Antibacterial agent composition

Abstract

To provide an antibacterial agent composition that is superior in antibacterial efficacy as well as prolonged antibacterial effectiveness.SOLUTION: The present invention relates to an antibacterial agent composition comprising (A) a specific cationic cellulose derivative and (B) at least one component selected from an anionic compound, a nonionic compound and an amphoteric compound, wherein the content of the component (A) in the antibacterial agent composition is 0.0005-20 mass% and the mass ratio [(A) / (B)] of the component (A) to the component (B) is 1.0-47 inclusive.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an antibacterial composition. [Background technology]

[0002] Cationic cellulose derivatives are known to have antibacterial properties and are used in a variety of applications. Patent Document 1 describes a hemostatic material containing cationic cellulose. Patent Document 2 describes a method for enhancing the antimicrobial efficacy of a composition against acanthamoebae, the method comprising the step of including a polycationic material in the composition, and the polycationic material includes a cationic cellulose polymer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2017-140231 A [Patent Document 2] Special Publication No. 2006-501301 Summary of the Invention [Problem to be solved by the invention]

[0004] Traditionally, in order to improve living environments and public health, antibacterial agents have been applied to objects such as tables, doors, walls, kitchen sinks, washstands, bathrooms, and toilets in homes, accommodations, restaurants, etc. to impart antibacterial properties. Furthermore, since the end of 2019, the number of times the above objects are disinfected or sterilized per day has increased dramatically due to the global spread of the new coronavirus infection (CoVid-19). Simple methods for disinfecting or sterilizing the above objects include spraying them with an ethanol-containing spray and wiping them off with a cloth, wiping them off with ethanol tissue, etc.

[0005] The present inventors have tried to apply an antibacterial composition containing a cationic cellulose derivative to the above-mentioned object, and have found that the composition can impart excellent antibacterial properties to the above-mentioned object. However, they have also found that the antibacterial properties imparted to the above-mentioned object are significantly reduced when the above-mentioned object is disinfected or sterilized with an ethanol product. Therefore, it is desired to develop an antibacterial composition that can suppress the reduction in antibacterial properties even when the above-mentioned object is disinfected or sterilized with an ethanol product, that is, an antibacterial composition that has excellent antibacterial durability.

[0006] The present invention relates to an antibacterial composition having excellent antibacterial properties and excellent durability of antibacterial properties. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by an antibacterial composition containing a cationic cellulose derivative having a specific structure and at least one compound selected from an anionic compound, a nonionic compound, and an amphoteric compound in a specific ratio, and containing the cationic cellulose derivative in a specific concentration. The present invention relates to the following [1]. [1] An antibacterial composition comprising the following components (A) and (B): (A) A cationic cellulose derivative represented by the following general formula (I): (B) at least one selected from an anionic compound, a nonionic compound, and an amphoteric compound The content of component (A) in the antibacterial composition is 0.0005 to 20% by mass, An antibacterial composition, wherein the mass ratio of component (A) to component (B) [(A) / (B)] is 1.0 or more and 47 or less. [ka] (In the formula, R 1 ~R 3 Each independently represents a hydrogen atom or a group represented by the following general formula (II), and d represents the average number of repetitions. However, all R 1 ~R 3 never represents a hydrogen atom.) [ka] (In general formula (II), R 4 represents a hydrogen atom or a group represented by the following general formula (III), L 1 represents C2H4 or C3H6. p is the average number of repetitions and is 0 to 10. However, all p's are not 0, and all R 4 does not represent a hydrogen atom, and all R 4 does not represent a group represented by the following general formula (III). [ka] (In general formula (III), R 5 ~R 7 each independently represents an alkyl group having 1 to 4 carbon atoms; L 2 represents an alkylene group having 1 to 6 carbon atoms; X - represents at least a portion of a halide ion. Effect of the Invention

[0008] According to the present invention, it is possible to provide an antibacterial composition having excellent antibacterial properties and excellent antibacterial durability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, preferred embodiments of the present invention will be described. In this specification, "X to Y" indicating a numerical range means "X or more and Y or less". In this specification, the upper and lower limits of the numerical range can be arbitrarily combined. In addition, in the general formula described in this specification, when there are multiple substituents or linking groups, etc., indicated by specific symbols (hereinafter, referred to as substituents, etc.), each of the substituents, etc. may be the same or different from each other.

