Light-controlled release composition and article

Abstract

To provide a light-controlled release composition that allows control of release of a functional component by light, an article containing the light-controlled release composition, an antimicrobial sheet, and an antifungal composition suitable for use as a fungicide.SOLUTION: A light-controlled release composition comprises a photosensitizer (A), a compound (B), and water, wherein the photosensitizer (A) includes a photosensitizer (A1) having a tricyclic condensed ring, and the compound (B) is a compound satisfying at least one of the following conditions (B1)-(B3): (B1) having a hetero atom and a carbon atom at the α-position of the hetero atom, the carbon atom being bonded to one or more hydrogen atoms; (B2) having a carboxyl group or a salt thereof and a carbon atom at the α-position of the carboxyl group or the salt thereof, the carbon atom being bonded to one or more hydrogen atoms; (B3) having an aryl group and a carbon atom at the α-position of the aryl group, the carbon atom being bonded to one or more hydrogen atoms.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a light-sustained-release composition and an article. [Background technology]

[0002] Antimicrobial drugs are widely used for various purposes, such as food preservation, water quality stabilization, and infection prevention. However, 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 may be a burden on the environment.

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

[0004] In Patent Document 2, the present inventors disclose 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.

[0005] Furthermore, Patent Document 3 discloses a composition for packaging fresh plant products and the like, which comprises a matrix incorporating a lipid phase, and the lipid phase contains an initiator that enables the controlled release of lipid oxidation products. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 2018-511607 [Patent Document 2] International Publication No. 2022 / 80101 [Patent Document 3] Special Publication No. 2022-506214 Summary of the Invention [Problem to be solved by the invention]

[0007] The present disclosure aims to provide a light-controlled release composition capable of controlling the release of a functional ingredient by light, and an article containing the light-controlled release composition. [Means for solving the problem]

[0008] One aspect of the light sustained-release composition according to the present disclosure is A composition comprising a photosensitizer (A), a compound (B), and water, the photosensitizer (A) contains a photosensitizer (A1) having a tricyclic fused ring, The light-sustained-release composition, wherein the compound (B) is a compound that satisfies at least one of the following (B1) to (B3): (B1) A heteroatom and a carbon atom at the alpha position of the heteroatom, the carbon atom being bonded to one or more hydrogen atoms; (B2) a carboxyl group or a salt thereof and a carbon atom at the α-position of the carboxyl group or the salt thereof, the carbon atom being bonded to one or more hydrogen atoms; (B3) An aryl group and a carbon atom at the α-position of the aryl group, the carbon atom being bonded to one or more hydrogen atoms.

[0009] One embodiment of the article according to the present disclosure is obtained by impregnating a porous substrate with the above-described light-sustained-release composition.

[0010] Another embodiment of the article according to the present disclosure is a molded article in which the light-sustained-release composition further contains a resin. [Effects of the Invention]

[0011] The present disclosure provides a light-controlled release composition capable of controlling the release of a functional ingredient by light, and an article including the light-controlled release composition. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic diagram for explaining a vapor-phase antifungal property test. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, an embodiment of the present invention will be described. In the present disclosure, the term "functional component" refers to a component that can exert a useful effect when released. In this disclosure, "antimicrobial" refers to having antimicrobial activity against microorganisms (bacteria, fungi, viruses, parasites), and is a general term that includes antiviral, antibacterial, antifungal, and antimold. In the present disclosure, the range of values ​​indicated by "to" includes the lower and upper limits unless otherwise specified. Furthermore, when there are multiple identical symbols in a chemical formula, the identical symbols are not limited to those that represent the same substituent, and may represent different substituents within the range defined by the symbol.

[0014] [Photosustained release composition] The light sustained-release composition of the present disclosure comprises: A composition comprising a photosensitizer (A), a compound (B), and water, the photosensitizer (A) contains a photosensitizer (A1) having a tricyclic fused ring, The compound (B) is a compound that satisfies at least one of the following (B1) to (B3). (B1) A heteroatom and a carbon atom at the alpha position of the heteroatom, the carbon atom being bonded to one or more hydrogen atoms; (B2) a carboxyl group or a salt thereof and a carbon atom at the α-position of the carboxyl group or the salt thereof, the carbon atom being bonded to one or more hydrogen atoms; (B3) An aryl group and a carbon atom at the α-position of the aryl group, the carbon atom being bonded to one or more hydrogen atoms.

