Antimicrobial agent, antimicrobial resin composition and quaternary ammonium salt

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

[0001] The present invention relates to an antibacterial agent, an antibacterial resin composition using the same, and a quaternary ammonium salt.

[0002] In recent years, the market for antibacterial resin compositions in which an antibacterial agent is added to a resin such as a urethane resin has expanded due to the need for hygiene in residential living spaces and automobile interiors. Various inorganic and organic antibacterial agents are known as antibacterial agents to be added to resins, and quaternary ammonium salts, which are cationic surfactants that exhibit antibacterial properties, have also been investigated.

[0003] As antibacterial agents composed of quaternary ammonium salts added to such resins, for example, Patent Document 1 (WO 2016 / 043202) describes didecyldimethylammonium bromide, didecyldimethylammonium chloride, alkyldimethylbenzylammonium chloride, didecyldimethylammonium adipate, and the like, as well as didecylmonomethylhydroxyethylammonium bromide, alkyldimethylhydroxyethylammonium chloride, N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate, didecylmonomethylhydroxyethylammonium adipate, didecylmonomethylhydroxyethylammonium gluconate, didecylmonomethylhydroxyethylammonium sulfonate, alkyldimethylhydroxyethylammonium adipate, alkyldimethylhydroxyethylammonium gluconate, didecylmethylpolyoxyethyleneammonium propionate, and the like.

[0004] Furthermore, Patent Document 2 (Japanese Patent No. 4053635) describes a urethane resin to which the following quaternary ammonium salt (in the following formula, R is a hydrogen atom or a hydrocarbon group, and x and y are integers of 1 to 4) has been added:

[0005]

[0006]

[0007]

[0008]

[0009] 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 The antibacterial activity of ) has been investigated.

[0010] International Publication No. 2016 / 043202 Patent No. 4053635 D. B. Kudryavtsev, et al. , Anticorrosive Effects and Antimicrobial Properties of Alkyldimethyl (hydroxyalkyl) ammonium Bromides, Petroleum Chemistry, 2011, Vol. 51, No. 4, pp. 293-298

[0011] In recent years, the level of antibacterial activity required of antibacterial agents has been increasing, and the level of antibacterial activity washability against alcohol washing has also been increasing due to the increasing number of opportunities for alcohol disinfection, etc. Conventional antibacterial agents described in Patent Document 1, Patent Document 2, Non-Patent Document 1, etc. do not necessarily have sufficient antibacterial activity or alcohol washability.

[0012] One aspect of the present invention has been made in consideration of the problems associated with the prior art, and aims to provide an antibacterial agent that has excellent antibacterial activity and, when added to a resin to form an antibacterial resin composition, exhibits excellent alcohol-washing resistance to the antibacterial activity; an antibacterial resin composition using the antibacterial agent; and a novel quaternary ammonium salt that functions as the antibacterial agent.

[0013] The present invention provides the following aspects.

[0014] [1] An antibacterial agent comprising a quaternary ammonium salt represented by formula (1):

[0015] (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, and R １ The number of carbon atoms in R is 4 to 11 when only one hydrogen atom is substituted with a hydroxyl group, and 3 to 11 when two or more hydrogen atoms are substituted with hydroxyl groups. 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, and X － is a conjugate base of an acid, a represents 1 or 2, b represents 1, c represents 1 or 2, and a+b+c=4 is satisfied, and R １ , R ２ and R ３ When a or c is 2, the total number of carbon atoms in the aliphatic hydrocarbon group represented by １ or R ３ may be the same or different.) [2] a is 1, c is 2, and R ３

[0023] The antibacterial agent according to [1], wherein

[0016] [3] R １ The antibacterial agent according to [1] or [2], wherein the aliphatic hydrocarbon group represented by the formula (I) 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.

[0017] [4] R １The antibacterial agent according to any one of [1] to [3], wherein the aliphatic hydrocarbon group represented by the formula (I) satisfies any one of the following conditions: only one hydrogen atom on the terminal carbon atom is substituted with a hydroxyl group, and at least one hydrogen atom on the terminal carbon atom and at least one hydrogen atom on the carbon atom adjacent thereto are each substituted with a hydroxyl group.

[0018] [5] The antibacterial agent according to any one of [1] to [4], wherein the aliphatic hydrocarbon group is a linear alkyl group.

[0019] [6] X － [6] The antibacterial agent according to any one of [1] to [5], wherein

[0020] [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 a hydroxyl group.

[0021] [8] The antibacterial resin composition according to [7], wherein the functional group is an isocyanate group.

[0022] [9] The antibacterial resin composition according to [7] or [8], wherein the resin is a urethane resin.

[0023]

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

[0024]

[0025] (In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, and m+n=16 to 21 is satisfied; X － represents a halide ion.)

[11] The quaternary ammonium salt according to

[10] , represented by formula (3):

[0026]

[0027] (In formula (3), n represents an integer of 12 to 14, and X － represents a halide ion.

[12] The quaternary ammonium salt according to

[10] , which is represented by formula (4):

[0028]

[0029] (In formula (4), X － represents a halide ion.)

[13] A quaternary ammonium salt represented by formula (5):

[0030]

[0031] (In formula (5), n represents an integer of 12 to 16, and X － represents a halide ion.)