[0010] [Antibacterial composition] The antibacterial composition of the present invention (hereinafter also simply referred to as "the composition of the present invention") contains the following components (A) and (B). (A) A cationic cellulose derivative represented by the following general formula (I): [ka] (In the formula, R 1 ~R 3 Each independently represents a hydrogen atom or a group represented by the following general formula (II), and d represents the average number of repetitions. However, all R 1 ~R 3 never represents a hydrogen atom.) [ka] (In general formula (II), R 4 represents a hydrogen atom or a group represented by the following general formula (III), L 1 represents C2H4 or C3H6. p is the average number of repetitions and is 0 to 10. However, all p's are not 0, and all R 4 does not represent a hydrogen atom, and all R 4 does not represent a group represented by the following general formula (III). [ka] (In general formula (III), R 5 ~R 7 each independently represents an alkyl group having 1 to 4 carbon atoms; L 2 represents an alkylene group having 1 to 6 carbon atoms; X - represents at least a portion of a halide ion. (B) at least one selected from an anionic compound, a nonionic compound, and an amphoteric compound The content of component (A) in the antibacterial composition of the present invention is 0.0005 to 20% by mass, and the mass ratio of component (A) to component (B) [(A) / (B)] is 1.0 or more and 47 or less.

[0011] The antibacterial composition of the present invention has excellent antibacterial properties and also has excellent antibacterial durability. Although the detailed mechanism behind this is not clear, it is thought to be as follows. The cationic cellulose derivative represented by general formula (I) contained in the antibacterial composition of the present invention has a (poly)oxyalkylene group represented by general formula (II) and a cationic group represented by general formula (III). The (poly)oxyalkylene group has the effect of forming a mesh-like network in the cationic cellulose derivative in water and dispersing or dissolving it uniformly. On the other hand, the cationic group has antibacterial properties, but the cationic cellulose derivatives aggregate with each other due to the cationic group, which becomes a factor that inhibits the maintenance of the network. In the present invention, the cationic cellulose derivative (component (A)) is used at a specific concentration in combination with at least one selected from an anionic compound, a nonionic compound, and an amphoteric compound (component (B)), and the mass ratio of component (A) to component (B) [(A) / (B)] is controlled within a specific range. As a result, the aggregation of the cationic group in water is suppressed, and the network is maintained not only in water but also after application to the target object. By maintaining the above network, the compound can be applied evenly to the target object, and by increasing adhesion to the target object, the antibacterial properties of the cationic groups are effectively expressed, and it is believed that the antibacterial properties are prevented from decreasing even when the target object is disinfected or sterilized with an ethanol product (excellent antibacterial durability). In the present invention, the (poly)oxyalkylene group refers to a concept including both those having one oxyalkylene group, i.e., an oxyalkylene group, and those having two or more oxyalkylene groups, i.e., a polyoxyalkylene group. An example of "those having one oxyalkylene group" is "-CH2-CH2-O-". Also, an example of "those having two or more oxyalkylene groups" is "-(CH2-CH2-O)2-". The above-mentioned mechanism regarding the effect of the present invention is merely a presumption, and the present invention is not limited thereto.

[0012] The components contained in the composition of the present invention and the components that may be contained therein are described below. The components contained in the composition of the present invention and the components that may be contained therein may each be used alone or in combination of two or more.

[0013] <Component (A): Cationic cellulose derivative represented by general formula (I)> The composition of the present invention contains, as component (A), a cationic cellulose derivative represented by the following general formula (I). Hereinafter, the "cationic cellulose derivative represented by general formula (I)" will also be simply referred to as the "cationic cellulose derivative".

[0014] [ka] (In the formula, R 1 ~R 3 Each independently represents a hydrogen atom or a group represented by the following general formula (II), and d represents the average number of repetitions. However, all R 1 ~R 3 never represents a hydrogen atom.)

[0015] From the viewpoints of antibacterial activity and antibacterial durability, d is preferably 100 or more, more preferably 500 or more, even more preferably 1000 or more, and is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less.

[0016] [ka] (In general formula (II), R 4 represents a hydrogen atom or a group represented by the following general formula (III), L 1 represents C2H4 or C3H6. p is the average number of repetitions, which is 0 to 10. However, all p's are not 0, and all R 4 does not represent a hydrogen atom, and all R 4 does not represent a group represented by the following general formula (III). L 1 The C3H6 represented by the formula may be either linear or branched. p is preferably 0 to 5, more preferably 0 to 3, from the viewpoints of antibacterial activity and antibacterial durability. In general formula (II), p is preferably 1. That is, preferred examples of the group represented by the general formula (II) include -(C2H4-O) p -R 4 and -(C3H6-O) p -R 4 Examples include:

[0017] [ka] (In general formula (III), R 5 ~R 7 each independently represents an alkyl group having 1 to 4 carbon atoms; L 2 represents an alkylene group having 1 to 6 carbon atoms; X - represents at least a portion of a halide ion.

