WO2016013370A1 - Antibacterial agent, sterilizing agent, antibacterial material, sterilizing material, antibacterial method, and sterilization method - Google Patents

Abstract

In order to provide an antibacterial and/or sterilizing agent having excellent antibacterial properties and sterilizing properties even at low concentration, the present invention provides an antibacterial agent, sterilizing agent, or antibacterial and sterilizing agent having a repeat unit represented by formula (1) and a repeat unit represented by formula (2), and having as an active component a copolymer having an Mw (Mw denoting weight average molecular weight in terms of polystyrene, measured by gel permeation chromatography, wherein the mobile phase in the gel permeation chromatography is tetrahydrofuran.) of 3,000 or less. [In formula (1), R¹ represents a hydrogen atom or methyl group, Z represents a group forming an organic ammonium salt, -NR⁵R⁶ (R⁵ and R⁶ each independently representing hydrogen atoms, or substituted or unsubstituted hydrocarbon groups.), or substituted or unsubstituted nitrogen-containing heterocyclic groups, and X represents a single-bond or divalent linking group.] [In formula (2), R⁷ represents a hydrogen atom or methyl group, and A represents an aromatic hydrocarbon group, -(C=O)OR⁸, -(C=O)NHR⁹, or -OR¹⁰ (R⁸-R¹⁰ representing a hydrocarbon group or a group having a chain or cyclic ether structure.)]

Description

Antibacterial agent, bactericidal agent, antibacterial material, bactericidal material, antibacterial method and bactericidal method

The present invention relates to an antibacterial agent, a bactericidal agent, an antibacterial material, a bactericidal material, an antibacterial method, a bactericidal method, and the like.

Antibacterial agents and bactericides are used in various fields such as daily necessities and medical supplies. For example, it is used for coating materials for medical and sanitary products, cleaning compositions for clothing and contact lenses, disinfectants and interior paints in food factories and hospitals. In addition, materials such as fibers, plastics and films imparted with antibacterial and bactericidal properties by blending antibacterial agents and bactericides are also widely used.

As an antibacterial and bactericidal polymer constituting such an antibacterial agent and bactericidal agent, for example, a cationic polymer proposed in Patent Document 1 is known.

Special table 2003-509546 gazette

However, the conventional cationic polymer has a problem that the antibacterial property and the bactericidal property are lowered at a low concentration.
Accordingly, an object of the present invention is to provide an antibacterial and / or bactericidal agent having excellent antibacterial and bactericidal properties even at low concentrations.

In view of such circumstances, the present inventors have conducted extensive research and found that the above-mentioned problems can be solved by using a specific vinyl copolymer, thereby completing the present invention.

That is, the present invention provides the following <1> to <7>.
<1> Antibacterial agent, bactericidal agent, or antibacterial and bactericidal agent (hereinafter collectively referred to as “antibacterial and / or bactericidal agent”), and a repeating unit represented by the following formula (1) (hereinafter, And a repeating unit represented by the following formula (2) (hereinafter also referred to as “repeating unit (2)”), and Mw (where Mw is gel permeation) This means a polystyrene-equivalent weight average molecular weight measured by chromatography, and the mobile phase in the gel permeation chromatography is tetrahydrofuran (hereinafter referred to as “specific copolymer”) of 3,000 or less. .)) As an active ingredient.

[In the formula (1), R ¹ represents a hydrogen atom or a methyl group, Z represents a group forming an organic ammonium salt, —NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently of each other; Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group), or a substituted or unsubstituted nitrogen-containing heterocyclic group, and X represents a single bond or a divalent linking group. ]

[In the formula (2), R ⁷ represents a hydrogen atom or a methyl group, and A represents an aromatic hydrocarbon group, — (C═O) OR ⁸ , — (C═O) NHR ⁹ , or —OR ^10. (Wherein R ⁸ to R ¹⁰ represent a hydrocarbon group or a group having a chain or cyclic ether structure). ]

<2> Antibacterial material, sterilizing material, or antibacterial and sterilizing material (hereinafter collectively referred to as “antibacterial and / or sterilizing material”), and a material containing the specific copolymer.

<3> Antibacterial method, sterilization method, or antibacterial and sterilization method (hereinafter collectively referred to as “antibacterial and / or sterilization method”), which uses the specific copolymer.

<4> Specific copolymer.

<5> Specific copolymer used for antibacterial, sterilization, or antibacterial and sterilization (hereinafter collectively referred to as “antibacterial and / or sterilization”).

<6> Use of a specific copolymer to produce an antibacterial agent, bactericidal agent, or antibacterial and bactericidal agent.

<7> Use of a specific copolymer for the production of antibacterial materials, sterilizing materials, or antibacterial and sterilizing materials.

The antibacterial and / or bactericidal agent of the present invention has an effect of suppressing the growth of bacteria against both gram-positive bacteria and gram-negative bacteria even at low concentrations. Therefore, the antibacterial and / or bactericidal agent of the present invention can be applied to a wide range of uses.

Hereinafter, the present invention will be described in detail.
Specific copolymer The specific copolymer of the present invention is a copolymer having a repeating unit (1) and a repeating unit (2) and having an Mw of 3,000 or less.

(Repeating unit (1))
The repeating unit (1) is represented by the above formula (1).
In the above formula (1), Z represents a group forming an organic ammonium salt, —NR ⁵ R ^6, or a substituted or unsubstituted nitrogen-containing heterocyclic group. Examples of the group capable of forming the organic ammonium salts, for example ^{-N + R 2 R 3 R 4} Y -, - (C = O) O - N + HR 2 R 3 R 4, - (C = O) O - A ⁺ , —OP (═O) (— O ⁻ ) OC ₂ H ₄ N ⁺ R ² R ³ R ⁴ (wherein R ² to R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted carbon Represents a hydrogen group, Y ⁻ represents a counter anion, and A ⁺ represents a quaternary ammonium cation.), Etc., and —N ⁺ R ² R ³ R ⁴ Y ⁻ is preferred.
R ² to R ⁶ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Here, in the present invention, the “hydrocarbon group” is a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and is any of linear, branched, and cyclic It may be in the form, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may have an unsaturated bond in the molecule or at the terminal.

