Antimicrobial composition, molded article, antimicrobial sheet, antifungal composition, and production method for compound

Abstract

To provide an antimicrobial composition having long-lasting antimicrobial efficacy.SOLUTION: An antimicrobial composition comprises a photosensitizer (A) and at least one compound (B) selected from alkanolamines and aminocarboxylic acids, with the content of iron ions being 50 mol% or less based on the photosensitizer (A).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an antimicrobial composition, a molded article, an antimicrobial sheet, an antifungal composition, and a method for producing the compound. [Background technology]

[0002] Antimicrobial drugs are widely used for various purposes, such as food preservation, stabilization of water quality, and prevention of infectious diseases. Many antimicrobial drugs are toxic to microorganisms. Therefore, depending on the type and method of use, there is a risk that they may have harmful effects on humans or be a burden on the environment.

[0003] Patent Document 1 discloses an antimicrobial composition that contains amino acids, specific antimicrobial components such as a quaternary ammonium compound, and a polar solvent, as an antimicrobial composition that has low toxicity and a short residence time in the environment.

[0004] Separately, the present inventors have disclosed a photocatalytic composition that contains a photosensitizer having an isoalloxazine skeleton or the like and a specific sacrificial agent, as a photocatalytic composition that can obtain a strong photocatalytic effect when exposed to visible light. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2018-511607 [Patent Document 2] WO 2022 / 80101 Summary of the Invention [Problem to be solved by the invention]

[0006] The present disclosure aims to provide an antimicrobial composition having excellent durability of antimicrobial activity, a molded body and an antimicrobial sheet using the antimicrobial composition, as well as an antifungal agent composition suitable as an antifungal agent, and a method for producing a compound having antifungal activity. [Means for solving the problem]

[0007] One aspect of the antimicrobial composition according to the present disclosure comprises: The composition contains a photosensitizer (A) and one or more compounds (B) selected from an alkanolamine and an aminocarboxylic acid, The content of iron ions is 50 mol % or less relative to the photosensitizer (A).

[0008] One embodiment of the molded article according to the present disclosure is produced by molding an antimicrobial composition containing a resin.

[0009] One embodiment of the antimicrobial sheet according to the present disclosure comprises a porous substrate impregnated with the antimicrobial composition.

[0010] One embodiment of the antifungal composition according to the present disclosure contains one or more antifungal agents selected from lactaldehyde, glycolaldehyde, and glyoxylic acid.

[0011] One embodiment of the method for producing a compound according to the present disclosure is a method for producing lactaldehyde, glycolaldehyde, or glyoxylic acid, comprising the steps of: A photosensitizer (A); and one or more selected from triisopropanolamine, triethanolamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and ethylenediaminetetraacetic acid; A composition having an iron ion content of 50 mol % or less based on the photosensitizer (A), This includes irradiating the surface with light. Effect of the Invention

[0012] The present disclosure can provide an antimicrobial composition having excellent durability of antimicrobial activity, a molded body and an antimicrobial sheet using the antimicrobial composition, as well as an antifungal agent composition suitable as an antifungal agent, and a method for producing a compound having antifungal properties. [Brief description of the drawings]

[0013] [Figure 1] FIG. 2 is a schematic diagram for explaining a gas-phase antifungal property test. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, an embodiment of the present invention will be described. In this disclosure, "antimicrobial" refers to having antimicrobial activity against microorganisms (bacteria, fungi, viruses, parasites), and is a general term including antiviral, antibacterial, antifungal, and anti-mold. In addition, in this disclosure, the term "to" indicating a range of values ​​includes the lower limit and the upper limit unless otherwise specified.

[0015] [Antimicrobial composition] The antimicrobial composition of the present disclosure contains a photosensitizer (A) and one or more compounds (B) selected from alkanolamines and aminocarboxylic acids (hereinafter also simply referred to as compound (B)), and the iron ion content is 50 mol % or less relative to the photosensitizer (A).