[0018] R 5 ~R 7 From the viewpoints of antibacterial activity and antibacterial durability, the number of carbon atoms in the alkyl group represented by R is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. 5 ~R 7 When the alkyl group represented by the formula (I) has 3 or 4 carbon atoms, the alkyl group may be either linear or branched. L 2 From the viewpoints of antibacterial activity and antibacterial durability, the number of carbon atoms in the alkylene group represented by the following formula is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. 2 When the alkylene group represented by the formula (I) has 3 to 6 carbon atoms, the alkylene group may be linear or branched. X - may all represent halide ions, some may represent halide ions and the other may represent phosphate ester anions (O=P(OR)2O - ), anion of carboxylic acid (RCOO - ), sulfonic acid anion (RSO3 - ), or the anion of sulfate ester (ROSO3 -) or the like. R is an organic group, preferably a hydrocarbon group. The halide ion is a fluoride ion, a chloride ion, a bromide ion, or an iodide ion, and is preferably a chloride ion.

[0019] (Substitution Degree of (Poly)oxyalkylene Group) From the viewpoints of antibacterial activity and antibacterial durability, the degree of substitution of the (poly)oxyalkylene group in the cationic cellulose derivative is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more, per mole of anhydroglucose unit, and is preferably 3.0 or less, more preferably 2.6 or less, and even more preferably 2.4 or less. In the present invention, the degree of substitution of X group refers to the molar average degree of substitution of X group, and means the number of substitutions of X group per mole of the constituent monosaccharide unit (anhydroglucose unit) of cellulose. For example, the "degree of substitution of (poly)oxyalkylene group" means the average number of moles of (poly)oxyalkylene group introduced (bonded) per mole of anhydroglucose unit. When the cationic cellulose derivative has both a (poly)oxyethylene group and a (poly)oxypropylene group, the degree of substitution of the (poly)oxyalkylene group is the sum of the degree of substitution of the (poly)oxyethylene group and the degree of substitution of the (poly)oxypropylene group.

[0020] (Substitution degree of cationic group) From the viewpoints of antibacterial activity and antibacterial durability, the degree of substitution of the cationic group in the cationic cellulose derivative is preferably 0.05 or more, more preferably 0.08 or more, even more preferably 0.1 or more, still more preferably 0.15 or more, and is preferably 0.9 or less, more preferably 0.8 or less, even more preferably 0.7 or less.

[0021] The degree of substitution of the hydroxyalkyl group and the cationic group of the cationic cellulose derivative is calculated as follows.

[0022] -Pretreatment- After dissolving 1 g of cationic cellulose derivative in 100 g of water, the aqueous solution is placed in a dialysis membrane (Spectrapore, molecular weight cutoff 1,000) and dialyzed for 2 days. The resulting aqueous solution is freeze-dried using a freeze dryer (eyela, FDU1100) to obtain a purified cationic cellulose derivative.

[0023] -Calculation of the amount of cationic substrate by Kjeldahl method- 200 mg of the purified cationic cellulose derivative is weighed out, 10 mL of sulfuric acid and one Kjeldahl tablet (Merck) are added, and the mixture is heated and decomposed in a Kjeldahl digestion apparatus (BUCHI, K-432). After the decomposition is complete, 30 mL of ion-exchanged water is added to the sample, and the nitrogen content (mass%) of the sample is determined using an automatic Kjeldahl distillation apparatus (BUCHI, K-370), to calculate the mass of the cationic group.

[0024] -Calculation of hydroxyalkyl group mass by Zeisel method- In the case where the (poly)oxyalkylene group of the cationic cellulose derivative is a monooxyethylene group and / or a monooxypropylene group, 200 mg of the purified cationic cellulose derivative and 220 mg of adipic acid are precisely weighed into a 10 mL vial (Mighty Vial No. 3), 3 mL of the internal standard solution (tetradecane / o-xylene = 1 / 25 (v / v)) and 3 mL of hydroiodic acid are added, and the vial is sealed. In addition, samples for the calibration curve are prepared by adding 2, 4, or 9 mg of 1-iodododecane instead of the cationic cellulose derivative. Each sample is heated at 160 ° C for 2 hours using a block heater (PIERCE, Reacti-ThermIII Heating / Stirring module) while stirring with a stirrer tip. After cooling the sample, the upper layer (o-xylene layer) is collected and the amount of 1-iodododecane is analyzed by gas chromatography (Shimadzu Corporation, GC-2010 plus). When the cationic cellulose derivative has both a monooxyethylene group and a monooxypropylene group as the (poly)oxyalkylene group, the amount of the (poly)oxyalkylene substrate is the sum of the amount of the monooxyethylene group and the amount of the monooxypropylene group.

[0025] -GC analysis conditions- Column: Agilent HP-1 (length: 30 m, liquid phase film thickness: 0.25 μL, inner diameter: 32 mm) Split ratio: 20 Column temperature: 100℃(2min)→10℃ / min→300℃(15min) Injector temperature: 300℃ Detector: FID Detector temperature: 330℃ Injection volume: 2μL The mass of the monooxyethylene group and / or monooxypropylene group in the sample is determined from the amount of 1-iodododecane detected by GC.