The aliphatic hydrocarbon group is preferably an alkyl group having 1 to 20 (preferably 1 to 12) carbon atoms. 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, and a tert-butyl group. The alicyclic hydrocarbon is preferably an alicyclic hydrocarbon group having 3 to 20 (preferably 3 to 12) carbon atoms, and a cycloalkyl group having 3 to 20 (preferably 3 to 12) carbon atoms. More preferred. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Further, the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 (preferably 6 to 10) carbon atoms, an aryl group having 6 to 20 (preferably 6 to 10) carbon atoms, An aralkyl group having 7 to 20 (preferably 7 to 16 carbon atoms) is more preferable. Here, the “aryl group” in the present invention means a monocyclic to tricyclic aromatic hydrocarbon group, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group, and an anthranyl group. Specific examples of the aralkyl group include benzyl group, phenethyl group, α-methylbenzyl group, 2-phenylpropan-2-yl group and the like.
Among these, as the hydrocarbon group for R ² to R ⁶ , an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 6 and particularly preferably 1 to 4), carbon atoms from the viewpoint of antibacterial and bactericidal properties. Aralkyl groups of 7 to 16 (more preferably 7 to 12, particularly preferably 7 to 9) are preferred, and are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl. A group, a tert-butyl group and a benzyl group are particularly preferred.
Examples of the substituent in R ² to R ⁶ include alkyl groups having 1 to 6 carbon atoms, halogen atoms, hydroxyl groups, benzoyl groups, substituted or unsubstituted amino groups, nitro groups, cyano groups, carboxyl groups, and carbon atoms. Examples of the alkoxy group include 1 to 6.

Examples of Y ⁻ include halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ , and counter-anions of acids such as ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ (C═O) O ⁻ and PF ₆ ⁻ .

In the present invention, the “nitrogen-containing heterocyclic group” refers to a heterocyclic group having at least one nitrogen atom as a ring component, and a heterocyclic monocyclic group or a condensed heterocyclic group formed by condensing two of these. A cyclic group is preferred. These heterocyclic groups may be an unsaturated ring or a saturated ring, and may have a hetero atom (for example, an oxygen atom or a sulfur atom) other than a nitrogen atom in the ring.
Examples of the unsaturated heterocycle include a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a triazole ring, a tetrazole ring, an imidazoline ring, and a tetrahydropyrimidine ring. Examples of the saturated heterocyclic ring include a morpholine ring, piperidine ring, piperazine ring, and pyrrolidine ring. Examples of the substituent in the nitrogen-containing heterocyclic group include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a carboxyl group, an ester group, an ether group, a hydroxyl group, an amino group, an amide group, a thiol group, and a thioether group. Is mentioned.

The heteromonocyclic group is preferably a 5- to 7-membered ring, and specific examples include groups having a basic skeleton represented by the following formula (1-1) or (1-2). The monocyclic group may have a substituent.

In the formula (1-1), R represents a hydrogen atom or an optionally substituted hydrocarbon group, Y ⁻ represents a counter anion, and “*” represents a bond, as the hydrocarbon group for R are the same as in the above R ^2, Y ^- Y in ^{- -} that similar to the are mentioned above ^{-N + R 2 R 3 R 4} Y as.

In formula (1-2), “*” indicates a bond.

Specific examples of the fused heterocyclic group include groups having a basic skeleton represented by the following formulas (1-3) to (1-5). These fused heterocyclic groups have a substituent. You may do it.

In formulas (1-3) to (1-5), “*” indicates a bond.

In the above formula (1), examples of the divalent linking group represented by X include a methylene group, an alkylene group, an arylene group, — (C═O) OR ¹¹ — (*), — (C═O) NHR. ¹² -(*), or -ArR ¹³ -(*) (wherein Ar represents an arylene group, and "*" represents a bond bonded to Z). Examples of the “arylene group” in the present invention include a phenylene group, a naphthylene group, a phenanthrenylene group and the like. R ¹¹ to R ¹³ are each independently a methylene group, an alkylene group, or an alkyleneoxyalkylene group.

The alkylene group represented by X and R ¹¹ to R ¹³ is preferably an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms). The alkylene group may be linear or branched, and specific examples include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
The alkylene group contained in the alkyleneoxyalkylene group is preferably the same as the above alkylene group. The alkyleneoxy alkylene group is preferably a C _2-4 alkyleneoxy C _2-4 alkylene group, specifically include such as ethylene oxyethylene group.

X is — (C═O) OR ¹¹ — (*), — (C═O) NHR ¹² — (*), or —ArR ¹³ — ((), from the viewpoint of ease of production of the specific copolymer. *) Is preferred, and — (C═O) OR ¹¹ — (*) is particularly preferred. R ¹¹ to R ¹³ are particularly preferably an alkylene group having 2 to 6 carbon atoms (more preferably 2 to 4 carbon atoms).

(Repeating unit (2))
The repeating unit (2) is represented by the above formula (2).
In A of the above formula (2), the aromatic hydrocarbon group is preferably an aryl group having 6 to 20 (preferably 6 to 10) carbon atoms, and particularly preferably a phenyl group.
In A of the above formula (2), R ⁸ to R ¹⁰ represent a hydrocarbon group or a group having a chain or cyclic ether structure. Examples of the hydrocarbon group include those similar to R ² above, and alicyclic carbon groups such as a saturated condensed polycyclic hydrocarbon group, a saturated bridged ring hydrocarbon group, a saturated spiro hydrocarbon group, and a saturated cyclic terpene hydrocarbon group. A hydrogen group is mentioned. Examples of the hydrocarbon group of R ⁸ to R ¹⁰ include an alkyl group having 1 to 20 carbon atoms (preferably 1 to 15), an aryl group having 6 to 20 carbon atoms (preferably 6 to 14 carbon atoms), and 7 to 20 carbon atoms ( An aralkyl group having 7 to 16 carbon atoms and an alicyclic hydrocarbon group having 3 to 20 carbon atoms (preferably 4 to 15 carbon atoms) are preferable, and a methyl group, ethyl group, n-propyl group, isopropyl group, n- Butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, isodecyl group, dodecyl group, phenyl group, benzyl group, phenylethyl group, cyclohexyl group, cyclohexenyl group, t-butylcyclohexyl group, decahydro-2-naphthyl group, a tricyclo [5.2.1.0 ^2,6] decan-8-yl group, an adamantyl group, a dicyclopentenyl group, penta cyclopentadiene Kaniru group, tri cyclopentenyl group, isobornyl group particularly preferred.