[0032] 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, has excellent alcohol-cleaning resistance to the antibacterial activity. Therefore, according to another aspect of the present invention, an antibacterial resin composition having excellent antibacterial activity and also excellent alcohol-cleaning resistance can be obtained. In yet another aspect of the present invention, a novel quaternary ammonium salt is provided that functions as an antibacterial agent having excellent antibacterial activity and alcohol-cleaning resistance.

[0033] The present invention will be described in detail below with reference to preferred embodiments thereof. First, an antibacterial agent according to one aspect of the present invention will be described.

[0034] The antibacterial agent is represented by the formula (1): 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, and R １ The number of carbon atoms in R is 4 to 11 when only one hydrogen atom is substituted with a hydroxyl group, and 3 to 11 when two or more hydrogen atoms are substituted with hydroxyl groups. 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, and X － is a conjugate base of an acid, a represents 1 or 2, b represents 1, c represents 1 or 2, and a+b+c=4 is satisfied, and R １ , R ２ and R３ When a or c is 2, the total number of carbon atoms in the aliphatic hydrocarbon group represented by １ or R ３ may be the same or different.)

[0035] 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, but is preferably an alkyl group, and particularly preferably a linear alkyl group. 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 alcohol washability. ３ Examples of R include a methyl group, an ethyl group, and a propyl group, and among these, a methyl group is preferred from the viewpoint that antibacterial activity and its resistance to alcohol washing tend to be further improved. ３ The number (c) of R is 1 or 2, and from the viewpoint that antibacterial activity and its resistance to alcohol cleaning tend to be further improved, c is preferably 2. ３ When a plurality of groups are present in one molecule, they may be the same or different.

[0036] In formula (1), R ２ R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and may be linear or branched, saturated or unsaturated. However, alkyl groups are preferred because they enhance antibacterial activity, and linear alkyl groups are particularly preferred. ２ The number of carbon atoms in R is 10 to 18, specifically, for example, 10, 11, 12, 13, 14, 15, 16, 17, or 18, and may be within a range with any two of the numerical values ​​exemplified here as upper and lower limits. ２ The inventors speculate that R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, which provides sufficient hydrophobicity and exhibits antibacterial properties based on its action on cell membranes, resulting in excellent antibacterial activity. ２ Examples of R include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.２ The number (b) is 1.

[0037] In formula (1), R １ is an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a hydroxyl group, and such aliphatic hydrocarbon group may be linear or branched, saturated or unsaturated, but is preferably an alkyl group, and particularly preferably a linear alkyl group, because it enhances antibacterial activity. By introducing a hydroxyl group into at least one aliphatic hydrocarbon group in this way, when an antibacterial agent is added to a production process for a resin such as urethane, the hydroxyl group reacts with a functional group in the resin raw material and is fixed to the resin by a bond such as a covalent bond (preferably a covalent bond), thereby improving the alcohol cleaning resistance of the antibacterial activity.

[0038] And, R in formula (1) １ However, when R has one substituted hydroxyl group, it must be an aliphatic hydrocarbon group having 4 to 11 carbon atoms. The hydrocarbon chain, which is a linker between the cationic moiety and the hydroxyl group, affects the antibacterial activity, and when there is one substituted hydroxyl group, if the aliphatic hydrocarbon group has less than 4 carbon atoms or more than 11 carbon atoms, the antibacterial activity decreases. １ has one substituted hydroxyl group, R １ The number of carbon atoms in is 4 to 11, and may be 5 to 11, specifically, for example, 4, 5, 6, 7, 8, 9, 10, or 11, and may be within a range with any two of the numerical values ​​exemplified here as upper and lower limits. １ As the aliphatic hydrocarbon group, a hydroxyalkyl group having 4 to 11 carbon atoms is preferred, and examples include a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, a hydroxynonyl group, a hydroxydecyl group, a hydroxyundecyl group, etc. The position at which the hydroxyl group is bonded to the aliphatic hydrocarbon group is not particularly limited, but from the viewpoint that when added to a resin, it becomes more likely to react with the functional groups of the resin and the alcohol cleaning resistance of the antibacterial activity tends to be further improved, it is preferable that the hydroxyl group be bonded to the terminal carbon atom on the side not bonded to the N atom.

[0039] Furthermore, R in formula (1)１ However, when R has two or more substituted hydroxyl groups, it is necessary that the aliphatic hydrocarbon group has 3 to 11 carbon atoms. The hydrocarbon chain, which is a linker between the cationic moiety and the hydroxyl group, affects the antibacterial activity, and when there are two or more substituted hydroxyl groups, if the aliphatic hydrocarbon group has less than 3 carbon atoms or more than 11 carbon atoms, the antibacterial activity decreases. １ has two or more substituted hydroxyl groups, R １ The number of carbon atoms in R is 3 to 11, specifically, for example, 3, 4, 5, 6, 7, 8, 9, 10, or 11, and may be within a range with any two of the numerical values ​​exemplified here as upper and lower limits. １ Examples of R include dihydroxypropyl group, dihydroxybutyl group, dihydroxypentyl group, dihydroxyhexyl group, dihydroxyheptyl group, dihydroxyoctyl group, dihydroxynonyl group, dihydroxydecyl group, dihydroxyundecyl group, trihydroxypropyl group, trihydroxybutyl group, trihydroxypentyl group, trihydroxyhexyl group, trihydroxyheptyl group, trihydroxyoctyl group, trihydroxynonyl group, trihydroxydecyl group, and 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 more preferably two. １ As the hydroxyl group, a dihydroxyalkyl group having 3 to 11 carbon atoms is preferred. The position at which the hydroxyl group is bonded to the aliphatic hydrocarbon group is not particularly limited, but from the viewpoint that when added to a resin, the hydroxyl group is more likely to react with the functional group of the resin and the alcohol-resistance of the antibacterial activity tends to be further improved, when there are two or more substituted hydroxyl groups, it is preferred that the hydroxyl groups are bonded to the terminal carbon atom on the side not bonded to the N atom and the second carbon atom from the end.