[0015] When this photo-sustained-release composition is irradiated with light, the light causes compound (B) to react with water in the air or solvent, producing the functional component, compound (C) having an aldehyde group (hereinafter simply referred to as compound (C)). In this composition, the reaction to produce compound (C) is photoresponsive and proceeds gradually depending on the amount of light irradiation, making it possible to control the amount of sustained release of compound (C). Furthermore, by controlling the release amount of compound (C), this composition has excellent sustained release of the functional component, allowing the functional component to be maintained for a long period of time.

[0016] The present light-sustained-release composition contains at least a photosensitizer (A), a compound (B), and water, and may further contain other components within the scope of the effects of the present invention. Each component that can be contained in the present light-sustained-release composition will be described below.

[0017] <Photosensitizer (A)> The photosensitizer (A) is a compound that exhibits a photocatalytic effect by the action of light and can decompose the compound (B). In the present light-sustained-release composition, the photosensitizer (A) contains a photosensitizer (A1) having a tricyclic fused ring, in order to obtain an excellent photocatalytic effect.

[0018] Examples of the photosensitizer (A1) include compounds having a skeleton such as anthracene, phenanthrene, fluorene, anthraquinone, xanthene, thioxanthene, xanthone, isoalloxazine, alloxazine, phenoxazine, fluorescein, thioxanthone, acridine, and phenothiazine. Of these, compounds having a skeleton selected from isoalloxazine, alloxazine, phenothiazine, fluorescein, anthraquinone, and acridine are preferred. Furthermore, compounds having an isoalloxazine skeleton or an alloxazine skeleton are more preferred because they exhibit a photocatalytic action when exposed to visible light (for example, a wavelength of 400 to 600 nm). The carbon atoms, nitrogen atoms, etc. constituting the various skeletons may have a substituent. Examples of the substituent include halogen atoms, hydroxyl groups; acidic groups such as carboxyl groups and sulfo groups; amino groups, and hydrocarbon groups. The acidic groups and amino groups may form salts, and the hydrocarbon groups may further have a substituent. Examples of the hydrocarbon groups include linear or branched alkyl groups having 1 to 6 carbon atoms. The photosensitizer (A1) may be used alone or in combination of two or more.

[0019] Specific examples of compounds having a phenothiazine skeleton include perfeazin, chlorpromazine, acepromazine, phenothiazine, methylphenothiazine, and methylene blue, and from the viewpoint of photocatalytic activity, perfeazin, chlorpromazine, and acepromazine are 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 photocatalytic activity, 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 compounds 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 (2) and compounds represented by the following general formula (3): These compounds exhibit excellent photocatalytic effects even when using a light source with a relatively low output, such as a white LED, and improve the production efficiency of compound (C) relative to the amount of light irradiation.

[0021] [ka] In formula (2), R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group which may have a substituent, R 25 and R 26 each independently represents a hydrogen atom or an optionally substituted hydrocarbon group, In formula (3), R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group which may have a substituent, R 35 and R 36 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent.

[0022] R 21 ~R 24 , R 31 ~R 34 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. R 21 ~R 24 , R 31 ~R 34 Examples of the hydrocarbon group in R include a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group or aryl group having 6 to 12 carbon atoms 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. 21 ~R 24 , R 31 ~R 34The substituents which the hydrocarbon group in the formula (I) may have include a hydroxy group, a carboxyl group, a halogen atom, etc., and the hydroxy group and the carboxyl group may be further esterified derivatives. In terms of photocatalytic activity, R 21 , R 24 , R 31 and R 34 are preferably each independently a hydrogen atom. 22 , R 23 , R 32 and R 33 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 even more preferably a methyl group.

[0023] R 26 , R 35 and R 36 The hydrocarbon group in R 21 In terms of photocatalytic activity, R 26 , R 35 and R 36 are each independently preferably a hydrogen atom.

[0024] R 25 The hydrocarbon group in R 21 R 25 Examples of the substituent that the hydrocarbon group in R may have include a hydroxy group or an esterified product thereof. 25 In particular, the substituent in is preferably a ribityl group (-CH2-CHOH-CHOH-CHOH-CH2OH) or an esterified version 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, so the photocontrolled release composition can be suitably used in applications where it comes into contact with food, such as container packaging, where it may be taken up by humans or other living organisms, or where it is released into the soil or atmosphere. Specific examples of riboflavin derivatives include riboflavin tetrabutyrate, riboflavin tetraacetate, lumichrome (7,8-dimethylalloxazine), riboflavin phosphate ester and salts thereof (sodium salt, potassium salt, etc.), flavin adenine dinucleotide, and the like.