[0016] When the present antimicrobial composition is irradiated with light, compound (B) reacts with water in the air or solvent by the action of the light to generate one or more compounds (C) selected from hydroxyaldehydes and aldehyde acids, which are the active ingredients of the antimicrobial agent (hereinafter, also simply referred to as compound (C)). In the present composition, the reaction for generating compound (C) is photoresponsive and proceeds gradually according to the amount of light irradiation, so that it is possible to control the amount of compound (C) released. Compound (C) exerts sufficient antimicrobial properties even at low concentrations. Therefore, the present composition can maintain antimicrobial properties for a long period of time while controlling the amount of compound (C) released. In addition, by making the iron ion content (amount of substance) of the present antimicrobial composition 50% or less of that of the photosensitizer (A), the generation of active oxygen during light irradiation is suppressed, thereby suppressing side reactions, and therefore improving the production efficiency of compound (C).

[0017] The present antimicrobial composition contains at least a photosensitizer (A) and one or more compounds (B) selected from alkanolamines and aminocarboxylic acids, and may further contain other components within the scope of the effects of the present invention. Each component that may be contained in the present antimicrobial composition will be described below.

[0018] <Photosensitizer (A)> The photosensitizer (A) may be any one that can decompose the compound (B) by the action of light, and may be appropriately selected from known photosensitizers. Examples of the photosensitizer (A) include compounds having a skeleton such as naphthalene, anthracene, phenanthrene, pyrene, perylene, benzophenone, fluorene, naphthoquinone, anthraquinone, xanthene, thioxanthene, xanthone, isoalloxazine, alloxazine, phenoxazine, fluorescein, phloxine, thioxanthone, coumarin, ketocoumarin, cyanine, merocyanine, oxonol, benzothiazole, acridine, thiazine, oxazine, indoline, azulene, azulenium, porphyrin, triarylmethane, phthalocyanine, phenothiazine, spiropyran, and spirooxazine; unsaturated ketones such as acridone, chalcone, and dibenzalacetone; 1,2-diketones such as benzil and camphorquinone; azo compounds, and organic metal complexes. The photosensitizer (A) can be used alone or in combination of two or more kinds. In the compounds having the above various skeletons, the carbon atoms and nitrogen atoms constituting the skeleton may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acidic group such as a carboxy group or a sulfo group, an amino group, and an organic group. The acidic group and the amino group may form a salt, and the organic group may further have a substituent. The photosensitizer (A) may be anionic, cationic or neutral, but is preferably anionic or neutral in terms of the reactivity of the compound (B).

[0019] The photosensitizer (A) is preferably one having a tricyclic condensed ring, because it can provide an excellent photocatalytic effect and is easily available. Examples of the tricyclic condensed ring include compounds having a skeleton such as anthracene, phenanthrene, fluorene, anthraquinone, xanthene, thioxanthene, xanthone, isoalloxazine, alloxazine, phenoxazine, fluorescein, thioxanthone, acridine, and phenothiazine. Among them, compounds having a skeleton selected from isoalloxazine, alloxazine, phenothiazine, fluorescein, anthraquinone, and acridine are preferred, and further, compounds having an isoalloxazine skeleton or an alloxazine skeleton are more preferred in terms of sustained release of the compound (C) by visible light (e.g., wavelength 400 to 600 nm). Specific examples of the compound having a phenothiazine skeleton include perfeazine, chlorpromazine, acepromazine, phenothiazine, methylphenothiazine, methylene blue, etc., and from the viewpoint of sustained release of compound (C), perfeazine, chlorpromazine, or acepromazine is preferred. Specific examples of compounds having a fluorescein skeleton include fluorescein, phloxine, dibromofluorescein, eosin Y, eosin B, rhodamine B, rhodamine 6G, and rose bengal. From the viewpoint of sustained release of the composition, fluorescein, phloxine, dibromofluorescein, eosin Y, eosin B, and rose bengal are preferred. Specific examples of the compound having an anthraquinone skeleton include anthraquinonesulfonic acid, anthraquinonedisulfonic acid, anthraquinonecarboxylic acid, 2-anthraquinonesulfonic acid, and alkali metal salts thereof. Specific examples of the compound having an acridine skeleton include acridine orange and acridine carboxylic acid.

[0020] Examples of compounds having an isoalloxazine skeleton or an alloxazine skeleton include compounds represented by the following general formula (1) and compounds represented by the following general formula (2). These compounds provide excellent photocatalytic effects even when a light source with a relatively low output, such as a white LED, is used, and the production efficiency of compound (C) relative to the amount of light irradiation is improved.

[0021] [ka] In formula (1), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group which may have a substituent, R 5 and R 6 each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, In formula (2), R 11 , R 12 , R 13 and R 14 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group which may have a substituent, R 15 and R 16 each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent.