[0040] Also, R １ The number (a) is 1 or 2, and a + b + c = 4 must be satisfied. From the viewpoint that antibacterial activity tends to be further improved, a is preferably 1.１ When a plurality of groups are present in one molecule, they may be the same or different.

[0041] Furthermore, R in one molecule of the quaternary ammonium salt represented by formula (1) １ , R ２ and R ３ The total number of carbon atoms in the aliphatic hydrocarbon group (R １ ~R ３ The total number of carbon atoms in R also affects the antibacterial activity. If the total number of carbon atoms is less than 15, the antibacterial activity decreases, while if the total number of carbon atoms exceeds 23, the antibacterial activity decreases. １ , R ２ and R ３ The total number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is 15 or more and 23 or less, specifically, for example, 15, 16, 17, 18, 19, 20, 21, 22, or 23, and may be within a range having any two of the numerical values ​​exemplified here as the upper and lower limits.

[0042] In addition, X in formula (1) － is the conjugate base of the acid. X － is preferably a conjugate base of a strong acid. By combining the specific quaternary ammonium cation and the conjugate base (anion) of a strong acid and using the resulting salt, the salt functions as an antibacterial agent having excellent antibacterial activity, and when added to a resin to form an antibacterial resin composition, the antibacterial activity tends to be improved. On the other hand, the conjugate base of a weak acid such as a carboxylate ion tends not to sufficiently improve the antibacterial activity. Examples of conjugate bases of strong acids include halide ions such as bromine (Br), chlorine (Cl), fluorine (F), and iodine (I), as well as nitrate ions, sulfate ions, phosphate ions, and perchlorate ions. Among these, halide ions are preferred, with bromine (Br) or chlorine (Cl) being particularly preferred, as they tend to further improve antibacterial activity.

[0043] The method for producing the antibacterial agent according to one embodiment of the present invention (the quaternary ammonium salt represented by formula (1) according to one embodiment of the present invention) is not particularly limited, but for example, the following method is preferably employed.

[0044] <Method 1> A compound of formula (1a) corresponding to the target quaternary ammonium salt: (R ２ ) (R ３ ) ２ N (1a) (In formula (1a), R ２ , R ３ has the same meaning as in formula (1).) is reacted with a tertiary amine represented by formula (1b): (R １ )X (1b) (In formula (1b), R １ and X has the same meaning as in formula (1). In a reaction medium, the resulting product is quaternized with a halogenated alcohol represented by the formula (1), and if necessary, washed and dried to obtain the desired quaternary ammonium salt.

[0045] <Method 2> A compound of formula (1c) corresponding to the target quaternary ammonium salt: (R １ ) (R ３ ) ２ N (1c) (In formula (1c), R １ , R ３ has the same meaning as in formula (1).) is converted into a tertiary amine represented by formula (1d): (R ２ )X (1d) (In formula (1d), R ２ and X has the same meaning as in formula (1). In a reaction medium, the resulting product is quaternized with an alkyl halide represented by the formula (1), and if necessary, washed and dried to obtain the desired quaternary ammonium salt.

[0046] <Method 3> A compound of formula (1e) corresponding to the target quaternary ammonium salt: (R １ ) ２ (R ３ )N (1e) (In formula (1e), R １ , R ３ has the same meaning as in formula (1).) is converted into a tertiary amine represented by formula (1f): (R ２ )X (1f) (In formula (1f), R ２and X has the same meaning as in formula (1). In a reaction medium, the resulting product is quaternized with an alkyl halide represented by the formula (1), and if necessary, washed and dried to obtain the desired quaternary ammonium salt.

[0047] <Method 4> A compound of the formula (1g) corresponding to the target quaternary ammonium salt: (R １ ) ２ (R ２ )N (1g) (In formula (1g), R １ , R ２ has the same meaning as in formula (1).) is converted into a tertiary amine represented by formula (1h): (R ３ )X (1h) (In formula (1h), R ３ and X has the same meaning as in formula (1). In a reaction medium, the resulting product is quaternized with an alkyl halide represented by the formula (1), and if necessary, washed and dried to obtain the desired quaternary ammonium salt.

[0048] The reaction solvent used in the quaternization reaction is not particularly limited, and examples thereof include acetonitrile, propanenitrile, dimethylformamide (hereinafter sometimes referred to as DMF), dimethyl sulfoxide (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-dichlorobenzene, m-dichlorobenzene, and nitrobenzene, and among these, acetonitrile is preferred from the viewpoint of good yield.

[0049] Next, an antibacterial resin composition according to one embodiment of the present invention will be described. The antibacterial resin composition is a resin containing a functional group reactive with a hydroxyl group, and the antibacterial agent is immobilized in the resin.