[0026] Among these, the photosensitizer (A1) is preferably riboflavin, riboflavin tetrabutylate, lumichrome, or riboflavin sodium phosphate ester in view of photocatalytic activity, safety, industrial availability, and the like.

[0027] The photosensitizer (A) may be used in combination with the photosensitizer (A1) having a tricyclic fused ring, and another photosensitizer (A2) may be used. Examples of the photosensitizer (A2) include compounds having a skeleton such as naphthalene, perylene, benzophenone, naphthoquinone, coumarin, ketocoumarin, cyanine, merocyanine, oxonol, benzothiazole, oxazine, indoline, azulene, azulenium, porphyrin, triarylmethane, phthalocyanine, spiropyran, and spirooxazine; unsaturated ketones such as acridone, chalcone, and dibenzalacetone; 1,2-diketones such as benzil and camphorquinone; azo compounds; and organometallic complexes. The various skeletons may have a substituent on the carbon atom, nitrogen atom, etc. Examples of the substituent include the same ones as those in the photosensitizer (A1).

[0028] The photosensitizer (A) may consist solely of the photosensitizer (A1), or may be a combination of the photosensitizer (A1) and the photosensitizer (A2). When the photosensitizer (A1) and the photosensitizer (A2) are used in combination, the proportion of the photosensitizer (A1) in the photosensitizer (A) is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0029] <Compound (B)> Compound (B) is a precursor that generates compound (C) under the action of light. Examples of compound (B) include compounds that satisfy at least one of the following (B1) to (B3). These compounds generate a compound having an aldehyde group. Hereinafter, for convenience, a compound that satisfies (B1) may be referred to as compound (B1). The same applies to (B2) and (B3). (B1) A heteroatom and a carbon atom at the alpha position of the heteroatom, the carbon atom being bonded to one or more hydrogen atoms; (B2) a carboxyl group or a salt thereof and a carbon atom at the α-position of the carboxyl group or the salt thereof, the carbon atom being bonded to one or more hydrogen atoms; (B3) An aryl group and a carbon atom at the α-position of the aryl group, the carbon atom being bonded to one or more hydrogen atoms.

[0030] The heteroatom in (B1) above includes N, O, S and P, with N, O or S being preferred. In the above (B2), the cation that constitutes the salt of the carboxyl group (carboxylate) is not particularly limited, and examples thereof include sodium ions, potassium ions, and ammonium ions. In the above (B3), the aryl group includes a heteroaryl group.

[0031] The compound (B) may be a compound that satisfies one of (B1) to (B3), or may be a compound that satisfies two or more of them. Furthermore, the compound (B) may have, for example, two or more moieties that satisfy (B1). When the compound (B) has two or more moieties that satisfy (B1) to (B3), the following reaction occurs at each of the moieties.

[0032] It is presumed that when this composition is irradiated with light, the action of the light causes the hydrogen atom of the carbon atom at the α-position in compound (B) (hereinafter also referred to as the α-carbon) to be eliminated and an oxygen atom to be added, thereby generating an aldehyde.

[0033] When irradiated with light, the compound (B1) generates the compound (C1) by the following reaction. [ka] where R is an organic group, X is an organic group with a heteroatom at the end, and α indicates the position of the α carbon.

[0034] When irradiated with light, the compound (B2) generates the compound (C2) by the following reaction. [ka] where R is an organic group and α indicates the position of the α carbon.

[0035] Furthermore, when irradiated with light, the compound (B3) generates the compound (C3) by the following reaction. [ka] Here, Ar is an aryl group, and α indicates the position of the α carbon. The compounds (B1) to (B3) are not limited to the formulae (B1) to (B3) in the above scheme.