[0022] R 1 ~R 4 , R 11 ~R 14 Examples of the halogen atom in include a fluorine atom, a chlorine atom, and a bromine atom. R 1 ~R 4 , R 11 ~R 14Examples of the hydrocarbon group in R include a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, or an aryl group which may have a linear or branched alkyl group as a substituent. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, and a hexyl group. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group. R 1 ~R 4 , R 11 ~R 14 The substituents which the hydrocarbon group in the formula may have include a hydroxy group, a carboxy group, a halogen atom, etc., and the hydroxy group and the carboxy group may be further esterified derivatives. In terms of photocatalytic activity, R 1 , R 4 , R 11 and R 14 are preferably each independently a hydrogen atom. 2 , R 3 , R 12 and R 13 are each independently preferably a linear or branched alkyl group having no substituent, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.

[0023] R 6 , R 15 and R 16 The hydrocarbon group in R 1 The same can be mentioned as above, and the preferred embodiments are also the same. From the viewpoint of photocatalytic activity, R 6 , R 15 and R 16 are each preferably a hydrogen atom.

[0024] R 5 The hydrocarbon group in R 1 The same as above can be mentioned. R 5 The substituent that the hydrocarbon group in R may have includes a hydroxyl group or an ester thereof. 5In particular, the substituent in is preferably a ribityl group (-CH2-CHOH-CHOH-CHOH-CH2OH) or an ester of the ribityl group.

[0025] Furthermore, the compound having an isoalloxazine skeleton or an alloxazine skeleton is particularly preferably riboflavin or a riboflavin derivative. Riboflavin is also known as vitamin B2 and is highly safe, and the present antimicrobial composition can be suitably used, for example, in applications in which it comes into contact with food, such as container packaging, applications in which it may be taken up by the human or other living organism, and applications in which it is released into the soil or air. Specific examples of riboflavin derivatives include riboflavin tetrabutyrate, riboflavin tetraacetate, lumichrome (7,8-dimethylalloxazine), riboflavin phosphate ester and its salts (sodium salt, potassium salt, etc.), flavin adenine dinucleotide, and the like.

[0026] Among these, the photosensitizer (A) is preferably riboflavin, riboflavin tetrabutylate, lumichrome, or riboflavin sodium phosphate in view of photocatalytic activity, safety, industrial availability, and the like.

[0027] <One or more compounds selected from alkanolamines and aminocarboxylic acids (B)> Compound (B) is a compound that becomes compound (C) when exposed to light. Alkanolamines produce hydroxyaldehydes when exposed to light. Also, aminocarboxylic acids produce aldehyde acids when exposed to light. Alkanolamines are compounds having one or more amino groups and one or more hydroxyl groups in one molecule, while aminocarboxylic acids are compounds having one or more amino groups and one or more carboxy groups in one molecule, and the carboxy groups may exist in the form of a salt or an ion.

[0028] Compound (B) may be appropriately selected in consideration of the structure of compound (C) to be produced. Compound (C) is preferably lactaldehyde, glycolaldehyde, or glyoxylic acid, from the viewpoint of achieving both antimicrobial properties and low impact on humans and the environment. These compounds (C) have excellent antimicrobial properties (especially antifungal and antifungal properties) and also have excellent antifungal properties in the gas phase. In addition, these compounds (C) are relatively easily oxidized to lactic acid, glycolic acid, and oxalic acid, respectively. These compounds exist in nature and are used as food additives and cosmetics, and their safety is guaranteed.

[0029] Compounds (B) that produce lactaldehyde include compounds having a partial structure of >N-CH2C(CH3)OH. Compounds (B) that produce glycolaldehyde include compounds having a partial structure of >N-CH2CH2OH. Compounds (B) that produce glyoxylic acid include compounds having a partial structure of >N-CH2COOH or a salt thereof. The molecular weight of compound (B) is not particularly limited, but is preferably 2,000 or less, more preferably 1,000 or less, and even more preferably 60 to 500, from the viewpoint of the production efficiency of compound (C).