On the other hand, the group having a chain ether structure in R ⁸ to R ¹⁰ is preferably a group represented by the following formula (3).

[In the formula (3), R ¹⁴ independently of each other represents an alkylene group having 2 to 4 carbon atoms, and R ¹⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group. N represents an integer of 2 to 150, and “*” represents a bond. ]

R ¹⁴ may be composed of two or more alkylene groups, and is preferably an ethylene group and / or a propylene group.
As the alkyl group having 1 to 6 carbon atoms in R ¹⁵ , an alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable. The alkyl group may be linear or branched, and examples thereof 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, and a tert-butyl group.
The aryl group for R ¹⁵ is preferably a phenyl group. The aryl group may be substituted with an α-cumyl group or the like.
R ¹⁵ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
n is preferably an integer of 2 to 20, more preferably an integer of 2 to 10, and particularly preferably an integer of 2 to 5.

Further, the group having a cyclic ether structure in R ⁸ to R ¹⁰ is preferably a group represented by the following formula (4).

[In the formula (4), R ¹⁶ represents a methylene group or an alkylene group having 2 to 12 carbon atoms, CE represents a cyclic ether group which may have an alkyl group as a substituent, and “*” represents a bond. Indicates that ]

In the above formula (4), R ¹⁶ is preferably a methylene group or an alkylene group having 1 to 6 carbon atoms. The alkylene group may be linear or branched. Specific examples of R ¹⁶ include methylene group, ethylene group, ethane-1,1-diyl group, trimethylene group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2, Examples thereof include a 2-diyl group, a tetramethylene group, a butane-1,2-diyl group, a butane-1,3-diyl group, a pentamethylene group, and a hexamethylene group.

In the above formula (4), CE is preferably a cyclic ether group having 3 to 7 atoms constituting the ring, and specific examples thereof are represented by the following formulas (i) to (viii). And cyclic ether groups.

[In the formulas (i) to (viii), “*” represents a bond that bonds to R ¹⁶ . ]

In the present invention, R ⁸ to R ¹⁰ are preferably hydrocarbon groups from the viewpoint of the effect of suppressing the growth of bacteria.

The specific copolymer may have a repeating unit other than the above. Examples of such repeating units include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p Vinyl monomers having acidic groups such as vinylbenzoic acid, p-hydroxystyrene, p-hydroxy-α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; 2-hydroxy (Meth) acrylic acid ester having a hydroxyl group such as ethyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate; (meth) acrylamide type single unit such as (meth) acrylamide and N-methylolacrylamide Repetitive unit derived from a mer Rank. Here, in the present invention, “(meth) acrylate” means “acrylate or methacrylate”.

In the specific copolymer, the copolymerization ratio of the repeating unit (1) is preferably 10 to 99% by mass, more preferably 15 to 95% by mass, and particularly preferably 20 to 90% by mass in all the repeating units. The copolymerization ratio of the repeating unit (2) is preferably 1 to 80% by mass, more preferably 5 to 75% by mass, and particularly preferably 10 to 70% by mass in all the repeating units. By copolymerizing each repeating unit at such a ratio, the desired effect can be further enhanced. Further, the mass ratio [(1) / (2)] of the copolymerization ratio of the repeating unit (1) and the copolymerization ratio of the repeating unit (2) is preferably 15/85 to 99/1, and 20/80 ~ 95/5 is more preferable, and 30/70 to 90/10 is particularly preferable.
The copolymerization ratio and copolymerization ratio can be measured by ¹³ C-NMR or the like.

The specific copolymer may have one or more of those corresponding to the repeating unit (1), and may have one or more of those corresponding to the repeating unit (2). Good. The repeating unit (1) is preferably a repeating unit in which Z is a group that forms an organic ammonium salt, preferably 20 mol% or more, more preferably 30 mol% or more, and particularly preferably, from the viewpoint of enhancing a desired effect. It is preferable to contain 50 mol% or more (In addition, the upper limit of this content is although it does not specifically limit, For example, it is 100 mol%, Preferably it is 99.9 mol%.). When Z includes both a repeating unit which is a group forming an organic ammonium salt and a repeating unit where Z is —NR ⁵ R ⁶ , Z is a repeating unit which is a group forming an organic ammonium salt; The copolymerization ratio (molar ratio) with the repeating unit of NR ⁵ R ⁶ is preferably 20/80 to 99/1, more preferably 30/70 to 98/2, and particularly preferably 50/50 to 98/2.

The specific copolymer may be either a block copolymer or a random copolymer as long as it has the repeating unit (1) and the repeating unit (2). From the viewpoint of enhancing, a random copolymer is preferable. Also, a block copolymer comprising an A block having no repeating unit (2) and having a repeating unit (1) and a B block having no repeating unit (1) and having a repeating unit (2) In some cases, functions other than sterilization / antibacterial can be imparted. The block copolymer is preferably an AB type block copolymer.

In the A block, the repeating unit (1) may be contained in two or more kinds in one A block. In that case, each repeating unit is randomly copolymerized or block copolymerized in the A block. It may be contained in any aspect. In the present invention, the A block contains, as the repeating unit (1), only the repeating unit (1) in which Z is a group that forms an organic ammonium salt, or Z is a group that forms an organic ammonium salt. It is preferable that both the repeating unit (1) and the repeating unit (1) in which Z is —NR ⁵ R ⁶ are contained.

On the other hand, in the B block, two or more kinds of repeating units (2) may be contained in one B block. In this case, each repeating unit is randomly copolymerized and block copolymerized in the B block. It may be contained in any mode of polymerization.

The molecular weight of the specific copolymer is such that the polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography (GPC, mobile phase: tetrahydrofuran) is 3,000 or less, preferably 300 to 3,000, particularly preferably. Is 500 to 2,500. The ratio (Mw / Mn) of Mw of the specific copolymer and the number average molecular weight Mn in terms of polystyrene measured by GPC (mobile phase: tetrahydrofuran) is preferably 1.0 to 1.8, more preferably 1.0 to 1.7, particularly preferably 1.0 to 1.5. By making the specific copolymer into such an embodiment, a desired effect can be enhanced.

The specific copolymer can be produced by a known method, but it is preferably produced by living polymerization of the monomer that gives each repeating unit. As the living polymerization method, known methods such as living radical polymerization and living anion polymerization can be employed.