[0050] Examples of functional groups reactive with hydroxyl groups include isocyanate groups and epoxy groups. Among these, isocyanate groups are preferred because they tend to form covalent bonds with hydroxyl groups in a temperature range where quaternary ammonium does not decompose, thereby immobilizing the quaternary ammonium to the resin and further improving the alcohol-cleaning resistance of the antibacterial activity.

[0051] Resins containing such functional groups are not particularly limited, but examples include urethane resins, urea resins, urethane urea resins, polyimide resins, polyoxazolidone resins, polycarbodiimide resins, polyisocyanurate resins, etc. Among these, urethane resins obtained from polyisocyanate and polyol, urea resins obtained from polyisocyanate and polyamine, and urethane urea resins obtained from polyisocyanate, polyol, and polyamine (monoamine) are preferred, as they tend to form covalent bonds by reaction with hydroxyl groups, thereby immobilizing the resin and further improving the alcohol-cleaning resistance of antibacterial activity. Furthermore, urethane resins obtained from polyisocyanate and polycarbonate polyol are more preferred, as they tend to form covalent bonds by reaction with hydroxyl groups, thereby immobilizing the resin and further improving the alcohol-cleaning resistance of antibacterial activity, as well as providing good appearance, mechanical properties, and durability.

[0052] The amount of the antibacterial agent added to the antibacterial resin composition is not particularly limited and is adjusted appropriately depending on the purpose, etc., but usually the amount of the antibacterial agent added to the resin composition is preferably 5 mass % or less, and more preferably 0.1 to 5 mass %.

[0053] Furthermore, in the antibacterial resin composition, additives such as antioxidants, ultraviolet absorbers, pigments, paints, solvents, flame retardants, hydrolysis inhibitors, lubricants, plasticizers, fillers, antistatic agents, dispersants, catalysts, storage stabilizers, surfactants, and leveling agents may be appropriately blended as needed.

[0054] The method for obtaining an antibacterial resin composition by immobilizing the antibacterial agent in the resin is not particularly limited, but the following methods are preferably used, for example: (i) A method in which the antibacterial agent is mixed into a resin-forming composition in a step prior to the reaction of resin raw materials (e.g., polyisocyanate and polyol), and the obtained resin-forming composition is reacted to obtain an antibacterial resin composition; (ii) A method in which the antibacterial agent is mixed with resin pellets or powder in a mixer, and then the mixture is heated, melted, and kneaded in an extruder to obtain an antibacterial resin composition; (iii) A method in which a high concentration of antibacterial agent is blended in a resin to prepare a so-called masterbatch, and the masterbatch is then diluted to a predetermined concentration with resin pellets or powder in order to obtain an antibacterial resin composition.

[0055] The shape of the antibacterial resin composition is not particularly limited, and it may be made into various resin molded products such as blocks, plates, sheets, films, fibers, etc. depending on the purpose, and used for various applications where hygiene is highly required, such as in living spaces of homes and interiors of automobiles.

[0056] Next, a quaternary ammonium salt according to one embodiment of the present invention will be described. A first quaternary ammonium salt according to one embodiment of the present invention is represented by formula (2):

[0057]

[0058] (In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, and m+n=16 to 21 is satisfied; X － represents a halide ion.) It is a quaternary ammonium salt represented by the formula:

[0059] m represents an integer from 6 to 11, specifically, for example, 6, 7, 8, 9, 10, or 11, and may be within a range with any two of the numerical values ​​exemplified here as upper and lower limits. n represents an integer from 10 to 14, specifically, for example, 10, 11, 12, 13, or 14, and may be within a range with any two of the numerical values ​​exemplified here as upper and lower limits. m+n satisfies 16 to 21, specifically, for example, 16, 17, 18, 19, 20, or 21, and may be within a range with any two of the numerical values ​​exemplified here as upper and lower limits.

[0060] Among the quaternary ammonium salts represented by formula (2), those in which m is 6 and n is an integer from 12 to 14 are preferred, and such quaternary ammonium salts are represented by formula (3):

[0061]

[0062] (In formula (3), n represents an integer of 12 to 14, and X － represents a halide ion.

[0063] Among the quaternary ammonium salts represented by formula (2), those in which m is 11 and n is 10 are also preferred, and such quaternary ammonium salts are represented by formula (4):

[0064]

[0065] (In formula (4), X － represents a halide ion.

[0066] Furthermore, the second quaternary ammonium salt according to one embodiment of the present invention is represented by formula (5):

[0067]

[0068] (In formula (5), n represents an integer of 12 to 16, and X － represents a halide ion.

[0069] The quaternary ammonium salts represented by formulas (2) to (5) are novel compounds that have excellent antibacterial activity and, when added to a resin to form an antibacterial resin composition, function as antibacterial agents that have excellent alcohol-cleaning resistance in terms of antibacterial activity.

[0070] The quaternary ammonium salts represented by formulas (2) to (5) can be produced in accordance with the above-mentioned methods 1 to 4. The quaternary ammonium salt represented by formula (2) has been actually produced in Examples 1 to 5, the quaternary ammonium salt represented by formula (3) in Examples 2 and 3, the quaternary ammonium salt represented by formula (4) in Example 1, and the quaternary ammonium salt represented by formula (5) in Examples 7 and 8.