[0030] Specific examples of the compound (B) include: Compounds from which lactaldehyde is produced, such as monoisopropanolamine, diisopropanolamine, triisopropanolamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, bis(2-hydroxypropyl)alkylamines, and dibutylpropanolamine; Compounds from which glycolaldehyde is produced, such as monoethanolamine, diethanolamine, triethanolamine, N,N-di(2-hydroxyethyl)cyclohexylamine, bis(2-hydroxyethyl)alkylamines, N-tertiarybutyldiethanolamine, and dibutylethanolamine; Compounds from which lactaldehyde and glycolaldehyde are produced, such as N-hydroxyethyl-N,N-di(2-hydroxypropyl)amine; Compounds that produce glyoxylic acid, such as ethylenediaminetetraacetic acid; and the like. In addition, the "alkyl" in the above examples is a moiety that is unrelated to the structure of the resulting compound (C) and is not particularly limited, and examples thereof include alkyl chains having 1 to 24 carbon atoms. Among these, triisopropanolamine, triethanolamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, or ethylenediaminetetraacetic acid is particularly preferred as compound (B) from the viewpoint of the production efficiency of compound (C). The compound (B) can be used alone or in combination of two or more kinds.

[0031] (Content of each ingredient) The ratio of photosensitizer (A) to compound (B) in the present antimicrobial composition is not particularly limited. When the ratio of photosensitizer (A) is high, the amount of compound (C) generated per light irradiation dose increases. On the other hand, when the ratio of compound (B) is high, the durability of antimicrobial properties increases. In consideration of these, the ratio of photosensitizer (A) is, for example, 0.1×10 to 100% by mass of the total mass of photosensitizer (A) and compound (B). -5 It can be appropriately adjusted to a range of 50% by mass to 40% by mass. From the viewpoint of the durability of the effect of the present antimicrobial composition and the viewpoint of the cost merit of the present antimicrobial composition, the ratio of the photosensitizer (A) to the total mass is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less, particularly preferably 5% by mass or less, and extremely preferably 0.5% by mass or less. Even if the present composition has a relatively high concentration of the photosensitizer (A) (for example, 30% by mass or more), the compound (C) is not released all at once when exposed to sunlight, and the antimicrobial effect can be sustained. In order to make the composition an antimicrobial composition having excellent photoresponsiveness, the ratio of the photosensitizer (A) is 0.1×10 -5 % by mass or more is preferable, and 0.2×10 -4 % by mass or more is more preferable, and 0.1×10 -3 % by mass or more is more preferable.

[0032] The content of iron ions in the composition is 50 mol % or less, preferably 30 mol % or less, more preferably 10 mol % or less, even more preferably 5 mol % or less, and particularly preferably 1 mol % or less, relative to the photosensitizer (A) in order to suppress the generation of active oxygen upon light irradiation and thereby suppress side reactions. In addition, from the viewpoint of suppressing side reactions and suppressing effects on humans and the environment, the total amount of heavy metal ions in the composition is preferably 50 mol % or less, more preferably 30 mol % or less, even more preferably 10 mol % or less, even more preferably 5 mol % or less, particularly preferably 1 mol % or less, and extremely preferably substantially free (0.1 mol % or less) relative to the photosensitizer (A). Here, heavy metal is a general term for metals with a specific gravity of 4 or more.

[0033] <Optional ingredients> The composition may contain other components within the scope of the effects of the present invention, such as a medium such as a solvent or resin, various additives such as a gelling agent, a surfactant, a defoaming agent, a preservative, and a pH adjuster, and a component for improving bacteriostasis.

[0034] (solvent) The solvent can be appropriately selected from those that can dissolve or disperse each component of the composition. In terms of ease of dissolving or dispersing each component, the solvent preferably contains one or more solvents selected from water and water-soluble solvents, and more preferably contains water. Examples of the water-soluble solvent include alcohol-based solvents such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin, dipropylene glycol, and diethylene glycol. When a mixed solvent of water and a water-soluble solvent is used, the water-soluble solvent is preferably 10% by mass or less, more preferably 5% by mass or less, based on 100% by mass of the solvent. Furthermore, the solvent may be a solvent consisting essentially of water, since it can be used for various purposes. The present composition containing a solvent may be used for applications such as spraying on soil or coating on wall surfaces. The present composition containing a solvent may also be applied to the surface of a substrate such as food utensils, containers, and packaging, and dried to form an antimicrobial layer. The present composition containing a solvent may also be used as a circulating liquid for cooling towers and chillers, or as a culture liquid for hydroponic cultivation or plant factories.