Examples of the monomer that gives the repeating unit (1) and in which Z in the formula (1) is a group that forms an organic ammonium salt or —NR ⁵ R ⁶ include, for example, (meth) acryloylaminopropyl Trimethylammonium chloride, (meth) acryloyloxyethyl trimethylammonium chloride, (meth) acryloyloxyethyl triethylammonium chloride, (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride , (Meth) acryloyloxyethylbenzyl diethylammonium chloride, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethyla Nopuropiru (meth) acrylate, containing ammonium salt type cationic functional group or an amino group such as diethylaminopropyl (meth) acrylate (meth) acrylic acid esters and, these corresponding (meth) acrylamide. The repeating unit (1) in which Z is a group that forms an organic ammonium salt is obtained by, for example, copolymerizing a monomer in which Z is —NR ⁵ R ⁶ (for example, dimethylaminoethyl (meth) acrylate). The copolymer can also be obtained by reacting a halogenated hydrocarbon compound such as benzyl chloride to quaternize the amino group.

Examples of the monomer that gives the repeating unit (1) and in which Z in the formula (1) is a nitrogen-containing heterocyclic group include, for example, a compound group α (monomer 1 to 18) represented by the following formula: , Compounds represented by the following formula (5), 4-vinylpyridine, and salts thereof. In addition, the monomer which gives repeating unit (1) can be used individually or in combination of 2 or more types.

Examples of the monomer that gives the repeating unit (2) include styrene and α-methylstyrene as the monomer that gives the repeating unit (2) in which A is an aromatic hydrocarbon group. Examples of the monomer that gives the repeating unit (2) in which R ⁸ to R ¹⁰ are hydrocarbon groups include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate. , Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butyl Cyclohexyl (meth) acrylate, cyclohexenyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, Adama (Meth) acrylic acid esters such as chill (meth) acrylate, decahydro-2-naphthyl (meth) acrylate, pentacyclopentadecanyl (meth) acrylate; corresponding (meth) acrylamides; vinyl ethers such as ethyl vinyl ether Kind. Further, as a monomer that gives the repeating unit (2) in which R ⁸ to R ¹⁰ are groups having a chain or cyclic ether structure, polyethylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polypropylene Glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) ethyl ether (meth) acrylate, polypropylene glycol (n = 2 to 10) ethyl ether (meth) acrylate, Polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl ( )) Acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, tetrahydrofurfuryl (meth) acrylate, etc. (Meth) acrylic acid esters; (meth) acrylamides corresponding to these; vinyl ethers such as 3- (vinyloxymethyl) -3-ethyloxetane. These can be used alone or in combination of two or more.

Examples of the monomer that gives a repeating unit other than the repeating unit (1) and the repeating unit (2) include (meth) acrylic acid, maleic acid, maleic anhydride, and succinic acid mono [2- (meth) acrylic acid. Vinyl monomers having acidic groups such as leuoxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylbenzoic acid, p-hydroxystyrene, p-hydroxy-α-methylstyrene; N-phenyl N-substituted maleimides such as maleimide and N-cyclohexylmaleimide; (meth) acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate and 4-hydroxyphenyl (meth) acrylate; (Meth) acrylamide, N-methylol acrylic And (meth) acrylamide monomers such as imide. These can be used alone or in combination of two or more.

And even if a specific copolymer is a low density | concentration, it is excellent in antibacterial property and bactericidal property. It also has water solubility.
Therefore, the specific copolymer can be used as an antibacterial and / or bactericidal agent, and an antibacterial and / or bactericidal material as it is or in combination with other components.

Antibacterial and / or bactericidal agent The antibacterial and / or bactericidal agent of the present invention comprises a specific copolymer as an active ingredient.
The antibacterial and / or bactericidal agent of the present invention is excellent in antibacterial and bactericidal properties even at low concentrations. The antibacterial and / or bactericidal agent of the present invention is particularly useful for suppressing the growth of bacteria.
Examples of bacteria include gram positive bacteria, gram negative bacteria, and the like, and both gram positive bacteria and gram negative bacteria can be antibacterial and sterilized.
Examples of the Gram-positive bacteria include staphylococci such as Staphylococcus aureus, Listeria bacteria, Bacillus bacteria, and Alicyclobacillus bacteria. Examples of Gram-negative bacteria include Escherichia bacteria such as Escherichia coli, Salmonella bacteria, Vibrio bacteria, and Pseudomonas bacteria.

Antibacterial and / or sterilizing material The antibacterial and / or sterilizing material of the present invention contains a specific copolymer, and the specific copolymer is used in combination with other components to form a solution, dispersion, gel, capsule, It is a material in an arbitrary form such as a pellet, a film, a sheet, or a fiber.

For example, the specific copolymer is a solvent such as water or an organic solvent; a surfactant such as anionic, cationic or nonionic; a thickener such as gelatin, polysaccharide or cellulose; a polyfunctional acrylate or a polyfunctional epoxy compound. By using in combination with a curable monomer or the like, a coating material for antibacterial and / or sterilization can be obtained. Such coating materials include, for example, coating materials for medical equipment such as medical equipment and medical equipment; coating materials for daily goods such as toilet goods and kitchen goods; interior paints in hospitals, elderly facilities, food factories, etc., and hulls and touches. It can be used as a coating material for screen panels.

In addition, specific copolymers can be blended with organic polymer materials such as polyolefin, polyurethane, ABS, polystyrene, polycarbonate, polyester, polyamide, acrylic polymer, vinyl chloride, silicone, cellulose, etc. Plastics, films, fibers, rubbers, ceramics, glass, etc. that have been given antibacterial and / or bactericidal properties by surface treatment with molded materials manufactured from inorganic materials such as materials, metals, and ceramics Can be a material. Such materials include, for example, medical supplies such as masks, surgical clothes, surgical coverings, blood bags, wound dressings; daily items such as bed sheets, towels, trash cans, and triangular corners; smartphones, tablet terminals, car navigation systems, etc. It can be used for touch panel devices. It can also be used as a packaging material for building materials such as wallpaper and tiles; food and medical equipment.

