WO2023013643A1 - Antimicrobial agent, antimicrobial resin composition and quaternary ammonium salt - Google Patents

Abstract

An antimicrobial agent comprising a quaternary ammonium salt represented by formula (1).　(1): (R1)a(R2)b(R3)cN+·X- [In formula (1): R1 is an aliphatic hydrocarbon group wherein at least one hydrogen atom is substituted by a hydroxyl group, provided that R1 has 4-11 carbon atoms when only one hydrogen atom is substituted by a hydroxyl group, and 3-11 carbon atoms when two or more hydrogen atoms are substituted by hydroxyl groups; R2 is an aliphatic hydrocarbon group having 10-18 carbon atoms; R3 is an aliphatic hydrocarbon group having 1-3 carbon atoms; X- is a conjugate base of acid; a represents 1 or 2, b represents 1, and c represents 1 or 2, provided that a+b+c=4; the sum of carbon atoms in the aliphatic hydrocarbon groups represented by R1, R2 and R3 is 15-23 inclusive; and when a or c is 2, the plurality of R1's or R3's may be either the same or different.]

Description

Antibacterial agent, antibacterial resin composition and quaternary ammonium salt

The present invention relates to an antibacterial agent, an antibacterial resin composition using the same, and a quaternary ammonium salt.

　In recent years, the market for antibacterial resin compositions, in which antibacterial agents are added to resins such as urethane resin, has been expanding due to hygiene needs in housing spaces and automobile cabins. Various inorganic and organic antibacterial agents are known as antibacterial agents added to resins, and quaternary ammonium salts, which are cationic surfactants exhibiting antibacterial properties, are also being investigated.

Antibacterial agents comprising quaternary ammonium salts added to such resins include, for example, Patent Document 1 (International Publication No. 2016/043202), didecyldimethylammonium bromide, didecyldimethylammonium chloride, alkyl In addition to dimethylbenzylammonium chloride, didecyldimethylammonium adipate, etc., didecylmonomethylhydroxyethylammonium bromide, alkyldimethylhydroxyethylammonium chloride, N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate -, didecylmonomethylhydroxyethylammonium adipate, didecylmonomethylhydroxyethylammonium gluconate, didecylmonomethylhydroxyethylammonium sulfonate, alkyldimethylhydroxyethylammonium adipate, alkyldimethylhydroxyethyl Ammonium gluconate, didecylmethylpolyoxyethylene ammonium propionate and the like are mentioned.

Further, Patent Document 2 (Japanese Patent No. 4053635) describes the following quaternary ammonium salt (wherein R is a hydrogen atom or a hydrocarbon group, and x and y are integers of 1-4. ) is added to the urethane resin.

Furthermore, in Non-Patent Document 1, R(CH ₃ ) ₂ N ⁺ (CH ₂ CH ₂ CH ₂ OH) Br ^- and R(CH ₃ ) ₂ N ⁺ (CH ₂ CH ₂ OH) Br ^- (R=C ₁₀ H ₂₁ -C ₁₈ H ₃₇ ) have been investigated for antibacterial activity.

WO2016/043202 Japanese Patent No. 4053635 D. B. Kudryavtsev, et al. , Anticorrosive Effects and Antimicrobial Properties of Alkyldimethyl (hydroxyl) ammonium Bromides, Petroleum Chemistry, 2011, Vol. 51, No. 4, pp. 293-298

In recent years, the level of antibacterial activity required for antibacterial agents has risen, and as the number of opportunities for alcohol sterilization has increased, the required level of antibacterial activity and washing resistance against alcohol washing has also increased. Conventional antibacterial agents described in Patent Document 1, Patent Document 2, Non-Patent Document 1, etc. do not necessarily have sufficient antibacterial activity and alcohol-resistant washability.

One aspect of the present invention has been made in view of the above-described problems of the prior art, and has excellent antibacterial activity, and when added to a resin to form an antibacterial resin composition, an alcohol-resistant cleaning agent with antibacterial activity An object of the present invention is to provide an antibacterial agent having excellent properties, an antibacterial resin composition using the same, and a novel quaternary ammonium salt functioning as the antibacterial agent.

The present invention provides the following aspects.

[1] An antibacterial agent comprising a quaternary ammonium salt represented by formula (1).

(R ¹ ) _a (R ² ) _b (R ³ ) _c N ⁺ ·X ⁻ (1)
(In formula (1),
R ¹ is an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a hydroxyl group,
The number of carbon atoms in ^R1 is
4 to 11 when only one hydrogen atom is substituted with a hydroxyl group;
3 to 11 when two or more hydrogen atoms are substituted with hydroxyl groups;
R ² is an aliphatic hydrocarbon group having 10 to 18 carbon atoms,
R ³ is an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
X ^- is the conjugate base of the acid,
a represents 1 or 2, b represents 1, c represents 1 or 2, and satisfies a+b+c=4, and
the total number of carbon atoms of the aliphatic hydrocarbon groups represented by R ¹ , R ² and R ³ is 15 or more and 23 or less,
When a or c is 2, a plurality of R ¹ or R ³ may be the same or different. )
[2] The antibacterial agent according to [1], wherein a is 1, c is 2, and ^R3 is a methyl group.

[3] The aliphatic hydrocarbon group represented by R ¹ is at least one selected from the group consisting of a hydroxyalkyl group having 4 to 11 carbon atoms and a dihydroxyalkyl group having 3 to 11 carbon atoms, [1 ] or the antibacterial agent according to [2].

[4] In the aliphatic hydrocarbon group represented by R ¹ , the following conditions:
only one hydrogen atom on the terminal carbon atom is replaced with a hydroxyl group,
at least one hydrogen atom on a terminal carbon atom and at least one hydrogen atom on an adjacent carbon atom are each substituted with a hydroxyl group;
The antibacterial agent according to any one of [1] to [3], which satisfies any one of

[5] The antibacterial agent according to any one of [1] to [4], wherein the aliphatic hydrocarbon group is a linear alkyl group.