[0035] (resin) The antimicrobial composition may contain a resin. The composition containing a resin may be molded into any shape and used as a molded product. The type of resin is not particularly limited, and may be appropriately selected depending on the application of the molded product. Examples of the resin include polyethylene, polypropylene, polyethylene terephthalate, nylon, cellulose, polyurethane, polycarbonate, acrylic, etc., and may be any of thermoplastic resins, thermosetting resins, and photocurable resins. The composition containing a resin may be prepared by blending a photosensitizer (A), a compound (B), a resin, and other components as necessary, and kneading them uniformly. Molded products of the composition containing a resin may be used, for example, as food utensils, containers, packaging, etc. The composition containing a resin may also be applied to a substrate to form an antimicrobial layer.

[0036] (Surfactant) The surfactant is used for the purpose of imparting wettability to a substrate, etc., and can be appropriately selected from known surfactants such as anionic surfactants, nonionic surfactants, and cationic surfactants depending on the application.

[0037] The composition may also contain a gelling agent and be used in the form of a gel. As the gelling agent, gelatin, thickening polysaccharides or crosslinked products thereof are preferred from the viewpoint of reducing environmental load, which are also used in food applications. When a gelling agent is used, the composition preferably contains water.

[0038] The above-mentioned gelatin refers to a denatured protein obtained by boiling collagen in water to make it water-soluble. For example, collagen that can be collected from the skin, bones, tendons, and other parts of various animal species such as cows, pigs, and fish is denatured by various processes such as alkaline hydrolysis, acid hydrolysis, and enzymatic decomposition. The thickening polysaccharide is a polymer of saccharides having many hydrogen bond groups in the molecule and capable of gelling. The thickening polysaccharide can be appropriately selected from commonly known natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides according to the purpose. Specific examples of the thickening polysaccharide include starch, glycogen, agarose, agaropectin, carrageenan, pectin, xanthan gum, locust bean gum, guar gum, gellan gum, gum arabic, alginic acid, hemicellulose, tara gum, tamarind seed gum, chitin, chitosan, glucomannan, and the like, and may also be agar, which is a mixture of agarose and agaropectin.

[0039] (Components for improving bacteriostasis) The composition may further contain a component that improves bacteriostasis. Examples of the component that improves bacteriostasis include bacteriostatic agents such as glycerin mono fatty acid ester, oxalic acid or its salt, itaconic acid or its salt, tartaric acid or its salt, citric acid or its salt, adipic acid or its salt, fumaric acid or its salt, malic acid or its salt, succinic acid or its salt, sorbic acid or its salt, lactic acid or its salt, glycine or its salt, thiamine lauryl sulfate or its salt, chitosan or its salt, dehydroacetic acid or its salt, lysozyme, egg white lysozyme, allyl isothiocyanate, nisin, polylysine, yucca extract, licorice extract, hop extract, and milt protein, and may be used alone or in combination of two or more. When the bacteriostatic agent is used, the content of the bacteriostatic agent in the composition is preferably 0.0001 to 10 mol %, more preferably 0.001 to 5 mol %, and even more preferably 0.01 to 2 mol %, relative to the photosensitizer (A).

[0040] <Method of preparing antimicrobial composition> The composition can be prepared by uniformly mixing the photosensitizer (A) and the compound (B), and specifically, a method of adding the photosensitizer (A), the compound (B), and other optional additive components to a medium such as a solvent and / or a resin, and mixing them, etc. Alternatively, a high-concentration composition may be prepared by the above method, and then diluted with a solvent such as water when used.

[0041] <Uses of the antimicrobial composition> The present antimicrobial composition is a composition that releases one or more compounds (C) selected from hydroxyaldehydes and aldehyde acids by irradiation with light, and can continuously produce these easily decomposed compounds (C) for a long period of time, resulting in an antimicrobial composition with excellent durability of antimicrobial properties. In addition, by selecting the photosensitizer (A), excellent antimicrobial properties can be obtained even when a light source with a relatively low output, such as a white LED, is used. The present composition can be used in various forms. For example, the present composition containing a solvent can be suitably used as an antifungal agent on the surface of an article or in the gas phase, as a circulating liquid for a cooling tower or chiller, or as a culture solution for hydroponic cultivation or a plant factory. The present composition containing a solvent may be impregnated into a porous substrate to form an antimicrobial sheet. Examples of porous substrates include, but are not limited to, paper, cloth, zeolite, and the like. The present composition may also be applied to the surface of an existing article and dried as necessary to form an antimicrobial layer. The resin-containing composition may itself be molded into a desired shape, such as a film, to form various articles with antimicrobial properties. Alternatively, the composition may be applied to the surface of an existing article and dried or cured as necessary to form an antimicrobial layer.