[0036] The compound (B) is preferably a compound represented by the following formula (1) in terms of stability as the compound (B), reactivity upon light irradiation, ease of availability, and the like. [ka] however, R a is an aryl group which may have a substituent, and X a is a hydrogen atom, or Or, R a is a hydrocarbon group which may have a substituent, and X a But, -NR 1 R 2 , -NR 1 C(=O)R 11 , -NR 1 C(=O)NR 2 R 3 , -OH, -OR 1 , -SH, -SR 1 , a carboxyl group, or a carboxylate; R 1 , R 2 and R 3 are each independently a hydrogen atom, a hydrocarbon group which may have a substituent, or -R 12 -X 1 (CH2R a ) m and R 11 represents a hydrogen atom, a hydrocarbon group which may have a substituent, or -R 12 -X 1 (CH2R a ) m and R 12 is an alkylene group having 1 to 12 carbon atoms, X 1 is N, O or S, m is X 1 is 2 if N, and X 1 is 1 if is O or S.

[0037] Above R a The compound (C) that is generated is R a It may be selected appropriately taking into consideration that CHO is included. R a When the aryl group optionally having a substituent is an aryl group, examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and also residues in which one hydrogen atom has been removed from heteroarenes such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, benzofuran, thionaphthene, indole, carbazole, coumarin, quinoline, phthalazine, and quinoxaline. Examples of the substituent that the aryl group may have include an alkyl group that may have a substituent, a halogen atom, a hydroxyl group, an amino group, a carboxyl group, a carboxylate, etc. Examples of the alkyl group include a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of the substituent that the alkyl group may have include a halogen atom, a hydroxyl group, an amino group, a carboxyl group, a carboxylate, etc.

[0038] R a However, in the case of a hydrocarbon group which may have a substituent, the hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may be linear or branched. Examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydroxyl group, an amino group, a carboxyl group, and an aryl group which may have a substituent.

[0039] R a When X is a hydrocarbon group which may have a substituent, a Ha-NR 1 R 2 , -NR 1 C(=O)R 11 , -NR 1 C(=O)NR 2 R 3 , -OH, -OR 1 , -SH, -SR 1 , a carboxyl group, or a carboxylate.

[0040] R 1 ~R 3 and R 11 The hydrocarbon group which may have a substituent in R a It is similar to that in R 1 ~R 3 or R 11 But -CH2R a It may also be a group represented by the following formula: R 12 The alkylene group in may be linear or branched.

[0041] R 1 ~R 3 or R 11 But -CH2R a or a hydrocarbon group represented by -R 12 -X 1 (CH2R a ) m In this case, R a CHO may occur. In addition, R 1 ~R 3 or R11 When R has a hydrocarbon group, 12 In cases where the compound (B) has the following structure, multiple types of aldehydes may be generated, and therefore it is preferable to select the structure of the compound (B) appropriately depending on the intended use of the present sustained-release composition.

[0042] 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).

[0043] Specific examples of the compound (B) and the compound (C) that can be generated from the compound (B) are shown below. Note that the carboxyl group in the formula may be in the form of a carboxylate salt. [ka] [ka]

[0044] All of the above-exemplified compounds (C) have excellent antimicrobial properties, and light-controlled release compositions that generate the compounds (C) can be used, for example, as antifungal agents, herbicides, and pest repellents. Furthermore, from the viewpoint of achieving both antimicrobial properties and minimizing impact on humans and the environment, it is preferable that the compound (C) contains lactaldehyde, glycolaldehyde, or glyoxylic acid. 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.

[0045] Specific examples of the compound (B) that generates lactaldehyde, glycolaldehyde, or glyoxylic acid include: Compounds that produce lactaldehyde, such as monoisopropanolamine, diisopropanolamine, triisopropanolamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, bis(2-hydroxypropyl)alkylamine, and dibutylpropanolamine; Compounds that produce glycolaldehyde, such as monoethanolamine, diethanolamine, triethanolamine, N,N-di(2-hydroxyethyl)cyclohexylamine, bis(2-hydroxyethyl)alkylamine, N-tertiarybutyldiethanolamine, and dibutylethanolamine; Compounds that produce lactaldehyde and glycolaldehyde, such as N-hydroxyethyl-N,N-di(2-hydroxypropyl)amine; Compounds that produce glyoxylic acid, such as ethylenediaminetetraacetic acid; and the like. The "alkyl" in the above examples is a moiety unrelated to the structure of the compound (C) to be produced, and is not particularly limited, and examples thereof include hydrocarbon chains having 1 to 12 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.