[0026] -Calculation of the substitution degree (molar average substitution degree) of (poly)oxyalkylene group and cationic group- When the (poly)oxyalkylene group of the cationic cellulose derivative is a monooxyethylene group and / or a monooxypropylene group, the mass of the hydroxyalkylmonooxyethylene group- and / or monooxypropylene group-containing cellulose skeleton is calculated from the mass of the cationic group, the mass of the monooxyethylene group and / or the monooxypropylene group, and the total sample mass, and each is converted into an amount of substance (mol), thereby determining the degree of substitution of the monooxyethylene group and / or the monooxypropylene group (MS H ), the degree of substitution of cationic groups (MS C ) is calculated.

[0027] (Weight average molecular weight) From the viewpoints of antibacterial activity and antibacterial durability, the weight average molecular weight of the cationic cellulose derivative is preferably 50,000 or more, more preferably 100,000 or more, even more preferably 150,000 or more, and is preferably 3,500,000 or less, more preferably 2,500,000 or less, even more preferably 2,000,000 or less.

[0028] The weight average molecular weight of the cationic cellulose derivative can be determined by, for example, the weight average molecular weight of the (poly)oxyalkylene group-modified cellulose used as the raw material and the MS C The weight average molecular weight of the (poly)oxyalkylene group-modified cellulose is calculated in terms of polyethylene glycol by GPC (gel permeation chromatography). The measurement conditions are as follows. -GPC analysis conditions- Column: TSKgel α-M × 2 Eluent: 50mmol / L LiBr, 1% CH3COOH, ethanol / water = 3 / 7 Temperature: 40℃ Flow rate: 0.6mL / min Detector: RI (Differential Refractive Index Detector)

[0029] Specific examples of cationic cellulose derivatives include cationized hydroxypropyl cellulose, O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethyl cellulose chloride, etc. The cationic cellulose derivatives can be synthesized by a conventional method. In the present invention, the cationic cellulose derivatives may be commercially available products. Examples of commercially available products include Poise C-60 and Poise C-150L (all manufactured by Kao Corporation), UCARE JR-125, JR-400, JR-30M, LR-400, LR-30M (all manufactured by Dow), and Catinal HC-100, HC-200, LC-100, LC-200 (all manufactured by Toho Chemical Industry Co., Ltd.).

[0030] (Content of component (A)) From the viewpoints of antibacterial activity and antibacterial durability, the content of component (A) in the composition of the present invention is 0.0005 mass% or more, preferably 0.001 mass% or more, more preferably 0.005 mass% or more, even more preferably 0.008 mass% or more, still more preferably 0.01 mass% or more, and is 20 mass% or less, preferably 15 mass% or less, more preferably 10 mass% or less, even more preferably 8 mass% or less, and still more preferably 5 mass% or less.

[0031] <Component (B): at least one selected from anionic compounds, nonionic compounds, and amphoteric compounds> The composition of the present invention contains, as component (B), at least one selected from an anionic compound, a nonionic compound, and an amphoteric compound. From the viewpoint of improving antibacterial properties and antibacterial durability, it is preferable that component (B) contains at least one selected from an anionic surfactant, an anionic polymer, a nonionic surfactant, a nonionic polymer, and an amphoteric surfactant, and it is more preferable that component (B) contains a nonionic polymer.

[0032] (anionic surfactant) Examples of the anionic surfactant include alkyl ether sulfates, alkyl sulfate esters, polyoxyalkylene alkyl ether sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phosphate esters, polyoxyalkylene alkyl ether phosphate esters, dialkyl sulfosuccinates, polyoxyalkylene alkyl ether sulfosuccinates, acylated alanine salts, acylated N-methyl-β-alanine salts, acylated glutamate salts, acylated isethionate salts, acylated sarcosinate salts, acylated methyl taurine salts, acylated taurine salts, α-sulfofatty acid ester salts, polyoxyalkylene alkyl ether carboxylate salts, polycarboxylate salts, ether carboxylate salts, long chain (8 to 24 carbon atoms) carboxylate salts, alkyl diphenyl ether sulfonate salts, and polyoxyalkylene fatty acid monoethanolamide sulfate salts. The number of carbon atoms of the alkyl group and acyl group in the anionic surfactant is, for example, 8 to 24. From the viewpoint of improving antibacterial properties and antibacterial durability, it is preferable to contain sodium dialkyl sulfosuccinate as the anionic surfactant.