[0042] (Other embodiments) The present disclosure also provides a suitable method for producing one or more compounds selected from lactaldehyde, glycolaldehyde, and glyoxylic acid. Specifically, a composition is prepared that contains a photosensitizer (A) and a compound having one or more partial structures selected from >N-CH2C(CH3)OH, >N-CH2CH2OH, and >N-CH2COOH and salts thereof, and has an iron ion content of 50 mol% or less relative to the photosensitizer (A), and the composition is irradiated with light, whereby lactaldehyde, glycolaldehyde, and glyoxylic acid can be easily produced. In the production method, the reaction temperature is not particularly limited, and may be, for example, 5 to 40°C. The light source may be appropriately selected in consideration of the absorption wavelength of the photosensitizer (A) and the desired reaction rate, and is not particularly limited, but examples thereof include a white LED light source and sunlight.

[0043] The present disclosure also provides an antifungal composition comprising one or more antifungal agents selected from lactaldehyde, glycolaldehyde, and glyoxylic acid. It has been found that these compounds, which are relatively easily oxidized, are effective as antifungal agents. EXAMPLES

[0044] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, "ppm" stands for "μg / g" and "%" stands for "mass %".

[0045] [Example Group 1: Developmental Test of Compound (C)] <Example 1> A composition was prepared by mixing 126 ppm of sodium riboflavinate, 1 mass % of N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (ADEKACARPOL MD-100, manufactured by ADEKA Corporation, hereinafter also referred to as "MD-100"), and 0.23% of citric acid, and adding water to obtain the composition shown in Table 1. In the table, the numerical value of each component is expressed as mass % unless otherwise indicated as ppm.

[0046] <Examples 2 to 3> In Example 1, the compound (B) was changed as shown in Table 1 to prepare compositions of Examples 2 and 3. Citric acid was added so that the pH was almost the same as in Examples 1 to 3. EDTA stands for disodium ethylenediaminetetraacetate.

[0047] (Compound (C) generation test) 5 mL of each of the above compositions was placed in a 500 mL Erlenmeyer flask and sealed with a rubber stopper. Then, light irradiation was performed under the following conditions. Examples 1 to 2: Blue LED light (450 nm, 5500 lx) was irradiated for 2 hours. Example 3: White LED light (500 lx) was irradiated for 3 hours. The composition after irradiation was sampled and analyzed by gas chromatography mass spectrometry (GC-MS) or ion chromatography (IC) under the following measurement conditions. The results are shown in Table 1. ·GC-MS measurement conditions Column: InertCap624 (GL Science) 60m x 0.32mm x 1.8μm Temperature: Inj.250℃ Col.40℃(5min)→(10℃ / min)→280℃(2min) Mobile phase: He 1.0ml / min MS ion source: 230°C MS quadrupole: 150℃ Injection volume: 1μl ·IC measurement conditions Column: ICE-AS1 (Thermo Fisher) 9mm x 250mm Eluent: Octanesulfonic acid 1mM Flow rate: 1.0ml / min Injection volume: 50.0μl Column temperature: 35℃ Suppressor: MMS

[0048] [Table 1]

[0049] As shown in Table 1, it was revealed that compound (C) is generated by irradiating a composition containing photosensitizer (A) and compound (B) with light.

[0050] [Example Group 2: Gas-phase antifungal effect] <Example 11> A composition having the composition shown in Table 2 was prepared by mixing riboflavin equivalent to 10 ppm and triisopropanolamine equivalent to 0.1 mass % and adding water.

[0051] <Example 12> Riboflavin equivalent to 10 ppm, triisopropanolamine equivalent to 0.1 mass %, and a gelling agent (Ina Food Industry Co., Ltd.'s "Calicolican" (agar)) equivalent to 0.8 mass % were mixed, and water was added to prepare the composition shown in Table 2, thereby obtaining a gel composition.

[0052] <Examples 13 to 14> Compositions of Examples 13 and 14 were obtained in the same manner as in Example 11, except that the types and amounts of the photosensitizer (A) and the compound (B) in Example 11 were changed as shown in Table 2.