Antibacterial and / or sterilization method The antibacterial and / or sterilization method of the present invention uses a specific copolymer.
Although the method is not particularly limited, for example, there is a method including a step of applying a liquid composition containing a specific copolymer and a solvent to the surface of the object, thereby antibacterial the object. And / or bactericidal properties can be imparted. At this time, in addition to the solvent, a surfactant, a thickener, a curable monomer, and the like can be blended with the liquid composition containing the specific copolymer. As the application means, usual application means such as spray coating, coater coating, dipping, brush coating, roll coating and the like can be employed. Examples of the object include base materials such as films, resin substrates, fibers, ceramics, metals, glass, and wood; interiors such as walls, floors, and ceilings; medical treatments such as catheters, infusion tubes, blood bags, and dressing materials. Appliances: Tableware such as tableware or kitchen appliances.

In addition, by applying a liquid composition containing the specific copolymer to a target using a spray or the like, the target is given antibacterial and / or bactericidal properties, or the target is sterilized. You can also. At this time, in addition to the solvent, a surfactant, a fragrance and the like can be blended with the liquid composition containing the specific copolymer.

Further, in addition to washing the object, antibacterial and / or sterilization can also be performed by a method including a step of washing the object using a cleaning agent containing the specific copolymer. At this time, the form of the cleaning agent is not particularly limited and may be solid or liquid. Moreover, surfactant, a fragrance | flavor, etc. other than a solvent can be mix | blended with a cleaning agent similarly to the above.

Further, the object can be sterilized and disinfected by a method including a step of immersing the object such as a contact lens in the liquid composition containing the specific copolymer. The object can be sterilized and disinfected by a method comprising a step of impregnating a nonwoven fabric with a liquid composition containing the specific copolymer and wiping the object. At this time, in addition to the solvent, a surfactant, a fragrance, an enzyme, a buffer solution, and the like can be blended with the liquid composition containing the specific copolymer.

Further, by a method including a step of blending the specific copolymer with an organic polymer material, it can be made into a material such as plastic, film, fiber, rubber or the like imparted with antibacterial and / or bactericidal properties.

Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

The abbreviations of the raw materials used below are as follows.
THF: Tetrahydrofuran nBMA: Normal butyl methacrylate MMA: Methyl methacrylate THFMA: Tetrahydrofurfuryl methacrylate EHMA: 2-ethylhexyl methacrylate DAMA: Dimethylaminoethyl methacrylate PME-200: Methoxypolyethylene glycol monomethacrylate (trade name PME, manufactured by NOF Corporation) -200, n≈4)
PGMEA: Propylene glycol monomethyl ether acetate

<Synthesis of specific copolymer>
Synthesis example 1
125 mL of THF and 2.62 g of lithium chloride were added to a 300 mL flask and cooled to −60 ° C. 15 mL of n-butyllithium hexane solution (concentration 1.6 mol / L) was added, and after stirring for 5 minutes, diphenylethylene (4.3 g) was added and stirred for 15 minutes. A mixed solution of MMA 10 g, nBMA 7.5 g, and EHMA 10 g was added dropwise, and the reaction was continued for 15 minutes. Gas chromatography (hereinafter abbreviated as GC) was measured to confirm the disappearance of the monomer. Next, 22.5 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MMA, nBMA, and EHMA was obtained.
Next, 7.3 g of benzyl chloride and 25.0 g of propylene glycol monomethyl ether were added to the obtained block copolymer solution, and then gently stirred to raise the temperature of the block copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, a block copolymer comprising an A block having a DAMA-derived repeating unit, a part of which was quaternary ammoniumated, and a B block having a repeating unit derived from MMA, nBMA and EHMA was obtained. . The resulting copolymer is referred to as “copolymer (P-1)”.

Synthesis example 2
125 mL of THF and 2.62 g of lithium chloride were added to a 300 mL flask and cooled to −60 ° C. 15 mL of n-butyllithium hexane solution (concentration 1.6 mol / L) was added, and after stirring for 5 minutes, diphenylethylene (4.3 g) was added and stirred for 15 minutes. A mixed solution of MMA 10 g and nBMA 7.5 g was dropped, and the reaction was continued for 15 minutes. GC was measured to confirm the disappearance of the monomer. Next, 10 g of EHMA was added dropwise, and the reaction was continued for 15 minutes after the addition. GC was measured to confirm the disappearance of the monomer. Next, 22.5 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, B1 block which has a repeating unit derived from EHMA, and B2 block which has a repeating unit derived from MMA and nBMA was obtained.
Next, 7.3 g of benzyl chloride and 25.0 g of propylene glycol monomethyl ether were added to the obtained block copolymer solution, and then gently stirred to raise the temperature of the block copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, the A block having a DAMA-derived repeating unit, a part of which is quaternary ammoniumated, a B1 block having a repeating unit derived from EHMA, and a B2 block having a repeating unit derived from MMA and nBMA A block copolymer was obtained. The resulting copolymer is referred to as “copolymer (P-2)”.

Synthesis example 3
125 mL of THF and 2.62 g of lithium chloride were added to a 300 mL flask and cooled to −60 ° C. 15 mL of n-butyllithium hexane solution (concentration 1.6 mol / L) was added, and after stirring for 5 minutes, diphenylethylene (4.3 g) was added and stirred for 15 minutes. A mixed solution of MMA 10 g and nBMA 7.5 g was dropped, and the reaction was continued for 15 minutes. GC was measured to confirm the disappearance of the monomer. Next, 10 g of EHMA was added dropwise, and the reaction was continued for 15 minutes after the addition. GC was measured to confirm the disappearance of the monomer. Next, 22.5 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, B1 block which has a repeating unit derived from EHMA, and B2 block which has a repeating unit derived from MMA and nBMA was obtained.
Next, 14.6 g of benzyl chloride and 25.0 g of propylene glycol monomethyl ether were added to the obtained block copolymer solution, and then gently stirred to raise the temperature of the block copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, the A block having a DAMA-derived repeating unit, a part of which is quaternary ammoniumated, a B1 block having a repeating unit derived from EHMA, and a B2 block having a repeating unit derived from MMA and nBMA A block copolymer was obtained. The resulting copolymer is referred to as “copolymer (P-3)”.