[6] The antibacterial agent according to any one of [1] to [5], wherein X ^- is a halide ion.

[7] An antibacterial resin composition in which the antibacterial agent according to any one of [1] to [6] is immobilized on a resin containing a functional group reactive with hydroxyl groups.

[8] The antibacterial resin composition according to [7], wherein the functional group is an isocyanate group.

[9] The antibacterial resin composition according to [7] or [8], wherein the resin is a urethane resin.

[10] A quaternary ammonium salt represented by formula (2).

(In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, satisfies m+n=16 to 21, and X ⁻ represents a halide ion.)
[11] The quaternary ammonium salt according to [10] represented by formula (3).

(In formula (3), n represents an integer from 12 to 14, and X ^- represents a halide ion.)
[12] The quaternary ammonium salt according to [10] represented by formula (4).

(In formula (4), X ⁻ represents a halide ion.)
[13] A quaternary ammonium salt represented by formula (5).

(In formula (5), n represents an integer from 12 to 16, and X ^- represents a halide ion.)

The antibacterial agent according to one aspect of the present invention has excellent antibacterial activity, and when it is added to a resin to form an antibacterial resin composition, the antibacterial activity and alcohol resistance are excellent. Therefore, according to another aspect of the present invention, it is possible to obtain an antibacterial resin composition having excellent antibacterial activity and excellent resistance to alcohol washing. In yet another aspect of the present invention, novel quaternary ammonium salts are provided that function as antibacterial agents with excellent antibacterial activity and resistance to alcohol washing.

The present invention will be described in detail below in accordance with its preferred embodiments. First, an antibacterial agent according to one aspect of the present invention will be described.

The antimicrobial agent has the formula (1):
(R ¹ ) _a (R ² ) _b (R ³ ) _c N ⁺ ·X ⁻ (1)
(In formula (1),
R ¹ is an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a hydroxyl group,
The number of carbon atoms in ^R1 is
4 to 11 when only one hydrogen atom is substituted with a hydroxyl group;
3 to 11 when two or more hydrogen atoms are substituted with hydroxyl groups;
R ² is an aliphatic hydrocarbon group having 10 to 18 carbon atoms,
R ³ is an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
X ^- is the conjugate base of the acid,
a represents 1 or 2, b represents 1, c represents 1 or 2, and satisfies a+b+c=4, and
the total number of carbon atoms of the aliphatic hydrocarbon groups represented by R ¹ , R ² and R ³ is 15 or more and 23 or less,
When a or c is 2, a plurality of R ¹ or R ³ may be the same or different. )
It consists of a quaternary ammonium salt represented by.

In formula (1), R ³ is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, which may be linear or branched, saturated or unsaturated, Alkyl groups are preferred, and linear alkyl groups are particularly preferred. Without such an aliphatic hydrocarbon group having 1 to 3 carbon atoms, the quaternary ammonium cation becomes less accessible to bacteria, resulting in a decrease in antibacterial activity and resistance to washing with alcohol. Examples of R ³ include a methyl group, an ethyl group, a propyl group, etc. Among them, a methyl group is preferable from the viewpoint that the antibacterial activity and its resistance to washing with alcohol tend to be further improved. The number (c) of R ³ is 1 or 2, and c is preferably 2 from the viewpoint that the antibacterial activity and its resistance to washing with alcohol tend to be further improved. Also, when there are multiple ^R3 's in one molecule, they may be the same or different.

In formula (1), R ² is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, which may be linear or branched, saturated or unsaturated, Alkyl groups are preferred, and straight-chain alkyl groups are particularly preferred, because of their increased antibacterial activity. The carbon number of R ² is 10 to 18, specifically, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, any two of the numerical values exemplified here It may be within the range of the upper and lower limits. The present inventors presume that R ² is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, so that it has sufficient hydrophobicity and exhibits antibacterial properties based on its action on cell membranes, so that the antibacterial activity is excellent. ing. Examples of ^R2 in terms of high antibacterial activity include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl groups. The number (b) of ^R2 is one.

In formula (1), R ¹ is an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a hydroxyl group, and the aliphatic hydrocarbon group may be linear or branched. , which may be saturated or unsaturated, an alkyl group is preferred, and a straight-chain alkyl group is particularly preferred, since the antibacterial activity is enhanced. By introducing a hydroxyl group into at least one aliphatic hydrocarbon group in this way, when an antibacterial agent is added to the manufacturing process of a resin such as urethane, the functional group of the resin raw material and the hydroxyl group react to form a covalent bond, etc. Since it is immobilized on the resin by a bond (preferably a covalent bond), the antibacterial activity is improved in alcohol washing resistance.

When R ¹ in formula (1) has one substituted hydroxyl group, it must be an aliphatic hydrocarbon group having 4 to 11 carbon atoms. The hydrocarbon chain that is the linker between the cationic site and the hydroxyl group affects the antibacterial activity, and when the number of substituted hydroxyl groups is one, the number of carbon atoms in the aliphatic hydrocarbon group is less than 4, or the aliphatic hydrocarbon group exceeds 11 carbon atoms, the antibacterial activity is reduced. When R ¹ in formula (1) has one substituted hydroxyl group, the number of carbon atoms in R ¹ is 4 to 11, or may be 5 to 11. Specifically, for example, 4 , 5, 6, 7, 8, 9, 10, and 11, and may be within a range having upper and lower limits of any two of the numerical values exemplified here. Such R ¹ is preferably a hydroxyalkyl group having 4 to 11 carbon atoms, such as a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, a hydroxynonyl group, a hydroxydecyl group, a hydroxyun A decyl group etc. are mentioned as an example. The position where the hydroxyl group is bonded to the aliphatic hydrocarbon group is not particularly limited, but when added to the resin, it tends to react more easily with the functional group of the resin, and the antibacterial activity tends to further improve the alcohol washing resistance. From the viewpoint of being in, it is preferable that a hydroxyl group is bonded to the terminal carbon atom on the side not bonded to the N atom.