[0033] (anionic polymer) The anionic polymer is a synthetic polymer containing a constituent unit derived from a monomer having an anionic group, a natural polymer having an anionic group, or an anion-modified natural polymer. The synthetic polymer may be a homopolymer or a copolymer. The copolymer may be in any of the following forms: random, block, and graft. Examples of the anionic polymer include (meth)acrylic acid derivatives (polyacrylic acid and its salts, acrylic acid / acrylamide / ethyl acrylate copolymers and their salts, polymethacrylic acid and its salts, methacrylic acid / acrylamide / diacetoneacrylamide / acrylic acid alkyl ester / methacrylic acid alkyl ester copolymers and their salts, hydrophobically modified acrylate / methacrylic acid copolymers and their salts, hydrophobically modified methacrylate / methacrylic acid copolymers and their salts, hydrophobically modified acrylate / methacrylic acid / acrylamide copolymers and their salts, etc.), acrylamidomethylpropane copolymers, Examples of the anionic polymer include polyacrylamidomethylpropanesulfonic acid derivatives (polyacrylamidomethylpropanesulfonic acid and its salts, copolymers of acrylamidomethylpropanesulfonic acid with at least one selected from acrylamide, dimethylacrylamide, vinylpyrrolidone, etc., and its salts), crotonic acid derivatives (vinyl acetate / crotonic acid copolymers, etc.), maleic acid derivatives (maleic anhydride / diisobutylene copolymers, isobutylene / maleic acid copolymers, etc.), polyglutamic acid and its salts, hyaluronic acid and its salts, carboxymethylcellulose and its salts, and carboxyvinyl polymers and its salts. From the viewpoint of improving antibacterial properties and antibacterial durability, it is preferable to contain carboxymethylcellulose and / or its salts as the anionic polymer. "(Meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid.

[0034] (Nonionic surfactant) Examples of nonionic surfactants include polyoxyalkylene alkylphenyl ethers, polyoxyalkylene alkyl ethers, polyhydric alcohol fatty acid ester alkylene oxide adducts, alkylamine alkylene oxide adducts, fatty acid amide alkylene oxide adducts, alkyl glycosides, sucrose fatty acid esters, alkanolamides, glycerin fatty acid esters, polyglycerin fatty acid ester polyoxyalkylene glycol ethers, polyoxyalkylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, sorbitol fatty acid esters, polyoxyalkylene glycerin fatty acid esters, tetrapolyoxyalkylene ethylenediamine condensates, sucrose fatty acid esters, polyoxyalkylene fatty acid amides, polyoxyalkylene glycol fatty acid esters, polyoxyalkylene castor oil derivatives, polyoxyalkylene hydrogenated castor oil derivatives, etc. From the viewpoint of improving antibacterial properties and antibacterial durability, it is preferable to contain polyoxyalkylene alkyl ethers as the nonionic surfactants.

[0035] (Nonionic polymer) The nonionic polymer is a synthetic polymer containing a constituent unit derived from a monomer having a nonionic group, a natural polymer having a nonionic group, or a nonionic modified natural polymer. The synthetic polymer may be a homopolymer or a copolymer. The copolymer may be in any of the following forms: random, block, and graft. Examples of nonionic polymers include acrylic acid derivatives (hydroxyethyl acrylate / methoxyethyl acrylate copolymers, polyacrylic acid amides, etc.), vinylpyrrolidone derivatives (polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, etc.), polyoxyalkylene glycol derivatives (polyethylene glycol, polypropylene glycol, etc.), associative nonionic polymers (hydrophobically modified polyether urethane, etc.), polysaccharides and their derivatives (cellulose derivatives (methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), guar gum, locust bean gum, dextran, etc.). From the viewpoint of improving antibacterial properties and antibacterial durability, it is preferable to contain hydroxyethyl cellulose as the nonionic polymer.

[0036] (Amphoteric surfactant) Examples of amphoteric surfactants include betaine-type amphoteric surfactants such as fatty acid (carbon number 8 to 24) amidopropyl betaine, fatty acid amidopropyl dimethylaminoacetate betaine, lauryl dimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, alkyl hydroxysulfobetaine, lauryl amidoethyl hydroxyethyl carboxymethyl betaine hydroxypropyl sodium phosphate, alkyl carboxybetaine, alkyl sulfobetaine, alkyl amidopropyl hydroxysulfobetaine, alkyl hydroxyphosphobetaine, and alkyl imidazolinium betaine; amino acid-type amphoteric surfactants such as sodium β-lauryl aminopropionate and alkyl amino carboxylate; amine oxide-type amphoteric surfactants such as lauryl dimethylamine oxide and alkyl amine oxide, and alkyl phosphate esters containing tertiary and quaternary nitrogen. The number of carbon atoms of the alkyl group in the amphoteric surfactant is, for example, 8 to 24. From the viewpoint of improving antibacterial properties and antibacterial durability, it is preferable to contain lauric acid amidopropyl betaine as the amphoteric surfactant.

[0037] From the viewpoint of improving antibacterial properties and antibacterial durability, the composition of the present invention preferably contains, as component (B), at least one selected from sodium dialkyl sulfosuccinate, carboxymethyl cellulose, polyoxyalkylene alkyl ether, hydroxyethyl cellulose, and lauric acid amidopropyl betaine, and more preferably contains hydroxyethyl cellulose.