Synthesis example 4
125 mL of THF and 2.62 g of lithium chloride were added to a 300 mL flask and cooled to −60 ° C. 15 mL of n-butyllithium hexane solution (concentration 1.6 mol / L) was added, and after stirring for 5 minutes, diphenylethylene (4.3 g) was added and stirred for 15 minutes. A mixed solution of MMA 10 g, nBMA 7.5 g, EHMA 10 g, and DAMA 22.5 g was added dropwise, and the reaction was continued for 30 minutes. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. In this way, a random copolymer having repeating units derived from DAMA, MMA, nBMA and EHMA was obtained.
Next, 7.3 g of benzyl chloride and 25.0 g of propylene glycol monomethyl ether were added to the obtained random copolymer solution, and then gently stirred to raise the temperature of the random copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, a random copolymer having DAMA, MMA, nBMA and EHMA-derived repeating units, and a part of the DAMA-derived repeating units being quaternized ammonium was obtained. The resulting copolymer is referred to as “copolymer (P-4)”.

Synthesis example 5
125 mL of THF and 2.62 g of lithium chloride were added to a 300 mL flask and cooled to −60 ° C. 15 mL of n-butyllithium hexane solution (concentration 1.6 mol / L) was added, and after stirring for 5 minutes, diphenylethylene (4.3 g) was added and stirred for 15 minutes. A mixed solution of MMA 7.5 g and nBMA 5 g was dropped, and the reaction was continued for 15 minutes. GC was measured to confirm the disappearance of the monomer. Next, 7.5 g of EHMA was added dropwise, and the reaction was continued for 15 minutes after the addition. GC was measured to confirm the disappearance of the monomer. Next, 30 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, B1 block which has a repeating unit derived from EHMA, and B2 block which has a repeating unit derived from MMA and nBMA was obtained.
Next, 9.8 g of benzyl chloride and 30.0 g of propylene glycol monomethyl ether were added to the obtained block copolymer solution, and then gently stirred to raise the temperature of the block copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, the A block having a DAMA-derived repeating unit, a part of which is quaternary ammoniumated, a B1 block having a repeating unit derived from EHMA, and a B2 block having a repeating unit derived from MMA and nBMA A block copolymer was obtained. The resulting copolymer is referred to as “copolymer (P-5)”.

Synthesis Example 6
125 mL of THF and 2.62 g of lithium chloride were added to a 300 mL flask and cooled to −60 ° C. 15 mL of n-butyllithium hexane solution (concentration 1.6 mol / L) was added, and after stirring for 5 minutes, diphenylethylene (4.3 g) was added and stirred for 15 minutes. 10 g of EHMA was added dropwise, and the reaction was continued for 15 minutes after the addition. GC was measured to confirm the disappearance of the monomer. Next, a mixed solution of 10 g of MMA and 7.5 g of nBMA was dropped, and the reaction was continued for 15 minutes. GC was measured to confirm the disappearance of the monomer. Next, 22.5 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, B1 block which has a repeating unit derived from MMA and nBMA, and B2 block which has a repeating unit derived from EHMA was obtained.
Next, 7.3 g of benzyl chloride and 25.0 g of propylene glycol monomethyl ether were added to the obtained block copolymer solution, and then gently stirred to raise the temperature of the block copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, A block having a DAMA-derived repeating unit, a part of which is quaternary ammonium-modified, a B1 block having a repeating unit derived from MMA and nBMA, and a B2 block having a repeating unit derived from EHMA A block copolymer was obtained. The resulting copolymer is referred to as “copolymer (P-6)”.

Synthesis example 7
125 mL of THF and 2.62 g of lithium chloride were added to a 300 mL flask and cooled to −60 ° C. 15 mL of n-butyllithium hexane solution (concentration 1.6 mol / L) was added, and after stirring for 5 minutes, diphenylethylene (4.3 g) was added and stirred for 15 minutes. A solution in which 11.5 g of MMA, 7.5 g of THFMA, and 8.5 g of PME-200 were mixed was dropped, and the reaction was continued for 15 minutes. GC was measured to confirm the disappearance of the monomer. Next, 22.5 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, a block copolymer comprising an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from MMA, THFMA and PME-200 was obtained.
Next, 7.3 g of benzyl chloride and 25.0 g of propylene glycol monomethyl ether were added to the obtained block copolymer solution, and then gently stirred to raise the temperature of the block copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. Thus, a block copolymer comprising an A block having a DAMA-derived repeating unit, a part of which is quaternary ammoniumated, and a B block having a repeating unit derived from MMA, THFMA and PME-200. Obtained. The resulting copolymer is referred to as “copolymer (P-7)”.

Synthesis Example 8
125 mL of THF, 1.31 g of lithium chloride, and 3.0 g of diisopropylamine were added to a 300 mL flask and cooled to −60 ° C. Thereafter, 18.8 mL of n-butyllithium hexane solution (concentration 1.6 mol / L) was added and stirred for 15 minutes, and then methyl isobutyrate (3.1 g) was added and stirred for 15 minutes. A mixed solution of MMA 7.5 g, nBMA 5.0 g, EHMA 7.5 g, and DAMA 30.0 g was dropped, and the reaction was continued for 30 minutes. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. In this way, a random copolymer having repeating units derived from DAMA, MMA, nBMA and EHMA was obtained.
Next, 19.3 g of benzyl chloride and 30.0 g of propylene glycol monomethyl ether were added to the obtained random copolymer solution, and then gently stirred to raise the temperature of the random copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, a random copolymer having DAMA, MMA, nBMA and EHMA-derived repeating units, and a part of the DAMA-derived repeating units being quaternized ammonium was obtained. The resulting copolymer is referred to as “copolymer (P-8)”.

Synthesis Example 9
125 mL of THF, 1.7 g of lithium chloride, and 25 mL of n-butyllithium hexane solution (concentration: 1.6 mol / L) were added to a 300 mL flask and cooled to −60 ° C. After stirring for 15 minutes, 4.1 g of diisopropylamine was added, and after stirring for 15 minutes, methyl isobutyrate (4.1 g) was added and stirred for 15 minutes. A mixed solution of MMA 5.5 g, nBMA 4.0 g, EHMA 5.5 g, and DAMA 35.0 g was added dropwise, and the reaction was continued for 30 minutes. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. In this way, a random copolymer having repeating units derived from DAMA, MMA, nBMA and EHMA was obtained.
Next, 25.4 g of benzyl chloride and 30.0 g of propylene glycol monomethyl ether were added to the obtained random copolymer solution, and then gently stirred to raise the temperature of the random copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, a random copolymer having DAMA, MMA, nBMA and EHMA-derived repeating units, and a part of the DAMA-derived repeating units being quaternized ammonium was obtained. The resulting copolymer is referred to as “copolymer (P-9)”.