When R ¹ in formula (1) has two or more substituted hydroxyl groups, it must be an aliphatic hydrocarbon group having 3 to 11 carbon atoms. The hydrocarbon chain that is the linker between the cationic site and the hydroxyl group affects the antibacterial activity, and when the number of substituted hydroxyl groups is two or more, the number of carbon atoms in the aliphatic hydrocarbon group is less than 3, or the aliphatic carbonization When the number of carbon atoms in the hydrogen group exceeds 11, the antibacterial activity is lowered. When R ¹ in formula (1) has two or more substituted hydroxyl groups, R ¹ has 3 to 11 carbon atoms, specifically, for example, 3, 4, 5, 6, 7. , 8, 9, 10, and 11, and may be within a range having upper and lower limits of any two of the numerical values exemplified here. Examples of such R ¹ include a dihydroxypropyl group, a dihydroxybutyl group, a dihydroxypentyl group, a dihydroxyhexyl group, a dihydroxyheptyl group, a dihydroxyoctyl group, a dihydroxynonyl group, a dihydroxydecyl group, a dihydroxyundecyl group, a trihydroxypropyl group, Examples include a trihydroxybutyl group, a trihydroxypentyl group, a trihydroxyhexyl group, a trihydroxyheptyl group, a trihydroxyoctyl group, a trihydroxynonyl group, a trihydroxydecyl group, and a trihydroxyundecyl group. From the viewpoint of suppressing the formation of unnecessary crosslinks when added to the resin production process and further improving the mechanical properties of the resin, the number of substituted hydroxyl groups is preferably three or less, and two. is more preferred. Such R ¹ is preferably a dihydroxyalkyl group having 3 to 11 carbon atoms. In addition, the position where the hydroxyl group is bonded to the aliphatic hydrocarbon group is not particularly limited, but when added to the resin, it becomes easier to react with the functional group of the resin, and the antibacterial activity and alcohol washing resistance are further improved. From the viewpoint that there is a tendency to preferable.

Also, the number (a) of ^R1 is 1 or 2, and it is necessary to satisfy a+b+c=4. From the viewpoint that the antibacterial activity tends to be further improved, a is preferably 1. In addition, when multiple R ^1s are present in one molecule, they may be the same or different.

Furthermore, the total number of carbon atoms of the aliphatic hydrocarbon groups represented by R ¹ , R ² and R ³ in one molecule of the quaternary ammonium salt represented by formula (1) is 15 or more and 23 or less. is necessary. The total number of carbon atoms in the aliphatic hydrocarbon groups (R ¹ to R ³ ) attached to the N atom of the quaternary ammonium salt also affects the antibacterial activity. If the total number of carbon atoms exceeds 23, the antibacterial activity will decrease. The total number of carbon atoms of the aliphatic hydrocarbon groups represented by R ¹ , R ² and R ³ is 15 or more and 23 or less. 22 and 23, and any two of the numerical values exemplified here may be within a range having upper and lower limits.

Also, X 1 ^- in formula (1) is a conjugate base of an acid. It is preferred that X ^- is the conjugate base of a strong acid. By combining the specific quaternary ammonium cation and the conjugate base (anion) of a strong acid and using them as a salt, it functions as an antibacterial agent having excellent antibacterial activity, and is added to the resin to provide an antibacterial resin. When it is made into a composition, the antibacterial activity tends to be improved. On the other hand, a conjugate base of a weak acid such as a carboxylate ion tends to fail to sufficiently obtain the antibacterial activity-enhancing effect. Conjugate bases of strong acids include halide ions such as bromine (Br), chlorine (Cl), fluorine (F), and iodine (I), nitrate ions, sulfate ions, phosphate ions, perchlorate ions, and the like. Among them, the halide ion is preferable, and bromine (Br) or chlorine (Cl) is particularly preferable, from the viewpoint that the antibacterial activity tends to be further improved.

The method for producing the antibacterial agent according to one aspect of the present invention (the quaternary ammonium salt represented by formula (1) according to one aspect of the present invention) is not particularly limited, but for example the following method. is preferably adopted.

<Method 1>
Formula (1a) corresponding to the desired quaternary ammonium salt:
(R ² )(R ³ ) ₂ N (1a)
(In formula (1a), R ² and R ³ have the same meanings as in formula (1).)
The tertiary amine represented by the formula (1b) corresponding to the desired quaternary ammonium salt:
(R ¹ )X (1b)
(In formula (1b), R ¹ and X have the same meanings as in formula (1).)
A method of obtaining the desired quaternary ammonium salt by subjecting it to a quaternization reaction in a reaction medium with a halogenated alcohol represented by the following, washing and drying if necessary.

<Method 2>
Formula (1c) corresponding to the desired quaternary ammonium salt:
(R ¹ )(R ³ ) ₂ N (1c)
(In formula (1c), R ¹ and R ³ have the same meanings as in formula (1).)
The tertiary amine represented by the formula (1d) corresponding to the desired quaternary ammonium salt:
(R ² )X (1d)
(In formula (1d), R ² and X have the same meanings as in formula (1).)
A method of quaternization reaction in a reaction medium with an alkyl halide represented by and optionally washing and drying to obtain the desired quaternary ammonium salt.

<Method 3>
Formula (1e) corresponding to the desired quaternary ammonium salt:
(R ¹ ) ₂ (R ³ ) N (1e)
(In formula (1e), R ¹ and R ³ have the same meanings as in formula (1).)
The tertiary amine represented by the formula (1f) corresponding to the desired quaternary ammonium salt:
(R ² )X (1f)
(In formula (1f), R ² and X have the same meanings as in formula (1).)
A method of quaternization reaction in a reaction medium with an alkyl halide represented by and optionally washing and drying to obtain the desired quaternary ammonium salt.

<Method 4>
Formula (1g) corresponding to the desired quaternary ammonium salt:
(R ¹ ) ₂ (R ² )N (1 g)
(In formula (1g), R ¹ and R ² have the same meanings as in formula (1).)
The tertiary amine represented by the formula (1h) corresponding to the desired quaternary ammonium salt:
(R ³ )X (1h)
(In formula (1h), R ³ and X have the same meanings as in formula (1).)
A method of quaternization reaction in a reaction medium with an alkyl halide represented by and optionally washing and drying to obtain the desired quaternary ammonium salt.