[0038] (Content of component (B)) The content of component (B) in the composition of the present invention is, from the viewpoints of antibacterial activity and antibacterial durability, 0.0001 mass% or more, preferably 0.0002 mass% or more, more preferably 0.001 mass% or more, and 5 mass% or less, preferably 2 mass% or less, more preferably 1 mass% or less, even more preferably 0.8 mass% or less, and still more preferably 0.5 mass% or less.

[0039] (mass ratio [(A) / (B)]) The mass ratio of component (A) to component (B) in the composition of the present invention [(A) / (B)] is 1.0 or more, preferably 1.4 or more, more preferably 1.8 or more, and is 47 or less, preferably 46 or less, from the viewpoint of improving antibacterial activity and antibacterial durability.

[0040] <Ingredient (C): Water> The composition of the present invention preferably contains water from the viewpoints of dispersion stability and uniform application to an object. The content of water in the composition of the present invention can be appropriately determined so that the content of component (A) in the composition of the present invention is 0.0005 to 20% by mass.

[0041] <Other ingredients> The composition of the present invention may contain components (other components) other than the components (A) to (C) as long as the effects of the present invention are not impaired. Examples of the other components include surfactants other than the component (B), cationic surfactants, silicone oils, inorganic salts, and water-soluble organic solvents. The content of the other components in the composition of the present invention is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, and is 0 parts by mass or more, preferably 0 parts by mass, relative to 100 parts by mass of the component (A).

[0042] The antibacterial composition of the present invention can be used, for example, as a spray by putting it in a container. The antibacterial composition of the present invention can also be impregnated into a base fabric such as a woven fabric or a nonwoven fabric to obtain a wet wiper. It can also be applied. That is, the antibacterial method of the present invention is preferably one selected from a method of spraying the antibacterial composition of the present invention, a method of wiping with a wet wiper having a base fabric impregnated with the antibacterial composition of the present invention, and a method of applying the antibacterial composition of the present invention. The object to be antibacterialized by the antibacterial method of the present invention is preferably one or more selected from hard objects and cloth.Preferable hard objects include metal, pottery, porcelain, plastic, wood (including those surface-treated with varnish, etc.), and glass.Preferable cloth includes woven fabric, nonwoven fabric, and knitted fabric.

[0043] More specific examples of objects that can be antibacterialized by the antibacterial composition of the present invention include building materials such as doors, doorknobs, bathtubs, sinks, washstands, toilets, window panes, handrails, handles, and switches; furniture such as tables and chairs; bedding such as futons and mats; electronic products such as personal computers, smartphones, and tablets; clothing such as shirts and coats; and on-vehicle parts for automobiles and airplanes.

[0044] The present invention discloses the following embodiments. [1] An antibacterial composition comprising the following components (A) and (B): (A) A cationic cellulose derivative represented by the following general formula (I): (B) at least one selected from an anionic compound, a nonionic compound, and an amphoteric compound The content of component (A) in the antibacterial composition is 0.0005 to 20% by mass, An antibacterial composition, wherein the mass ratio of component (A) to component (B) [(A) / (B)] is 1.0 or more and 47 or less. [ka] (In the formula, R 1 ~R 3 Each independently represents a hydrogen atom or a group represented by the following general formula (II), and d represents the average number of repetitions. However, all R 1 ~R 3 never represents a hydrogen atom.) [ka] (In general formula (II), R 4 represents a hydrogen atom or a group represented by the following general formula (III), L 1 represents C2H4 or C3H6. p is the average number of repetitions and is 0 to 10. However, all p's are not 0, and all R 4 does not represent a hydrogen atom, and all R 4 does not represent a group represented by the following general formula (III). [ka] (In general formula (III), R 5 ~R 7 each independently represents an alkyl group having 1 to 4 carbon atoms; L 2 represents an alkylene group having 1 to 6 carbon atoms; X - represents at least a portion of a halide ion. [2] The antibacterial composition according to the above [1], comprising, as component (B), at least one selected from an anionic surfactant, an anionic polymer, a nonionic surfactant, a nonionic polymer, and an amphoteric surfactant. [3] The antibacterial composition according to the above [1] or [2], wherein the degree of substitution of the cationic group in component (A) is 0.05 or more and 0.9 or less, preferably 0.08 or more and 0.9 or less, more preferably 0.1 or more and 0.8 or less, and even more preferably 0.15 or more and 0.7 or less. [4] The antibacterial composition according to any one of the above [1] to [3], wherein the degree of substitution of the (poly)oxyalkylene group in component (A) is 0.1 or more and 3.0 or less, preferably 0.5 or more and 2.6 or less, and more preferably 1.0 or more and 2.4 or less. [5] The antibacterial composition according to any one of the above [1] to [4], wherein in general formula (II), p is 1. [6] The antibacterial composition according to any one of the above [1] to [5], wherein the content of component (A) is from 0.001% by mass to 15% by mass. [7] The antibacterial composition according to any one of the above [1] to [6], wherein the content of component (B) is from 0.0001% by mass to 5% by mass. [8] In general formula (III), L 2 The antibacterial composition according to any one of the above [1] to [7], wherein represents an alkylene group having 1 to 4 carbon atoms, preferably a methylene group or an ethylene group, more preferably a methylene group. [9] The antibacterial composition according to any one of the above [1] to [8], wherein the weight average molecular weight of component (A) is 50,000 or more and 2,000,000 or less, preferably 100,000 or more and 2,000,000 or less, and more preferably 150,000 or more and 2,000,000 or less.

