and bactericidal material, which contains the copolymer according to any one of claims 1 to 6.

10. The material according to claim 9, which is for bacteria selected from gram-positive and gram-negative bacteria.

11. An antibacterial method, a sterilization method, or an antibacterial and sterilization method, which uses the copolymer according to any one of claims 1 to 6.

12. The method according to claim 11, which is an antibacterial method for bacteria selected from gram-positive bacteria and gram-negative bacteria, a method for sterilizing bacteria selected from gram-positive bacteria and gram-negative bacteria, or a method for antibacterial and sterilizing bacteria selected from gram-positive bacteria and gram-negative bacteria.

13. A method for producing the copolymer according to any one of claims 1 to 6, comprising a polymerization step of polymerizing a monomer represented by the following formula (M1) and a monomer represented by the following formula (M2): [In formula (M1), X 1 represents a protected amino group, a halogen atom, -N + R 3 R 4 R 5 Y - or -NR 6 R 7 (R 3 , R 4 , R 5 , R 6 , R 7 and Y - has the same meaning as above), R 1 has the same meaning as above.] [In formula (M2), R 8 has the same meaning as above.] 14. X 1 is a halogen atom, and the method for producing a polymer according to claim 13 further comprises an amination or quaternary ammonium conversion step of amminating or quaternizing the polymer obtained in the polymerization step.

15. X 1 is a protected amino group, and the method for producing the compound according to claim 13 further comprises a deprotection step of deprotecting the polymer obtained in the polymerization step.

16. The copolymer according to any one of claims 1 to 6, which is used for antibacterial, bactericidal, or both antibacterial and bactericidal purposes.

17. The copolymer according to any one of claims 1 to 6 for producing an antibacterial agent, a bactericide, an antibacterial and bactericidal agent, an antibacterial material, a bactericidal material, or an antibacterial and bactericidal material.

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