The reaction solvent used in the quaternization reaction is not particularly limited, and acetonitrile, propanenitrile, dimethylformamide (hereinafter sometimes referred to as DMF), dimethylsulfoxide (hereinafter sometimes referred to as DMSO), nitromethane, Nitroethane, benzonitrile, nitrobenzene, methanol, ethanol, propanol, 2-propanol, butanol, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, toluene, xylene, chlorobenzene, o- Examples include dichlorobenzene, m-dichlorobenzene, nitrobenzene, etc. Among them, acetonitrile is preferable from the viewpoint of good yield.

Next, an antibacterial resin composition according to one aspect of the present invention will be described. The antibacterial resin composition is obtained by immobilizing the antibacterial agent on a resin containing functional groups reactive with hydroxyl groups.

Examples of functional groups reactive with hydroxyl groups include isocyanate groups and epoxy groups. Among them, covalent bonds are formed by reaction with hydroxyl groups in a temperature range where quaternary ammonium does not decompose, and are immobilized on the resin. An isocyanate group is preferable from the viewpoint that the antibacterial activity tends to further improve the alcohol-resistant washability.

Resins containing such functional groups are not particularly limited, but examples thereof include urethane resins, urea resins, urethane urea resins, polyimide resins, polyoxazolidone resins, polycarbodiimide resins, polyisocyanurate resins, and the like. Among them, urethane resins obtained from polyisocyanate and polyol, poly Urea resins obtained from isocyanates and polyamines, and urethane urea resins obtained from polyisocyanates, polyols and polyamines (monoamines) are preferred. In addition, covalent bonds are formed by reaction with hydroxyl groups and fixed to the resin, which further improves the antibacterial activity and alcohol washing resistance, and from the viewpoint of good appearance and excellent mechanical properties and durability, polyisocyanate and Urethane resins obtained from polycarbonate polyols are more preferred.

The amount of the antibacterial agent added in the antibacterial resin composition is not particularly limited, and is appropriately adjusted according to the purpose, etc., but usually the amount of the antibacterial agent added in the resin composition is 5% by mass or less. and more preferably 0.1 to 5% by mass.

In addition, in the antibacterial resin composition, if necessary, for example, antioxidants, ultraviolet absorbers, pigments, paints, solvents, flame retardants, hydrolysis inhibitors, lubricants, plasticizers, fillers, antistatic Additives such as agents, dispersants, catalysts, storage stabilizers, surfactants, leveling agents, etc., can be added as appropriate.

Although the method for obtaining the antibacterial resin composition by immobilizing the antibacterial agent on the resin is not particularly limited, for example, the following method is preferably employed.
(i) An antibacterial agent is mixed in a resin-forming composition in the previous step of reacting resin raw materials (e.g., polyisocyanate and polyol), and the resulting resin-forming composition is reacted to obtain an antibacterial resin. A method of obtaining the composition.
(ii) A method for obtaining an antibacterial resin composition by mixing resin pellets or powdery resin and an antibacterial agent in a mixer, and then heat-melting and kneading them in an extruder.
(iii) A method of preparing a so-called masterbatch in which a high-concentration antibacterial agent is blended in a resin in advance, and diluting it to a predetermined concentration with resin pellets or powdered resin to obtain an antibacterial resin composition.

The shape and the like of the antibacterial resin composition are not particularly limited. It is used for various applications with high hygienic needs in automobile cabins.

Next, the quaternary ammonium salt according to one aspect of the present invention will be described. A first quaternary ammonium salt according to one aspect of the present invention has the formula (2):

(In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, satisfies m+n=16 to 21, and X ⁻ represents a halide ion.)
is a quaternary ammonium salt represented by

m represents an integer of 6 to 11, specifically, for example, 6, 7, 8, 9, 10, 11, within the range of upper and lower limits any two of the numerical values exemplified here good too. n represents an integer from 10 to 14, specifically, for example, 10, 11, 12, 13, 14, any two of the numerical values exemplified here may be within a range of upper and lower limits . m+n satisfies 16 to 21, specifically, for example, 16, 17, 18, 19, 20, 21, any two of the numerical values exemplified here may be within the range of upper and lower limits .

Among the quaternary ammonium salts represented by formula (2), those in which m is 6 and n is an integer of 12 to 14 are preferred, and such quaternary ammonium salts are represented by formula (3):

(In formula (3), n represents an integer from 12 to 14, and X ^- represents a halide ion.)
is represented by

Further, among the quaternary ammonium salts represented by formula (2), those in which m is 11 and n is 10 are also preferable, and such quaternary ammonium salts are represented by formula (4):

(In formula (4), X ⁻ represents a halide ion.)
is represented by

Furthermore, the second quaternary ammonium salt according to one aspect of the present invention has the formula (5):

(In formula (5), n represents an integer from 12 to 16, and X ^- represents a halide ion.)
is represented by

The quaternary ammonium salts represented by formulas (2) to (5) have excellent antibacterial activity, and when added to a resin to form an antibacterial resin composition, the antibacterial activity and alcohol resistance are excellent. It is a novel compound that functions as an antibacterial agent.

In addition, the quaternary ammonium salts represented by formulas (2) to (5) can be produced according to the above-described methods 1 to 4, and the quaternary ammonium salts represented by formula (2) The salts are Examples 1 to 5 described later, the quaternary ammonium salts represented by the formula (3) are described later as Examples 2 and 3, and the quaternary ammonium salts represented by the formula (4) are described later. As Example 1, the quaternary ammonium salt represented by formula (5) was actually produced as Examples 7 and 8, which will be described later.