[10] The antibacterial composition according to any one of the above [1] to [9], further comprising water as component (C).

[11] One antibacterial method selected from a method of spraying the antibacterial composition described in any one of the above [1] to

[10] , a method of wiping with a wet wiper having a base fabric impregnated with the antibacterial composition described in any one of the above [1] to

[10] , and a method of coating the antibacterial composition described in any one of the above [1] to

[10] .

[12] The antibacterial method according to the above

[11] , wherein the object to be antibacterialized by the method according to the above

[11] is one or more selected from hard objects and cloth.

[13] An object to be treated that has been antibacterialized by the antibacterial method described in

[11] or

[12] above. EXAMPLES

[0045] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples in any way.

[0046] <Preparation of antibacterial composition> Example 1 The antibacterial composition of Example 1 was prepared by mixing 100 parts by mass of component (A) (component A-(2) in Table 1: polyquaternium-10 (O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride), 50 parts by mass of component (B) (component B-(2) in Table 1: lauric acid amidopropyl betaine), and an amount of water such that the concentration of component (A) in the composition was 0.05% by mass.

[0047] Examples 2 to 16, Comparative Examples 1 to 6 The antibacterial compositions of Examples 2 to 16 and Comparative Examples 1 to 6 were prepared in the same manner as in Example 1, except that in the preparation of the antibacterial composition of Example 1, the compositions were changed to those shown in Table 1. The contents shown in Table 1 are the amounts of active ingredients (parts by mass or %) of each ingredient.

[0048] The components (components listed in Table 1) used in the antibacterial compositions of Examples 1 to 16 and Comparative Examples 1 to 6 are described in detail below. A-(1): Cationic hydroxypropyl cellulose Degree of substitution of cationic group: 0.2, weight average molecular weight: 300,000 A-(2): Polyquaternium-10 (O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethyl cellulose chloride) Degree of substitution of cationic group: 0.7, weight average molecular weight: 600,000 A-(3): Polyquaternium-10 (O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethyl cellulose chloride) Degree of substitution of cationic group: 0.3, weight average molecular weight: 1,500,000 B-(1): Pelex OTP (Kao Corporation, sodium dialkyl sulfosuccinate, 70% by mass solids aqueous solution, the content of B-(1) in Table 1 is the solids content.) B-(2): Amphitol 20AB (Kao Corporation, lauric acid amide propyl betaine, 30% by mass solids aqueous solution, the content of B-(2) in Table 1 is the solids content.) B-(3): Emulgen LS110 (Kao Corporation, polyoxyalkylene alkyl ether) B-(4): Softanol 70H (Nihon Shokubai Co., Ltd., secondary alcohol ethoxylate) B-(5): Hydroxyethyl cellulose (Tokyo Chemical Industry Co., Ltd.) B-(6): Sodium carboxymethylcellulose (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0049] <Antibacterial evaluation> With reference to "5. Test Method" of JIS Z 2801:2010 "Antibacterial processed products - Antibacterial test method, antibacterial effect", antibacterial performance tests were carried out for each of the antibacterial compositions prepared in the examples and comparative examples. Three test pieces cut into 50 mm squares from the polypropylene film were used as unprocessed test pieces for measuring the viable cell count immediately after inoculation with the test bacteria liquid.An antibacterial layer was formed by coating one side of the polypropylene film with the antibacterial composition, and three test pieces cut into 50 mm squares were used as processed test pieces for measuring the viable cell count after 24 hours of incubation. Each test specimen was placed in a sterile petri dish with the test surface facing up, and the number of bacteria in contact with the test specimen was 2.5 × 10 5 ~10×10 50.1 ml of Escherichia coli solution prepared to give a concentration of bacteria / ml was inoculated, and a covering film (polyethylene film, size approximately 4 cm x 4 cm) was placed on top, carefully ensuring that the test bacteria solution was spread over the entire film, and the dish was then covered with a lid and cultured in an incubator at a temperature of 37°C and a relative humidity of 90%. The "test surface" may be either side for untreated test pieces, and the treated test pieces are the side with the antibacterial layer formed. After culturing for 24 hours, the bacteria liquid was washed out using a liquid medium and completely recovered. The washed out liquid was serially diluted in a 10-fold dilution series, and each dilution was mixed with a standard agar medium. After the medium solidified, the specimens were cultured for 40 to 48 hours in an incubator at a temperature of 37°C and a relative humidity of 90%, and the number of colonies was measured by colony counting. The number of live bacteria per test piece was calculated, and the antibacterial activity value R1 was calculated using the following formula 1. The results are shown in Table 1. Formula 1: R1 = Ut1 - At1 R1: Antibacterial activity value Ut1: Average logarithm of the number of viable bacteria ( / unit) on untreated test pieces At1: The average logarithm of the number of viable bacteria ( / unit) on the processed test piece after 24 hours In addition, an R1 value of 2.0 or more is considered to have excellent antibacterial properties.