[0053] <Examples 15 to 18> The aldehydes shown in Table 2 were dissolved in water to obtain the compositions of Examples 15-18.

[0054] <Comparative Example 1> A composition of Comparative Example 1 was obtained in the same manner as in Example 11, except that the triisopropanolamine in Example 11 was changed to 1 mass % of sodium ascorbate.

[0055] <Comparative Example 2> In Example 4, ferrous chloride tetrahydrate was further added in an amount equivalent to 1 mass % to obtain the composition of Comparative Example 2.

[0056] <Comparative Examples 3 to 6> As shown in Table 2, the compositions of Comparative Examples 3 to 5 were obtained by dissolving only either the photosensitizer (A) or the compound (B) in water.

[0057] (Gas-phase anti-mold test) The gas-phase antifungal test method will be described with reference to Figure 1. 20 ml of potato dextrose agar medium 21 sterilized and dissolved in an autoclave was poured into a deep sterilized petri dish 20 (depth 2 cm, diameter 90 mm) and allowed to solidify. A suspension of black mold (NBRC9455) was painted in a single line onto the medium. Separately, 5 ml of the composition 11 of the above-mentioned Example or Comparative Example was poured into a sterile Petri dish 10 having a diameter of 60 mm. Also, as a blank test, a sterile Petri dish 10 into which 5 ml of water was poured was prepared. As shown in FIG. 1, the petri dish 10 was placed on the lid 30 corresponding to the petri dish 20, the petri dish 20 was then covered, and the periphery of the petri dish 20 and the lid 30 were sealed with vinyl tape. The plates were stored at 25° C. and exposed to white LED light (2000 lx) for 16 hours per day, while the mycelium on the plates was visually observed. Note that, for Reference Example 1, the plates were covered with aluminum foil and stored to avoid exposure to light. The vapor phase antifungal properties were evaluated according to the following criteria, and the results are shown in Table 2. (Evaluation Criteria) A: Mold growth was inhibited 100%. B: Compared to the blank, mold growth was inhibited by 80% or more but less than 100%. C: Mold growth was inhibited by 50% or more but less than 80% compared to the blank. D: Mold growth was inhibited by 10% or more but less than 50% compared to the blank. E: Inhibition of mold growth was less than 10% compared to the blank.

[0058] [Table 2]

[0059] As shown in Examples 15 to 18, the composition containing hydroxyaldehyde or aldehyde acid (compound (C)) was confirmed to have gas-phase antifungal properties. From the results of Example Group 1 above, it is considered that in Examples 11 to 14, compound (C) is gradually generated by light irradiation. Therefore, it is considered that the compositions of Examples 11 to 14 have excellent durability of gas-phase antifungal properties. Although the composition of Example 11 was used, no gas-phase antifungal effect was obtained in Reference Example 1, which was stored in a dark place. From this, it is presumed that compound (C) was not generated in a dark place. In addition, it was shown that the composition of Comparative Example 2, which contains a large amount of iron ions, did not generate enough compound (C) even though it contained photosensitizer (A) and compound (B).

[0060] [Example group 3: Bactericidal effect of liquid phase] <Example 21> A composition was prepared by mixing 12.6 ppm of sodium riboflavinate, 1000 ppm of N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and 230 ppm of citric acid, and adding water to obtain the composition shown in Table 3.

[0061] <Example 22> The composition of Example 22 was prepared by further mixing the composition of Example 21 with 220 ppm of lactaldehyde.

[0062] (Liquid Phase Bactericidal Test) 100 mL of the above composition was placed in a 300 mL beaker. Two compositions of Example 21 were prepared (one of them was designated Reference Example 2). In addition, a beaker containing 100 mL of water was prepared as a blank test. The beakers of Examples 21 and 22 were irradiated from above with blue LED light (5000 lx) for 10 minutes. 5 mL of the composition 72 hours after light irradiation was collected into a sterilized test tube by sterilizing and filtering. For Reference Example 2 and the blank test, 5 mL of the composition 72 hours after preparation was collected. Each composition was stored in a dark place at 25°C after light irradiation or preparation. Add 0.1 ml (approximately 105 The bacteria count was measured after 2 hours of contact with the composition (CFU / mL). The bactericidal rate of each composition was calculated based on the blank bacteria count. The results are shown in Table 3.