As described above, the antibacterial agent according to one aspect of the present invention has excellent antibacterial activity, and when added to a resin to form an antibacterial resin composition, the antibacterial activity and alcohol-resistant washability are excellent. . Therefore, according to another aspect of the present invention, it is possible to obtain an antibacterial resin composition having excellent antibacterial activity and excellent resistance to alcohol washing. In yet another aspect of the present invention, novel quaternary ammonium salts are provided that function as antibacterial agents with excellent antibacterial activity and resistance to alcohol washing.

The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.

In addition, the structural analysis of the antibacterial agent, the antibacterial evaluation of the antibacterial agent, and the antibacterial evaluation of the antibacterial treated urethane resin were performed and evaluated by the following methods.

(Structural analysis of antibacterial agents)
The structure of each antibacterial agent was determined by NMR spectroscopy. Deuterated chloroform (manufactured by ambridge Isotope Laboratories, Inc., hereinafter referred to as CDCl ₃ ) or deuterated dimethyl sulfoxide (manufactured by ambridge Isotope Laboratories, Inc., hereinafter Using DMSO-d ₆ ), each antibacterial agent was dissolved at a concentration of 1% by mass based on the chemical shift standard, and a nuclear magnetic resonance apparatus (manufactured by Bruker, "AVANCE II") was used to analyze at 400 MHz ( ¹ H- NMR) frequency.

(Antibacterial property evaluation of antibacterial agents)
The antibacterial activity of each antibacterial agent was evaluated by measuring the minimum inhibitory concentration (MIC).

(1) Method for measuring minimum growth inhibitory concentration Each test strain cultured at 30 ° C. for 1 day using Nutrient agar medium (Nutrient liquid medium (Nutrient broth, manufactured by Difco) + 1.5% (w / v) agar) It was suspended in sterilized ion-exchanged water to a concentration equivalent to 0.5 McFarland to prepare a bacterial solution for inoculum.
Test fungus: Staphylococcus epidermidis NBRC 100911
A water-soluble test substance was adjusted to a concentration of 8.0 mg/mL with ion-exchanged water and sterilized with a filter to obtain a stock solution. The stock solution was diluted 10-fold with the Nutrient liquid medium to obtain a solution with the maximum diluted concentration (800 μg/mL). On the other hand, the poorly water-soluble test substance was adjusted to a concentration of 80 mg/mL with dimethyl sulfoxide (manufactured by Tokyo Kasei Kogyo Reagent Co., Ltd.), and the unsterilized one was used as the stock solution. The stock solution was diluted 100-fold with the Nutrient liquid medium to obtain a solution with the maximum diluted concentration (800 μg/mL).

A test substance solution was prepared by diluting the test substance (antibacterial agent) with the Nutrient liquid medium so that there were 11 levels, including the maximum concentration at a dilution rate of 2, with the solution with the maximum diluted concentration as the maximum concentration. 100 μL of each test substance solution was dispensed into a 96-well microplate (U-shaped well), and each well was inoculated with 5 μL of the inoculum solution of each test bacterium. In addition, 100 μL of Nutrient liquid medium containing no test substance (Nutrient liquid medium containing no test substance) was dispensed into a 96-well microplate and inoculated with 5 μL of the inoculum solution of each test bacterium. served as a growth control.

A 96-well microplate was sealed with an air-permeable sheet, and the test solution was allowed to stand and culture at 30°C for 48 hours. After culturing, when no turbidity or sedimentation was observed with the naked eye, and even if there was one sedimentation with a diameter of 1 mm or less, the growth inhibition was determined. After confirming the growth of test bacteria in the nutrient liquid medium containing no test substance used as a control, the lowest test substance concentration in wells in which no growth of bacteria was visually observed was taken as the MIC. Each test substance was tested twice, and the average value was used as the measured value.

(2) Determination of Minimum Inhibitory Concentration Based on the measurement results of the minimum inhibitory concentration for each antibacterial agent, the antibacterial properties of the antibacterial agent were evaluated according to the following criteria.
<Criteria for minimum growth inhibitory concentration>
A: Minimum inhibitory concentration (μg/mL) <30
B: Minimum inhibitory concentration (μg/mL) = 30-100
C: Minimum inhibitory concentration (μg/mL)>100.

(Evaluation of antibacterial activity of antibacterial urethane resin against alcohol washing)
Alcohol-resistant antibacterial activity of each antibacterial treated urethane resin Antibacterial activity is evaluated by using each antibacterial treated urethane resin after manufacturing each antibacterial treated urethane resin as a post-treatment (washing), immersing it in ethanol and boiling it for 6 hours. It was evaluated by measuring the bacterial growth inhibition rate.

(1) Preparation of used medium and physiological saline 1) NA medium (double concentration Nutrient liquid medium (manufactured by Difco) + 5.0 g / L: NaCl + 15 g / L: agar)
2) NB medium (ordinary bouillon medium, manufactured by Eiken Chemical Co., Ltd.)
3) SCDLP medium (Daigo, manufactured by Nihon Pharmaceutical Co., Ltd.)
4) SA medium (2.5 g / L: yeast extract, 5.0 g / L: tryptone peptone, 1.0 g / L: glucose, 15 g / L: agar)
5) Phosphate buffered saline (42.5 mg/L: _KH2PO4 , 8.5 g/L: NaCl, pH _: 7.2).

(2) Preparation of test bacteria and test bacterial solution 1) Test bacteria Staphylococcus epidermidis NBRC 100911
2) Preparation of Test Bacterial Solution A strain that had been cryopreserved was cultured in NA medium at 35° C. for 24 hours. This culture was transferred to new NA medium and cultured at 35° C. for 24 hours. The grown colonies were scraped off and adjusted to about 1×10 ⁶ cells/mL with 1/100 concentration NB medium, and this was used as a test fungus solution.