Comparative Synthesis Example 1
125 mL of THF and 0.66 g of lithium chloride were added to a 300 mL flask and cooled to −60 ° C. 3.8 mL of n-butyllithium hexane solution (concentration 1.6 mol / L) was added, and after stirring for 5 minutes, diphenylethylene (1.1 g) was added and stirred for 15 minutes. A mixed solution of MMA 10 g, nBMA 7.5 g, and EHMA 10 g was added dropwise, and the reaction was continued for 15 minutes. GC was measured to confirm the disappearance of the monomer. Next, 22.5 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MMA, nBMA, and EHMA was obtained.
Next, 7.3 g of benzyl chloride and 25.0 g of propylene glycol monomethyl ether were added to the obtained block copolymer solution, and then gently stirred to raise the temperature of the block copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, a block copolymer comprising an A block having a DAMA-derived repeating unit, a part of which was quaternary ammoniumated, and a B block having a repeating unit derived from MMA, nBMA and EHMA was obtained. . The resulting copolymer is referred to as “copolymer (p-1)”.

Comparative Synthesis Example 2
125 mL of THF and 0.66 g of lithium chloride were added to a 300 mL flask and cooled to −60 ° C. 3.8 mL of n-butyllithium hexane solution (concentration 1.6 mol / L) was added, and after stirring for 5 minutes, diphenylethylene (1.1 g) was added and stirred for 15 minutes. A mixed solution of MMA 10 g and nBMA 7.5 g was dropped, and the reaction was continued for 15 minutes. GC was measured to confirm the disappearance of the monomer. Next, 10 g of EHMA was added dropwise, and the reaction was continued for 15 minutes after the addition. GC was measured to confirm the disappearance of the monomer. Next, 22.5 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. After measuring GC and confirming the loss | disappearance of a monomer, ethanol 2g was added and reaction was stopped. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, B1 block which has a repeating unit derived from EHMA, and B2 block which has a repeating unit derived from MMA and nBMA was obtained.
Next, 7.3 g of benzyl chloride and 25.0 g of propylene glycol monomethyl ether were added to the obtained block copolymer solution, and then gently stirred to raise the temperature of the block copolymer solution to 90 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, the A block having a DAMA-derived repeating unit, a part of which is quaternary ammoniumated, a B1 block having a repeating unit derived from EHMA, and a B2 block having a repeating unit derived from MMA and nBMA A block copolymer was obtained. The resulting copolymer is referred to as “copolymer (p-2)”.

Table 1 shows the copolymerization ratio (% by mass) of each monomer of the copolymer before quaternary ammonium conversion obtained in each of the above synthesis examples and comparative synthesis examples.
Table 1 also shows the Mw, Mw / Mn and quaternary ammonium conversion ratios of the copolymers (P-1) to (P-9) and (p-1) to (p-2). In addition, about the measuring method of Mw and Mw / Mn, it is as follows.

(Measurement of Mw and Mw / Mn)
Mw and Mw / Mn were measured by GPC having the following specifications. The measured value is based on polystyrene.
Apparatus: GPC-104 (manufactured by Showa Denko KK).
Column: Three LF-604 and KF-602 were used in combination.
Mobile phase: THF.

<Evaluation of the effect of inhibiting the growth of bacteria>
10 g of the specific copolymer solution obtained in the above synthesis example was added dropwise to 500 mL of hexane over 2 hours, and then dried by vacuum drying at 40 ° C. for 24 hours. Using the copolymer powder thus obtained, the effect of suppressing the growth of bacteria was evaluated.

Example 1
Preparation of liquid medium 16.8 g of Difco Mueller-Hinton Bros medium manufactured by BD was measured in an Erlenmeyer flask and dissolved in 800 mL of sterilized water. The mouth of the Erlenmeyer flask was covered with aluminum foil twice, an indicator seal was put on, and the flask was treated with an autoclave at 120 ° C. for 15 minutes. In this way, a liquid medium was prepared.

Preparation of Bacterial Solution The following bacteria were suspended in 10 mL of the liquid medium obtained in the above “ Preparation of liquid medium” to adjust OD600 to 1.0. When OD600 is 1.0, the amount of bacteria is about 1.8 × 10 ⁸ cfu / mL. 8 mL of the above liquid medium was further added to prepare a bacterial solution having a bacterial amount of 1.0 × 10 ⁸ cfu / mL.
S. aureus ATCC29213 strain (Gram positive bacteria)
E. coli DH5α strain (Gram-negative bacteria)

A 10 mg / mL aqueous solution of the measurement copolymer (P-1) and the liquid medium obtained in the above-mentioned “Preparation of liquid medium” were mixed, and the copolymer (P-1) concentration was 1024 μg / mL, 512 μg / mL. Measurement samples of mL, 256 μg / mL, 128 μg / mL, 64 μg / mL, 32 μg / mL and 16 μg / mL were prepared. On the well plate, 5 μL of the bacterial solution obtained in the above “Preparation of bacterial solution” was added to 100 μL of the obtained measurement sample. After incubating at 37 ° C. for 16 hours, the turbidity of each well was visually observed, and the growth state of the bacteria was evaluated according to the following criteria. Table 2 shows the evaluation results of S. aureus ATCC29213 strain (gram-positive bacteria), and Table 3 shows the evaluation results of E. coli DH5α strain (gram-negative bacteria). It can be said that the transparent one has a higher effect of suppressing the growth of bacteria.

(Evaluation criteria)
-: Transparent +: Turbidity is observed

Examples 2 to 9 and Comparative Examples 1 to 4
In Example 1, the growth state of the fungus was evaluated in the same manner as in Example 1 except that each compound shown in Tables 2 and 3 was used instead of the copolymer (P-1). Tables 2 and 3 show the evaluation results.

Claims (16)

1. An antibacterial agent, a bactericidal agent, or an antibacterial and bactericidal agent, having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), Mw (where Mw is gel perme An agent comprising, as an active ingredient, a copolymer having a polystyrene-reduced weight average molecular weight measured by an association chromatography, wherein the mobile phase in the gel permeation chromatography is tetrahydrofuran.
   