[0071] 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, has excellent alcohol-cleaning resistance to the antibacterial activity. Therefore, according to another aspect of the present invention, an antibacterial resin composition having excellent antibacterial activity and also excellent alcohol-cleaning resistance can be obtained. In yet another aspect of the present invention, a novel quaternary ammonium salt is provided that functions as an antibacterial agent having excellent antibacterial activity and alcohol-cleaning resistance.

[0072] 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.

[0073] The structural analysis of the antibacterial agent, the antibacterial property evaluation of the antibacterial agent, and the antibacterial property evaluation of the antibacterial-treated urethane resin were carried out and evaluated by the following methods.

[0074] (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) was used as the chemical shift standard. ３ ) or deuterated dimethyl sulfoxide (manufactured by Ambridge Isotope Laboratories, Inc., hereinafter referred to as DMSO-d ６ Each antibacterial agent was dissolved at a concentration of 1% by mass based on the chemical shift, and a nuclear magnetic resonance spectrometer (manufactured by Bruker, "AVANCE II") was used to measure the chemical shift. １ The frequency was measured by 1 H-NMR.

[0075] (Evaluation of Antibacterial Activity of Antibacterial Agents) The antibacterial activity of each antibacterial agent was evaluated by measuring the minimum inhibitory concentration (MIC).

[0076] (1) Measurement method of minimum inhibitory concentration Each test bacterium was cultured for 1 day at 30 ° C. using Nutrient agar medium (Nutrient liquid medium (Nutrient broth, manufactured by Difco) + 1.5% (w / v) agar) and suspended in sterilized ion-exchanged water to a concentration equivalent to 0.5 McFarland to prepare a bacterial solution for inoculation. Test bacterium: Staphylococcus epidermidis NBRC 100911. The water-soluble test substance was adjusted to a concentration of 8.0 mg / mL with ion-exchanged water and filter-sterilized to prepare a stock solution. The stock solution was diluted 10-fold with Nutrient liquid medium to prepare a solution with the maximum diluted concentration (800 μg / mL). On the other hand, the water-insoluble test substance was prepared in dimethyl sulfoxide (Tokyo Chemical Industry Reagents Co., Ltd.) at a concentration of 80 mg / mL, and the unsterilized solution was used as a stock solution. The stock solution was diluted 100-fold with Nutrient liquid medium to obtain a solution with the maximum diluted concentration (800 μg / mL).

[0077] The test substance (antibacterial agent) was diluted with Nutrient liquid medium at a dilution ratio of 2x to prepare 11 levels of test substance solutions, including the highest concentration, with the maximum dilution being the highest concentration. 100 μL of each test substance solution was dispensed into a 96-well microplate (U-shaped wells), and 5 μL of the inoculum solution of each test bacterium was inoculated into each well. 100 μL of Nutrient liquid medium (test substance-free Nutrient liquid medium) not containing the test substance was dispensed into the 96-well microplate, and 5 μL of the inoculum solution of each test bacterium was inoculated to serve as a control for test bacterium growth.

[0078] The 96-well microplate was sealed with a breathable sheet, and the test solution was incubated statically at 30°C for 48 hours. After incubation, the criteria for determining growth inhibition were whether no turbidity or precipitation was visible to the naked eye, or whether there was a single precipitate with a diameter of 1 mm or less. After confirming the growth of the test bacteria in the control Nutrient liquid medium containing no test substance, the MIC was determined as the lowest test substance concentration among the wells in which bacterial growth was not visible to the naked eye. Each test substance was tested twice, and the average value was used as the measured value.

[0079] (2) Determination of minimum inhibitory concentration Based on the measurement results of the minimum inhibitory concentration for each antibacterial agent, the antibacterial activity of the antibacterial agent was evaluated according to the following criteria: <Criteria for determining minimum inhibitory concentration> A: Minimum inhibitory concentration (μg / mL) < 30 B: Minimum inhibitory concentration (μg / mL) = 30 to 100 C: Minimum inhibitory concentration (μg / mL) > 100.

[0080] (Evaluation of alcohol-washing resistance of antibacterial activity of antibacterial urethane resin) The alcohol-washing resistance of the antibacterial activity of each antibacterial urethane resin was evaluated by immersing each antibacterial urethane resin in ethanol after production and boiling it for 6 hours to wash it, and then measuring the bacterial growth inhibition rate using each antibacterial urethane resin.

[0081] (1) Preparation of media and physiological saline solutions used: 1) NA medium (double-concentration Nutrient liquid medium (manufactured by Difco) + 5.0 g / L NaCl + 15 g / L agar) 2) NB medium (normal bouillon medium, manufactured by Eiken Chemical Co., Ltd.) 3) SCDLP medium (Daigo, manufactured by Nippon 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 KH ２ P.O. ４ , 8.5 g / L: NaCl, pH: 7.2).

[0082] (2) Preparation of test bacteria and test bacterial solution 1) Test bacteria: Staphylococcus epidermidis (Staphylococcus epidermidis NBRC 100911) 2) Preparation of test bacterial solution: A frozen and preserved strain was cultured in NA medium at 35°C for 24 hours. This cultured strain was transferred to a new NA medium and cultured at 35°C for 24 hours. The grown colonies were scraped off and cultured in NB medium at a concentration of 1 / 100 to a concentration of approximately 1 x 10 ６ The concentration was adjusted to cells / mL, and this was used as a test bacterial solution.