(3) Test method The test method was carried out as follows with reference to "JIS Z2801:2012 Antibacterial processed products Antibacterial test method/antibacterial effect".
1) Inoculation and culture of test bacteria solution Cut into 50 mm squares, wipe and disinfect the entire surface with a paper wipe soaked with 99% ethanol, and then completely dry the test product (antibacterial treated urethane resin and untreated urethane resin ) was placed on a Petri dish, and 0.4 mL of the test bacterial solution was dropped. A 40 mm square covering film (polyethylene film) was placed on the dripped test fungus solution, and the test fungus solution was brought into close contact with the entire test article. After inoculation of the fungus solution, the test product was allowed to act for a predetermined period of time under the operating temperature and humidity conditions. Three specimens (n=3) were tested under each condition.
2) Bacterial Count Measurement After the action for a predetermined time, 10 mL of SCDLP medium was added to the petri dish containing the test product, and the test bacteria were washed out from the test product using a Pipetman (1000 μL). The washed-out liquid was used as a sample liquid for bacterial count measurement. A serial dilution of the sample solution was prepared using phosphate-buffered saline, and 100 μL each of the undiluted sample solution and the diluted solution were spread in SA medium and cultured at 35° C. for 24 hours. After culturing, the growing colonies were counted to determine the number of test bacteria per 1 cm ² of the test product (quantification lower limit: 0.63 cells/cm ² ), and the average value was taken as the measured value.

(4) Calculation of bacterial growth inhibition rate The bacterial growth inhibition rate was calculated based on the following (Equation 1) using the measured number of test bacteria obtained above.
Bacterial growth inhibition rate (%) = {1-(test bacteria count of antibacterial urethane resin 24 hours after inoculation) / (test bacteria count of unprocessed urethane resin 24 hours after inoculation)} × 100 (formula 1).

(5) Determination of bacterial growth inhibition rate Based on the measurement results of the bacterial growth inhibition rate for each antibacterial urethane resin, the antibacterial properties (alcohol resistance of antibacterial activity) of the antibacterial urethane resin were evaluated according to the following criteria. .
<Criteria for bacterial growth inhibition rate>
A: fungal growth inhibition rate (%)>90
B: bacterial growth inhibition rate (%) = 50-90
C: Bacterial growth inhibition rate (%) <50.

(Antibacterial Agent Synthesis Example 1: Example 1/Antibacterial Agent A)
Synthesis of N-decyl-N-(11-hydroxyundecyl)-N,N-dimethylammonium bromide. 1-Undecanol (1.50 g, 5.97 mmol), N,N-dimethyldecylamine (1.42 mL, 5.98 mmol) and acetonitrile (10 mL) were charged and stirred under reflux (82° C.) for 5 hours. After allowing to cool, acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and dried under reduced pressure to give N-decyl-N-(11-hydroxyundecyl)-N,N - A white solid of dimethylammonium bromide (yield: 2.58 g, yield: 99%) was obtained. The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 4.34 (m, 1H), 3.40-3.36 (m, 2H), 3.26-3.18 (m, 4H), 2. 98 (s, 6H), 1.68-1.56 (m, 4H), 1.44-1.20 (m, 30H), 0.90-0.83 (m, 3H).

(Antibacterial Agent Synthesis Example 2: Example 2/Antibacterial Agent B)
Synthesis of N-(6-hydroxyhexyl)-N,N-dimethyltetradecylammonium bromide Into a 100 mL 3-necked round bottom flask equipped with a reflux condenser and a thermometer was added a stir bar, 6-dimethylamino-1- Hexanol (7.49 g, 50.0 mmol), 1-bromotetradecane (14.3 g, 50.0 mmol) and acetonitrile (25 mL) were added and stirred under reflux (82° C.) for 5 hours. After allowing to cool, acetonitrile is distilled off under reduced pressure, and the resulting crude product is washed with ethyl acetate and dried under reduced pressure to give N-(6-hydroxyhexyl)-N,N-dimethyltetradecylammonium. A white bromide solid (yield: 20.9 g, yield: 99%) was obtained. The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 4.38 (m, 1H), 3.43-3.36 (m, 2H), 3.26-3.18 (m, 4H), 2. 99 (s, 6H), 1.70-1.58 (m, 4H), 1.49-1.18 (m, 28H), 0.89-0.82 (m, 3H).

(Antibacterial Agent Synthesis Example 3: Example 3/Antibacterial Agent C)
Synthesis of N-dodecyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium bromide. -Hexanol (3.62 g, 20.0 mmol), acetonitrile (30 mL) and N,N-dimethyldodecylamine (4.27 g, 20.0 mmol) were charged and stirred under reflux (82°C) for 7 hours. After allowing to cool, acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and dried under reduced pressure to give N-dodecyl-N-(6-hydroxyhexyl)-N,N- A colorless viscous substance of dimethylammonium bromide (yield: 7.81 g, yield: 99%) was obtained. The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 4.38 (m, 1H), 3.43-3.36 (m, 2H), 3.26-3.18 (m, 4H), 2. 99 (s, 6H), 1.70-1.58 (m, 4H), 1.49-1.18 (m, 24H), 0.89-0.82 (m, 3H).

(Antibacterial Agent Synthesis Example 4: Example 4/Antibacterial Agent D)
Synthesis of N-decyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium bromide. -Hexanol (3.62 g, 20.0 mmol), acetonitrile (30 mL) and N,N-dimethyldecylamine (3.71 g, 20.0 mmol) were charged and stirred under reflux (82°C) for 7 hours. After allowing to cool, acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and dried under reduced pressure to give N-decyl-N-(6-hydroxyhexyl)-N,N- A colorless viscous substance of dimethylammonium bromide (yield: 7.26 g, yield: 99%) was obtained. The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.65-3.59 (m, 4H), 3.47-3.43 (m, 2H), 3.36 (s, 6H), 2.79 ( brs, 1H), 1.81-1.26 (m, 24H), 0.90-0.87 (m, 3H).