   

   [In the formula (1), R ¹ represents a hydrogen atom or a methyl group, Z represents a group forming an organic ammonium salt, —NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently of each other; Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group), or a substituted or unsubstituted nitrogen-containing heterocyclic group, and X represents a single bond or a divalent linking group. ]
   

   

   [In the formula (2), R ⁷ represents a hydrogen atom or a methyl group, and A represents an aromatic hydrocarbon group, — (C═O) OR ⁸ , — (C═O) NHR ⁹ , or —OR ^10. (Wherein R ⁸ to R ¹⁰ represent a hydrocarbon group or a group having a chain or cyclic ether structure). ]
2. The agent according to claim 1, wherein the Mw is 500 to 2,500.
3. The group forming the organic ammonium salt in the formula (1) is —N ⁺ R ² R ³ R ⁴ Y ⁻ (wherein R ² to R ⁴ are independently of each other a hydrogen atom or a substituted or unsubstituted group. The agent according to claim 1 or 2, which represents a hydrocarbon group, and Y ^- represents a counter anion.
4. X in the formula (1) is — (C═O) OR ¹¹ — (*), — (C═O) NHR ¹² — (*), or —ArR ¹³ — (*) (where R ¹¹ to R ¹³ represents a methylene group, an alkylene group or an alkyleneoxyalkylene group, Ar represents an arylene group, and “*” represents a bond bonded to Z.) 4. The agent according to any one of 3.
5. An antibacterial material, a sterilizing material, or an antibacterial and sterilizing material, having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), Mw (where Mw is gel perme A material containing a copolymer having a polystyrene-reduced weight average molecular weight measured by an association chromatography, wherein the mobile phase in the gel permeation chromatography is tetrahydrofuran.
   

   

   [In the formula (1), R ¹ represents a hydrogen atom or a methyl group, Z represents a group forming an organic ammonium salt, —NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently of each other; Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group), or a substituted or unsubstituted nitrogen-containing heterocyclic group, and X represents a single bond or a divalent linking group. ]
   

   

   [In the formula (2), R ⁷ represents a hydrogen atom or a methyl group, and A represents an aromatic hydrocarbon group, — (C═O) OR ⁸ , — (C═O) NHR ⁹ , or —OR ^10. (Wherein R ⁸ to R ¹⁰ represent a hydrocarbon group or a group having a chain or cyclic ether structure). ]
6. The material according to claim 5, wherein the Mw is 500 to 2,500.
7. The group forming the organic ammonium salt in the formula (1) is —N ⁺ R ² R ³ R ⁴ Y ⁻ (wherein R ² to R ⁴ are independently of each other a hydrogen atom or a substituted or unsubstituted group. The material according to claim 5, wherein the material represents a hydrocarbon group, and Y ⁻ represents a counter anion.
8. X in the formula (1) is — (C═O) OR ¹¹ — (*), — (C═O) NHR ¹² — (*), or —ArR ¹³ — (*) (where R ¹¹ to R ¹³ represents a methylene group, an alkylene group or an alkyleneoxyalkylene group, Ar represents an arylene group, and “*” represents a bond bonded to Z.) 8. The material according to any one of 7 above.
9. An antibacterial method, a sterilization method, or an antibacterial and sterilization method, having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and Mw (where Mw is gel perme A method using a copolymer having a polystyrene-reduced weight average molecular weight measured by an association chromatography, wherein the mobile phase in the gel permeation chromatography is tetrahydrofuran.
   

   

   [In the formula (1), R ¹ represents a hydrogen atom or a methyl group, Z represents a group forming an organic ammonium salt, —NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently of each other; Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group), or a substituted or unsubstituted nitrogen-containing heterocyclic group, and X represents a single bond or a divalent linking group. ]
   

   

   [In the formula (2), R ⁷ represents a hydrogen atom or a methyl group, and A represents an aromatic hydrocarbon group, — (C═O) OR ⁸ , — (C═O) NHR ⁹ , or —OR ^10. (Wherein R ⁸ to R ¹⁰ represent a hydrocarbon group or a group having a chain or cyclic ether structure). ]
10. The method according to claim 9, wherein the Mw is 500 to 2,500.
11. The group forming the organic ammonium salt in the formula (1) is —N ⁺ R ² R ³ R ⁴ Y ⁻ (wherein R ² to R ⁴ are independently of each other a hydrogen atom or a substituted or unsubstituted group. The method according to claim 9 or 10, wherein the hydrocarbon group is represented by Y ^- represents a counter anion.
12. X in the formula (1) is — (C═O) OR ¹¹ — (*), — (C═O) NHR ¹² — (*), or —ArR ¹³ — (*) (where R ¹¹ to R ¹³ represents a methylene group, an alkylene group or an alkyleneoxyalkylene group, Ar represents an arylene group, and “*” represents a bond bonded to Z.) 12. The method according to any one of 11 above.
13. It has a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and Mw (where Mw means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography, A copolymer in which the mobile phase in the gel permeation chromatography is tetrahydrofuran) is 3,000 or less.
    

    

    [In the formula (1), R ¹ represents a hydrogen atom or a methyl group, Z represents a group forming an organic ammonium salt, —NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently of each other; Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group), or a substituted or unsubstituted nitrogen-containing heterocyclic group, and X represents a single bond or a divalent linking group. ]
    

    

    [In the formula (2), R ⁷ represents a hydrogen atom or a methyl group, and A represents an aromatic hydrocarbon group, — (C═O) OR ⁸ , — (C═O) NHR ⁹ , or —OR ^10. (Wherein R ⁸ to R ¹⁰ represent a hydrocarbon group or a group having a chain or cyclic ether structure). ]
14. The copolymer according to claim 13, wherein the Mw is 500 to 2,500.
15. The group forming the organic ammonium salt in the formula (1) is —N ⁺ R ² R ³ R ⁴ Y ⁻ (wherein R ² to R ⁴ are independently of each other a hydrogen atom or a substituted or unsubstituted group. The copolymer according to claim 13 or 14, wherein the copolymer represents a hydrocarbon group, and Y ^- represents a counter anion.
16. X in the formula (1) is — (C═O) OR ¹¹ — (*), — (C═O) NHR ¹² — (*), or —ArR ¹³ — (*) (where R ¹¹ to R ¹³ represents a methylene group, an alkylene group or an alkyleneoxyalkylene group, Ar represents an arylene group, and “*” represents a bond bonded to Z.) 16. The copolymer according to any one of 15.