[0083] (3) Test Method The test method was performed as follows, with reference to "JIS Z2801:2012 Antibacterial Products - Antibacterial Test Methods and Antibacterial Effect." 1) Inoculation and Cultivation of Test Bacterial Solution: Test samples (antibacterial urethane resin and untreated urethane resin) were cut into 50 mm squares, wiped and disinfected on the entire surface with a paper wipe soaked in 99% ethanol, and then completely dried. They were placed in a petri dish and 0.4 mL of test bacterial solution was dropped onto them. A 40 mm square covering film (polyethylene film) was placed on top of the dropped test bacterial solution and tightly attached so that the test bacterial solution was distributed throughout the test sample. After inoculation, the test sample was allowed to act for a predetermined time under the test temperature and humidity conditions. Three test samples (n = 3) were tested for each condition. 2) Bacterial Count Measurement: After the predetermined time of action, 10 mL of SCDLP medium was added to the petri dish containing the test sample, and the test bacteria were washed out of the test sample using a pipette (1000 μL). The washed liquid was used as a sample liquid for measuring the number of bacteria. A series of dilutions of the sample liquid was prepared using phosphate buffered saline, and 100 μL of each of the original sample liquid and the diluted liquid was spread on SA medium and cultured at 35°C for 24 hours. After the culture, the number of grown colonies was counted and 1 cm of the test sample was measured. ２ Number of test bacteria per unit area (quantitative lower limit: 0.63 / cm ２ ) was calculated and the average value was used as the measured value.

[0084] (4) Calculation of bacterial growth inhibition rate The bacterial growth inhibition rate was calculated using the measured value of the number of test bacteria obtained above according to the following formula (1): Bacterial growth inhibition rate (%) = {1 - (number of test bacteria on antibacterial-treated urethane resin 24 hours after inoculation) / (number of test bacteria on untreated urethane resin 24 hours after inoculation)} × 100 (formula 1).

[0085] (5) Judgment 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 cleaning resistance of antibacterial activity) of the antibacterial urethane resin were evaluated according to the following criteria: <Judgment criteria for bacterial growth inhibition rate> A: Bacterial growth inhibition rate (%) > 90 B: Bacterial growth inhibition rate (%) = 50 to 90 C: Bacterial growth inhibition rate (%) < 50.

[0086] (Antibacterial Agent Synthesis Example 1: Example 1 / Antibacterial Agent A) Synthesis of N-decyl-N-(11-hydroxyundecyl)-N,N-dimethylammonium bromide A stirrer, 11-bromo-1-undecanol (1.50 g, 5.97 mmol), N,N-dimethyldecylamine (1.42 mL, 5.98 mmol), and acetonitrile (10 mL) were placed in a 50 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 5 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and then dried under reduced pressure to obtain a white solid of N-decyl-N-(11-hydroxyundecyl)-N,N-dimethylammonium bromide (yield: 2.58 g, 99%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial activity evaluation results are shown in Table 1.

[0087] １ H-NMR (400MHz, DMSO-d ６ ): δ4.34 (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).

[0088] (Antibacterial Agent Synthesis Example 2: Example 2 / Antibacterial Agent B) Synthesis of N-(6-hydroxyhexyl)-N,N-dimethyltetradecylammonium bromide A stirrer, 6-dimethylamino-1-hexanol (7.49 g, 50.0 mmol), 1-bromotetradecane (14.3 g, 50.0 mmol), and acetonitrile (25 mL) were placed in a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 5 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and then dried under reduced pressure to obtain a white solid of N-(6-hydroxyhexyl)-N,N-dimethyltetradecylammonium bromide (yield: 20.9 g, 99%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial activity evaluation results are shown in Table 1.

[0089] １ H-NMR (400MHz, DMSO-d ６ ​​): δ4.38 (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).

[0090] (Antibacterial Agent Synthesis Example 3: Example 3 / Antibacterial Agent C) Synthesis of N-dodecyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium bromide A stirrer, 6-bromo-1-hexanol (3.62 g, 20.0 mmol), acetonitrile (30 mL), and N,N-dimethyldodecylamine (4.27 g, 20.0 mmol) were placed in a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 7 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and then dried under reduced pressure to obtain a colorless viscous product of N-dodecyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium bromide (yield: 7.81 g, 99%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial property evaluation results are shown in Table 1.

[0091] １ H-NMR (400MHz, DMSO-d ６ ): δ4.38 (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).

[0092] ​(Antibacterial Agent Synthesis Example 4: Example 4 / Antibacterial Agent D) Synthesis of N-decyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium bromide A stirrer, 6-bromo-1-hexanol (3.62 g, 20.0 mmol), acetonitrile (30 mL), and N,N-dimethyldecylamine (3.71 g, 20.0 mmol) were placed in a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 7 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and then dried under reduced pressure to obtain a colorless viscous product of N-decyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium bromide (yield: 7.26 g, 99%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial property evaluation results are shown in Table 1.

[0093] １ H-NMR (400MHz, CDCl ３ ): δ3.65-3.59 (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).