(Antibacterial Agent Synthesis Example 5: Example 5/Antibacterial Agent E)
Synthesis of N-decyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium chloride Into a 100 mL 3-necked round-bottom flask equipped with a reflux condenser and a thermometer, stir bar, 6-chloro-1. -Hexanol (3.00 g, 22.0 mmol), acetonitrile (33 mL) and N,N-dimethyldecylamine (5.22 mL, 22.0 mmol) were charged and stirred under reflux (82°C) for 22 hours. After allowing to cool, acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with diethyl ether and ethyl acetate and dried under reduced pressure to give N-decyl-N-(6-hydroxyhexyl)-N , N-dimethylammonium chloride as a white solid (yield: 4.04 g, yield: 57%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.64-3.59 (m, 4H), 3.46-3.42 (m, 3H), 3.37 (s, 6H), 1.94- 1.26 (m, 24H), 0.90-0.86 (m, 3H).

(Antibacterial Agent Synthesis Example 6: Example 6 / Antibacterial Agent F)
Synthesis of N-(4-hydroxybutyl)-N-hexadecyl-N,N-dimethylammonium bromide A 100 mL 3-necked round-bottom flask equipped with a reflux condenser and a thermometer was charged with a stir bar, 4-(dimethylamino )-1-butanol (5.98 g, 50.0 mmol), 1-bromohexadecane (15.9 g, 50.0 mmol) and acetonitrile (25 mL) were charged and stirred under reflux (82° C.) for 5 hours. After allowing to cool, acetonitrile is distilled off under reduced pressure, and the resulting crude product is washed with ethyl acetate and dried under reduced pressure to give N-(4-hydroxybutyl)-N-hexadecyl-N,N- A white solid of dimethylammonium bromide (yield: 20.4 g, yield: 97%) was obtained. The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 4.56 (m, 1H), 3.48-3.41 (m, 2H), 3.29-3.21 (m, 4H), 3. 00 (s, 6H), 1.76-1.59 (m, 4H), 1.48-1.37 (m, 2H), 1.34-1.19 (m, 26H), 0.90- 0.83 (m, 3H).

(Antibacterial Agent Synthesis Example 7: Example 7/Antibacterial Agent G)
Synthesis of N-(2,3-dihydroxypropyl)-N-hexadecyl-N,N-dimethylammonium bromide. -1,2-Propanediol (2.35 g, 15.2 mmol), N,N-dimethylhexadecylamine (4.16 g, 15.4 mmol) and acetonitrile (25 mL) were charged and refluxed (82°C). Stirred for 5 hours. After allowing to cool, acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and dried under reduced pressure to give N-(2,3-dihydroxypropyl)-N-hexadecyl-N, A white solid of N-dimethylammonium bromide (yield: 5.47 g, yield: 85%) was obtained. The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 5.36 (d, J = 8.2 Hz, 1 H), 5.00 (t, J = 5.8 Hz, 1 H), 4.00 (m, 1 H ), 3.45-3.37 (m, 2H), 3.30-3.18 (m, 2H), 3.08 (s, 3H), 3.07 (s, 3H), 1.78- 1.56 (m, 2H), 1.47-1.00 (m, 28H), 0.86 (t, J=6.6Hz, 3H).

(Antibacterial Agent Synthesis Example 8: Example 8/Antibacterial Agent H)
Synthesis of N-dodecyl-N-(2,3-dihydroxypropyl)-N,N-dimethylammonium bromide. -1,2-Propanediol (2.35 g, 15.2 mmol), N,N-dimethyldodecylamine (3.29 g, 15.4 mmol), and acetonitrile (25 mL) were charged and heated under reflux (82°C)5. Stirred for an hour. After allowing to cool, acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and dried under reduced pressure to give N-dodecyl-N-(2,3-dihydroxypropyl)-N, A white solid of N-dimethylammonium bromide (yield: 4.82 g, yield: 85%) was obtained. The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 5.36 (d, J = 8.2 Hz, 1 H), 5.00 (t, J = 5.8 Hz, 1 H), 4.00 (m, 1 H ), 3.45-3.37 (m, 2H), 3.30-3.18 (m, 2H), 3.08 (s, 3H), 3.07 (s, 3H), 1.78- 1.56 (m, 2H), 1.47-1.00 (m, 20H), 0.86 (t, J=6.6Hz, 3H).

(Antibacterial Agent Synthesis Example 9: Comparative Example 1/Antibacterial Agent I)
Synthesis of N-(11-hydroxyundecyl)-N-hexadecyl-N,N-dimethylammonium bromide Into a 50 mL 3-necked round bottom flask equipped with a reflux condenser and a thermometer, a stir bar, 11-bromo- 1-Undecanol (1.40 g, 5.57 mmol), N,N-dimethylhexadecylamine (1.88 mL, 5.57 mmol) and acetonitrile (10 mL) were charged and stirred under reflux (82° C.) for 7 hours. . After allowing to cool, the solvent was distilled off under reduced pressure, and the resulting crude product was washed with diethyl ether to give N-(11-hydroxyundecyl)-N-hexadecyl-N,N-dimethylammonium bromide as a white solid. (yield: 2.81 g, yield: 97%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.67-3.62 (m, 2H), 3.55-3.48 (m, 4H), 3.40 (s, 6H), 1.74- 1.66 (m, 4H), 1.60-1.26 (m, 43H), 0.90-0.86 (m, 3H).

(Antibacterial Agent Synthesis Example 10: Comparative Example 2/Antibacterial Agent J)
Synthesis of N-butyl-N-(11-hydroxyundecyl)-N,N-dimethylammonium bromide A 50 mL 3-necked round-bottom flask equipped with a reflux condenser and a thermometer was charged with a stir bar, 11-bromo- 1-Undecanol (1.70 g, 6.77 mmol), N,N-dimethylbutylamine (0.96 mL, 6.82 mmol) and acetonitrile (12 mL) were charged and stirred under reflux (82° C.) for 7 hours. After allowing to cool, the solvent was distilled off under reduced pressure, and the resulting crude product was washed with diethyl ether to give N-butyl-N-(11-hydroxyundecyl)-N,N-dimethylammonium bromide as a white solid. (yield: 2.22 g, yield: 93%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.65-3.62 (m, 2H), 3.56-3.51 (m, 4H), 3.40 (s, 6H), 1.80- 1.28 (m, 23H), 1.03-0.99 (m, 3H).