[0050] <Sustained antibacterial evaluation> To evaluate the duration of antibacterial activity, the antibacterial layer side of the processed test piece was manually wiped back and forth twice with Kimtowel (product name, manufactured by Nippon Paper Crecia Co., Ltd.) soaked in a 78% ethanol aqueous solution and then dried. The number of live bacteria per wiped test piece after drying was measured, and the antibacterial activity value R2 was calculated using the following formula 2. The results are shown in Table 1. Formula 2: R2=Ut1-At2 Ut1: Same as Ut1 in formula 1 At2: The average logarithmic value of the number of viable bacteria ( / unit) on the processed test piece after wiping off the antibacterial layer (after wiping off the ethanol aqueous solution) In addition, an R2 value of 2.0 or more is considered to indicate excellent antibacterial durability.

[0051] [Table 1]

[0052] From Table 1, it is seen that antibacterial compositions containing components (A) and (B) defined in the present invention, in which the content of component (A) in the antibacterial composition is 0.0005 to 20 mass %, and the mass ratio of component (A) to component (B) [(A) / (B)] is 1.0 or more and 47 or less, have excellent antibacterial properties and excellent antibacterial durability (Examples 1 to 16). In contrast, it is found that antibacterial compositions containing component (A) but not component (B) and antibacterial compositions containing component (B) but not component (A) have poor antibacterial durability (Comparative Examples 1 and 2). In addition, it is found that antibacterial compositions containing components (A) and (B) and in which the concentration of component (A) in the composition satisfies the provisions of the present invention, but in which the mass ratio of component (A) to component (B) [(A) / (B)] is less than 1.0 or exceeds 47, have poor antibacterial durability (Comparative Examples 3 and 4). In addition, it is found that antibacterial compositions containing components (A) and (B) and in which the mass ratio of component (A) to component (B) [(A) / (B)] satisfies the provisions of the present invention, but in which the concentration of component (A) in the composition is less than the lower limit or exceeds the upper limit of the provisions of the present invention, have poor antibacterial activity and antibacterial durability (Comparative Examples 5 and 6).

Claims

1. An antibacterial composition comprising the following components (A) and (B): (A) A cationic cellulose derivative represented by the following general formula (I): (B) at least one selected from an anionic compound, a nonionic compound, and an amphoteric compound The content of component (A) in the antibacterial composition is 0.0005 to 20 mass %, An antibacterial composition, wherein the mass ratio of component (A) to component (B) [(A) / (B)] is 1.0 or more and 47 or less. 【Chemistry 1】 (In the formula, R １ ~R ３ Each independently represents a hydrogen atom or a group represented by the following general formula (II), and d represents the average number of repetitions. １ ~R ３ does not represent a hydrogen atom.) 【Chemistry 2】 (In general formula (II), R ４ represents a hydrogen atom or a group represented by the following general formula (III), L １ is C ２ H ４ Or C ３ H ６ p is the average number of repetitions, ranging from 0 to 10. However, all p's are not 0, and all R ４ does not represent a hydrogen atom, and all R ４ does not represent a group represented by the following general formula (III). 【Chemistry 3】 (In general formula (III), R ５ ~R ７ each independently represents an alkyl group having 1 to 4 carbon atoms; L ２ represents an alkylene group having 1 to 6 carbon atoms; X － represents at least a portion of a halide ion.

2. 2. The antibacterial composition according to claim 1, comprising, as component (B), at least one selected from the group consisting of anionic surfactants, anionic polymers, nonionic surfactants, nonionic polymers, and amphoteric surfactants.

3. 3. The antibacterial composition according to claim 1, wherein the degree of substitution of the cationic group in component (A) is 0.1 or more and 0.8 or less.

4. 3. The antibacterial composition according to claim 1, wherein the weight average molecular weight of component (A) is 50,000 or more and 2,000,000 or less.

5. The antibacterial composition according to claim 1 or 2, further comprising water as a component (C).

6. 3. An antibacterial method selected from the group consisting of a method of spraying the antibacterial composition according to claim 1 or 2, a method of wiping with a wet wiper having a base fabric impregnated with the antibacterial composition according to claim 1 or 2, and a method of coating the antibacterial composition according to claim 1 or 2.

7. An object to be treated that has been antibacterialized by the antibacterial method according to claim 6.

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