[0094] (Antibacterial Agent Synthesis Example 5: Example 5 / Antibacterial Agent E) Synthesis of N-decyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium chloride A stirrer, 6-chloro-1-hexanol (3.00 g, 22.0 mmol), acetonitrile (33 mL), and N,N-dimethyldecylamine (5.22 mL, 22.0 mmol) were placed in a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 22 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with diethyl ether and ethyl acetate and then dried under reduced pressure to obtain a white solid of N-decyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium chloride (yield: 4.04 g, 57%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial activity evaluation results are shown in Table 1.

[0095] １ H-NMR (400MHz, CDCl ３ ​​): δ3.64-3.59 (m, 4H), 3.46-3.42 (m, 3H), 3.37 (s, 6H), 1.94-1.26 (m, 24H), 0.90-0.86 (m, 3H).

[0096] (Antibacterial Agent Synthesis Example 6: Example 6 / Antibacterial Agent F) Synthesis of N-(4-hydroxybutyl)-N-hexadecyl-N,N-dimethylammonium bromide A stirrer, 4-(dimethylamino)-1-butanol (5.98 g, 50.0 mmol), 1-bromohexadecane (15.9 g, 50.0 mmol), and acetonitrile (25 mL) were placed in a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 5 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and then dried under reduced pressure to obtain a white solid of N-(4-hydroxybutyl)-N-hexadecyl-N,N-dimethylammonium bromide (yield: 20.4 g, 97%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial activity evaluation results are shown in Table 1.

[0097] １ H-NMR (400MHz, DMSO-d ６ ): δ4.56 (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).

[0098] ​(Antibacterial Agent Synthesis Example 7: Example 7 / Antibacterial Agent G) Synthesis of N-(2,3-dihydroxypropyl)-N-hexadecyl-N,N-dimethylammonium bromide A stirrer, 3-bromo-1,2-propanediol (2.35 g, 15.2 mmol), N,N-dimethylhexadecylamine (4.16 g, 15.4 mmol), and acetonitrile (25 mL) were placed in a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 5 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and then dried under reduced pressure to obtain a white solid of N-(2,3-dihydroxypropyl)-N-hexadecyl-N,N-dimethylammonium bromide (yield: 5.47 g, 85%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial activity evaluation results are shown in Table 1.

[0099] １ H-NMR (400MHz, DMSO-d ６ ): δ5.36 (d, J=8.2Hz, 1H), 5.00 (t, J=5.8Hz, 1H), 4.00 (m, 1H), 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).

[0100] ​(Antibacterial Agent Synthesis Example 8: Example 8 / Antibacterial Agent H) Synthesis of N-dodecyl-N-(2,3-dihydroxypropyl)-N,N-dimethylammonium bromide A stirrer, 3-bromo-1,2-propanediol (2.35 g, 15.2 mmol), N,N-dimethyldodecylamine (3.29 g, 15.4 mmol), and acetonitrile (25 mL) were placed in a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 5 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and then dried under reduced pressure to obtain a white solid of N-dodecyl-N-(2,3-dihydroxypropyl)-N,N-dimethylammonium bromide (yield: 4.82 g, 85%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial activity evaluation results are shown in Table 1.

[0101] １ H-NMR (400MHz, DMSO-d ６ ): δ5.36 (d, J=8.2Hz, 1H), 5.00 (t, J=5.8Hz, 1H), 4.00 (m, 1H), 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).

[0102] (Antibacterial Agent Synthesis Example 9: Comparative Example 1 / Antibacterial Agent I) Synthesis of N-(11-hydroxyundecyl)-N-hexadecyl-N,N-dimethylammonium bromide A stirrer, 11-bromo-1-undecanol (1.40 g, 5.57 mmol), N,N-dimethylhexadecylamine (1.88 mL, 5.57 mmol), and acetonitrile (10 mL) were placed in a 50 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 7 hours. After cooling, the solvent was distilled off under reduced pressure, and the resulting crude product was washed with diethyl ether to obtain a white solid of N-(11-hydroxyundecyl)-N-hexadecyl-N,N-dimethylammonium bromide (yield: 2.81 g, 97%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial activity evaluation results are shown in Table 1. ​

[0103] １ H-NMR (400MHz, CDCl ３ ): δ3.67-3.62 (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).

[0104] (Antibacterial Agent Synthesis Example 10: Comparative Example 2 / Antibacterial Agent J) Synthesis of N-butyl-N-(11-hydroxyundecyl)-N,N-dimethylammonium bromide A stirrer, 11-bromo-1-undecanol (1.70 g, 6.77 mmol), N,N-dimethylbutylamine (0.96 mL, 6.82 mmol), and acetonitrile (12 mL) were placed in a 50 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 7 hours. After cooling, the solvent was distilled off under reduced pressure, and the resulting crude product was washed with diethyl ether to obtain a white solid of N-butyl-N-(11-hydroxyundecyl)-N,N-dimethylammonium bromide (yield: 2.22 g, 93%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial activity evaluation results are shown in Table 1.

[0105] １ H-NMR (400MHz, CDCl ３ ): δ3.65-3.62 (m, 2H), 3.56-3.51 (m, 4H), 3.40 (s, 6H), 1.80-1.28 (m, 23H), 1.03-0.99 (m, 3H).