(Antibacterial Agent Synthesis Example 11: Comparative Example 3/Antibacterial Agent K)
Synthesis of N-decyl-N-(3-hydroxypropyl)-N,N-dimethylammonium bromide. -Propanol (2.78 g, 20.0 mmol), N,N-dimethyldecylamine (3.71 g, 20.0 mmol) and acetonitrile (30 mL) were charged and stirred under reflux (82°C) for 5 hours. After allowing to cool, acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and dried under reduced pressure to give N-decyl-N-(3-hydroxypropyl)-N,N- A white solid of dimethylammonium bromide (yield: 4.45 g, yield: 69%) was obtained. The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the antibacterial evaluation results.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 4.55 (brs, 1H), 3.77-3.73 (m, 4H), 3.44-3.39 (m, 2H), 3.31 ( s, 6H), 2.54 (brs, 2H), 2.08-2.07 (m, 2H), 1.75 (brs, 2H), 1.33-1.26 (m, 12H), 0 .90-0.86 (m, 3H).

(Antibacterial Urethane Resin Production Example 1: Example 1/PU-A)
45.7 g of polyisocyanate (isocyanurate-type polyisocyanate based on hexamethylene diisocyanate: "Coronate HXR" manufactured by Tosoh Corporation, NCO average functionality 3.5, NCO content 21.0%) temperature-controlled to 60 ° C.; 54.3 g of polyol (polycarbonate diol based on hexanediol: manufactured by Tosoh Corporation, OH functionality: 2, molecular weight: 500) and 1 g of antibacterial agent A were mixed, and dioctyl was used as a catalyst. A urethane resin-forming composition was prepared by adding 0.01 g of tin dilaurate (“special grade reagent” manufactured by Tokyo Chemical Industry Co., Ltd.) and mixing. This composition was sufficiently defoamed under a reduced pressure of 5 mmHg, poured into a mold for forming a flat plate of 2 mm thickness preheated to 100 to 120° C., and cured in an atmosphere of 100° C. for 30 minutes. After that, the cured urethane resin composition was taken out and cured in an atmosphere of 40 to 50° C. for 24 hours to obtain an antibacterial urethane resin composition (PU-A). Table 1 shows the evaluation results of the antibacterial properties of the obtained antibacterial urethane resin composition.

(Antibacterial Urethane Resin Production Examples 2-11: Examples 2-8/PU-B-PU-H, Comparative Examples 1-3/PU-I-PU-K)
Antibacterial urethane resin compositions (Examples 2 to 8/ PU-B to PU-H) and comparative antibacterial urethane resin compositions (Comparative Examples 1 to 3/PU-I to PU-K) were obtained. Table 1 shows the evaluation results of the antibacterial properties of the obtained antibacterial urethane resin composition.

(Unprocessed urethane resin production example: PU-N for control)
An unprocessed product (unprocessed urethane Resin composition) was obtained.

As is clear from the results shown in Table 1, the antibacterial agent according to one aspect of the present invention comprising a quaternary ammonium salt according to one aspect of the present invention has excellent antibacterial activity compared to the antibacterial agent for comparison. Furthermore, when added to a urethane resin to form an antibacterial resin composition, the antibacterial resin composition according to one aspect of the present invention has an antibacterial activity and alcohol resistance compared to the antibacterial resin composition for comparison. It was confirmed that the washability was excellent.

Claims (13)

An antibacterial agent comprising a quaternary ammonium salt represented by formula (1).
(R ¹ ) _a (R ² ) _b (R ³ ) _c N ⁺ ·X ⁻ (1)
(In formula (1),
R ¹ is an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a hydroxyl group,
The number of carbon atoms in ^R1 is
4 to 11 when only one hydrogen atom is substituted with a hydroxyl group;
3 to 11 when two or more hydrogen atoms are substituted with hydroxyl groups;
R ² is an aliphatic hydrocarbon group having 10 to 18 carbon atoms,
R ³ is an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
X ^- is the conjugate base of the acid,
a represents 1 or 2, b represents 1, c represents 1 or 2, and satisfies a+b+c=4, and
the total number of carbon atoms of the aliphatic hydrocarbon groups represented by R ¹ , R ² and R ³ is 15 or more and 23 or less,
When a or c is 2, a plurality of R ¹ or R ³ may be the same or different. ) 2. The antimicrobial agent of claim 1, wherein a is 1, c is 2, and ^R3 is a methyl group. Claim 1, wherein the aliphatic hydrocarbon group represented by R ¹ is at least one selected from the group consisting of a hydroxyalkyl group having 4 to 11 carbon atoms and a dihydroxyalkyl group having 3 to 11 carbon atoms. antibacterial agent. In the aliphatic hydrocarbon group represented by R ¹ , the following conditions:
only one hydrogen atom on the terminal carbon atom is replaced with a hydroxyl group,
at least one hydrogen atom on a terminal carbon atom and at least one hydrogen atom on an adjacent carbon atom are each substituted with a hydroxyl group;
The antibacterial agent according to claim 1, wherein any of The antibacterial agent according to claim 1, wherein the aliphatic hydrocarbon group is a linear alkyl group. 2. The antimicrobial agent of claim 1, wherein X ^- is a halide ion. An antibacterial resin composition in which the antibacterial agent according to any one of claims 1 to 6 is immobilized on a resin containing a functional group reactive with hydroxyl groups. The antibacterial resin composition according to claim 7, wherein the functional group is an isocyanate group. The antibacterial resin composition according to claim 7, wherein the resin is a urethane resin. A quaternary ammonium salt represented by formula (2).

(In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, satisfies m+n=16 to 21, and X ⁻ represents a halide ion.) The quaternary ammonium salt according to claim 10, represented by formula (3).

(In formula (3), n represents an integer from 12 to 14, and X ^- represents a halide ion.) The quaternary ammonium salt according to claim 10, represented by formula (4).

(In formula (4), X ⁻ represents a halide ion.) A quaternary ammonium salt represented by formula (5).

(In formula (5), n represents an integer from 12 to 16, and X ^- represents a halide ion.)