[0063] [Table 3]

[0064] Comparison of Reference Example 2 and Example 22 shows that lactaldehyde is an active ingredient for sterilization. Comparison of Reference Example 2 and Example 21 and the results of Example Group 1 show that the composition of Example 21 generates lactaldehyde by light irradiation and exhibits sterilizing properties.

[0065] [Example Group 4: Evaluation of antimicrobial durability] <Example 31> A composition was prepared by mixing 10 ppm of riboflavin, 1000 ppm of disodium ethylenediaminetetraacetate, 50 ppm of glycine, 200 ppm of potassium sorbate, and 50 ppm of nisin, and adding water. Two 500 mL Erlenmeyer flasks were filled with the composition (one of which was designated Reference Example 3). 7 1 ml of CFU / ml decay fluid was added and incubated with shaking at 30°C. In Example 31, a 3 mm bullet-shaped blue LED (wavelength 450 nm) was used, and irradiation was performed in water at intervals of 8 hours / day. In Reference Example 3, no light irradiation was performed. The change in the viable cell count over time was observed. The results are shown in Table 4. The viable cell count was measured by the plate count method.

[0066] [Table 4]

[0067] As shown in Example 31, the composition exhibited sustained antimicrobial activity even after 28 days. [Industrial Applicability]

[0068] The antimicrobial composition of the present disclosure can be used as an antifungal composition for food, for example, by applying it to food utensils, containers, packaging, etc. In addition, for example, the present composition containing a solvent can be used as a circulating fluid for a cooling tower or a chiller.

[0069] The present invention is not limited to the above-described embodiment, and can be modified as appropriate without departing from the spirit and scope of the present invention. [Explanation of symbols]

[0070] 10... Petri dish, 11... composition, 20... Petri dish, 21... culture medium, 30... lid.

Claims

1. The composition contains a photosensitizer (A) and one or more compounds (B) selected from an alkanolamine and an aminocarboxylic acid, An antimicrobial composition having an iron ion content of 50 mol % or less relative to the photosensitizer (A).

2. The compound (B) is >N-CH ２ C (CH ３ )OH, >N-CH ２ CH ２ OH and >N-CH ２ The antimicrobial composition of claim 1 , having one or more moieties selected from COOH and salts thereof.

3. The antimicrobial composition according to claim 1, wherein the photosensitizer (A) comprises at least one selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2): 【Chemistry 1】 In formula (1), R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group which may have a substituent, R ５ and R ６ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, In formula (2), R １１ , R １２ , R １３ and R １４ each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group which may have a substituent, R １５ and R １６ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent.

4. 2. The antimicrobial composition according to claim 1, wherein the total amount of heavy metal ions is 50 mol % or less relative to the photosensitizer (A).

5. 2. The antimicrobial composition according to claim 1, which generates one or more compounds (C) selected from hydroxyaldehydes and aldehyde acids under the action of light.

6. 6. The antimicrobial composition of claim 5, wherein the compound (C) comprises one or more selected from lactaldehyde, glycolaldehyde, and glyoxylic acid.

7. The antimicrobial composition of claim 1 further comprising a gelling agent.

8. The antimicrobial composition of claim 1 further comprising a resin.

9. An antimicrobial composition according to any one of claims 1 to 8, which has vapour phase mould resistance.

10. The antimicrobial composition according to any one of claims 1 to 8, further comprising one or more selected from the group consisting of sorbic acid, itaconic acid, dehydroacetic acid, glycine, thiamine sulfate, chitosan, lysozyme, and nisin, and having bacteriostatic properties.

11. A molded article obtained by molding the antimicrobial composition according to claim 8.

12. An antimicrobial sheet comprising a porous substrate impregnated with the antimicrobial composition according to any one of claims 1 to 8.

13. A fungicide composition comprising one or more fungicides selected from lactaldehyde, glycolaldehyde, and glyoxylic acid as a fungicide.

14. A method for producing one or more compounds selected from lactaldehyde, glycolaldehyde, and glyoxylic acid, comprising the steps of: A photosensitizer (A); >N-CH ２ C (CH ３ )OH, >N-CH ２ CH ２ OH and >N-CH ２ and a compound having one or more partial structures selected from COOH and its salts, A composition having an iron ion content of 50 mol % or less based on the photosensitizer (A), A manufacturing method comprising irradiating the material with light.

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