[0106] ​​(Antibacterial Agent Synthesis Example 11: Comparative Example 3 / Antibacterial Agent K) Synthesis of N-decyl-N-(3-hydroxypropyl)-N,N-dimethylammonium bromide A stirrer, 3-bromo-1-propanol (2.78 g, 20.0 mmol), N,N-dimethyldecylamine (3.71 g, 20.0 mmol), and acetonitrile (30 mL) were placed in a 100 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer, and the mixture was stirred under reflux (82°C) for 5 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and then dried under reduced pressure to obtain a white solid of N-decyl-N-(3-hydroxypropyl)-N,N-dimethylammonium bromide (yield: 4.45 g, 69%). The NMR analysis results of the obtained antibacterial agent are as follows, and the antibacterial activity evaluation results are shown in Table 1.

[0107] １ H-NMR (400MHz, CDCl ３ ): δ4.55 (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).

[0108] ​(Antibacterial urethane resin production example 1: Example 1 / PU-A) 45.7 g of polyisocyanate (isocyanurate type polyisocyanate based on hexamethylene diisocyanate: manufactured by Tosoh Corporation "Coronate HXR", NCO average functionality 3.5, NCO content 21.0%) adjusted to 60 ° C., 54.3 g of polyol (polycarbonate diol based on hexanediol: manufactured by Tosoh Corporation "Nippolan 970", OH functionality 2, molecular weight 500) adjusted to 40 ° C., and 1 g of antibacterial agent were mixed, and 0.01 g of dioctyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd. "Special Grade Reagent") was added as a catalyst and mixed to prepare a urethane resin-forming composition. This composition was thoroughly degassed under a reduced pressure of 5 mmHg, then poured into a 2 mm thick plate mold preheated to 100-120°C, and cured for 30 minutes in a 100°C atmosphere. The cured urethane resin composition was then removed and further aged for 24 hours in a 40-50°C atmosphere to obtain an antibacterial urethane resin composition (PU-A). The results of evaluating the antibacterial properties of the obtained antibacterial urethane resin composition are shown in Table 1.

[0109] (Antibacterial Urethane Resin Production Examples 2 to 11: Examples 2 to 8 / PU-B to PU-H, Comparative Examples 1 to 3 / PU-I to 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 in the same manner as in Antibacterial Urethane Resin Production Example 1 (Example 1 / PU-A), except that antibacterial agent A was replaced with antibacterial agents B to K. The evaluation results of the antibacterial properties of the obtained antibacterial urethane resin compositions are shown in Table 1.

[0110] (Untreated Urethane Resin Production Example: Control PU-N) An untreated product (untreated urethane resin composition) to be used as a control for evaluating antibacterial properties was obtained in the same manner as in Antibacterial Urethane Resin Production Example 1 (Example 1 / PU-A), except that antibacterial agent A was not added.

[0111]

[0112] As is clear from the results shown in Table 1, the antibacterial agent according to one embodiment of the present invention, which is composed of a quaternary ammonium salt according to one embodiment of the present invention, has superior antibacterial activity compared to the comparative antibacterial agent. Furthermore, when added to a urethane resin to form an antibacterial resin composition, it was confirmed that the antibacterial resin composition according to one embodiment of the present invention has superior alcohol cleaning resistance of antibacterial activity compared to the comparative antibacterial resin composition.

Claims

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 one hydrogen atom is replaced by a hydroxyl group, R １ has 4 to 11 carbon atoms, 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 a+b+c=4 is satisfied; and R １ , R ２ and R ３ The total number of carbon atoms in the aliphatic hydrocarbon groups represented by the formula: When a or c is 2, a plurality of R １ Or R ３ may be the same or different.)

2. a is 1, c is 2, and R ３ The antibacterial agent according to claim 1 , wherein is a methyl group.

3. R １ The antibacterial agent according to claim 1, wherein the aliphatic hydrocarbon group represented by the following formula (I) is a hydroxyalkyl group having 4 to 11 carbon atoms.

4. R １ 2. The antibacterial agent according to claim 1, wherein in the aliphatic hydrocarbon group represented by the formula: wherein only one hydrogen atom on a terminal carbon atom is substituted with a hydroxyl group.

5. The antibacterial agent according to claim 1 , wherein the aliphatic hydrocarbon group is a straight-chain alkyl group.

6. X － The antimicrobial agent of claim 1 , wherein is a halide ion.

7. The antibacterial agent described in claim 1, which consists of a quaternary ammonium salt represented by formula (2). 【Chemistry 1】 (In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, and m+n=16 to 21 is satisfied, and X − represents a halide ion.)

8. The antibacterial agent described in claim 1, which consists of a quaternary ammonium salt represented by formula (3). 【Chemistry 2】 (In formula (3), n represents an integer of 12 to 14, and X − represents a halide ion.)

9. The antibacterial agent described in claim 1, which consists of a quaternary ammonium salt represented by the following formula: 【Chemistry 3】

10. 10. An antibacterial resin composition comprising the antibacterial agent according to claim 1 immobilized on a resin containing a functional group reactive with a hydroxyl group.

11. The antibacterial resin composition according to claim 10, wherein the functional group is an isocyanate group.

12. The antibacterial resin composition according to claim 10, wherein the resin is a urethane resin.

13. A quaternary ammonium salt represented by formula (4): 【Chemistry 4】 (In formula (4), X － represents a halide ion.)

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