[0046] [Water (solvent)] The present light-controlled release composition contains water to facilitate dissolving or dispersing each component, and to improve the ease of handling and storage stability of the composition. Furthermore, depending on the intended use, a water-soluble solvent may be further used in combination. 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 preferably accounts for 10% by mass or less, and more preferably 5% by mass or less, of 100% by mass of the solvent. Furthermore, the solvent may be a solvent consisting essentially of water, which can be used for various purposes. The solvent-containing composition may be used for applications such as soil spraying or wall application. The solvent-containing composition may also be applied to the surface of a substrate such as food utensils, containers, or packaging, and then dried to form an antimicrobial layer. The solvent-containing composition may also be used as a circulating fluid for cooling towers and chillers, or as a culture medium for hydroponic cultivation or plant factories. When the present light-sustained-release composition is added with a resin or the like and used as a molded product, the composition may contain water to an extent that compound (C) can be produced.

[0047] (percentage of each ingredient) The ratio of photosensitizer (A) to compound (B) in the present sustained-release 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 amount of compound (C) generated per unit time increases and the sustainability of functional component generation increases. The ratio may be adjusted taking these factors into consideration. The proportion of photosensitizer (A) in the sustained-release composition may be adjusted within a range of 0.00001% to 10% by mass, preferably 0.0001% to 5% by mass, and more preferably 0.001% to 0.5% by mass, based on 100% by mass of the total composition. The proportion of compound (B) in the sustained-release composition may be adjusted within a range of 0.1% to 90% by mass, preferably 5% to 70% by mass, and more preferably 10% to 60% by mass, based on 100% by mass of the total composition. The concentration of compound (B) is adjusted appropriately depending on the intended use, environment of use, target organism, etc. of the composition. The mass ratio (A:B) of the photosensitizer (A) to the compound (B) is, for example, 1:0.01 to 1:9 × 10 6 The ratio can be adjusted appropriately within the range of 1:1 to 1:7 × 10 5 is preferable, and 1:20 to 6 × 10 4 is more preferred.

[0048] The content of iron ions in the composition is preferably 50 mol % or less, more preferably 30 mol % or less, even more preferably 10 mol % or less, still more preferably 5 mol % or less, and particularly preferably 1 mol % or less, relative to the photosensitizer (A), from the viewpoint of suppressing the generation of active oxygen during light irradiation and suppressing side reactions. In order to suppress side reactions and to suppress 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 most preferably substantially no heavy metal ions (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.

[0049] <Optional ingredients> The composition may contain other components within the scope of the effects of the present invention, such as various additives such as resins, gelling agents, surfactants, antifoaming agents, preservatives, and pH adjusters, and components for improving bacteriostasis.

[0050] (resin) The present optically sustained-release composition may contain a resin. The present resin-containing composition can 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 intended use of the molded product. Examples of resins include polyethylene, polypropylene, polyethylene terephthalate, nylon, cellulose, polyurethane, polycarbonate, and acrylic, and may be any of thermoplastic resins, thermosetting resins, and photocurable resins. The present resin-containing composition can be prepared by blending and uniformly kneading the photosensitizer (A), the compound (B), the resin, and, if necessary, other components. Molded articles of the present resin-containing composition can be used, for example, as food utensils, containers, and packaging. The present resin-containing composition may also be applied to a substrate to form a film.

[0051] (surfactant) The surfactant is used for the purpose of imparting wettability to a substrate or the like, and can be appropriately selected from known surfactants such as anionic surfactants, nonionic surfactants, and cationic surfactants depending on the application.

[0052] The present 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 being used in food applications and reducing the environmental load.

[0053] The above-mentioned gelatin refers to a denatured protein obtained by boiling collagen in water to make it water-soluble, and examples thereof include collagen obtained by denaturing collagen collected from the skin, bones, tendons, etc. of various animal species such as cows, pigs, and fish through various processes such as alkaline hydrolysis, acid hydrolysis, and enzymatic decomposition. Thickening polysaccharides are saccharide polymers that have many hydrogen-bonding groups within the molecule and can gel. Thickening polysaccharides can be appropriately selected from commonly known natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides depending on the intended use. Specific examples of thickening polysaccharides 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, and glucomannan. Agar, which is a mixture of agarose and agaropectin, may also be used.

[0054] (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 monofatty acid ester, oxalic acid or a salt thereof, itaconic acid or a salt thereof, tartaric acid or a salt thereof, citric acid or a salt thereof, adipic acid or a salt thereof, fumaric acid or a salt thereof, malic acid or a salt thereof, succinic acid or a salt thereof, sorbic acid or a salt thereof, lactic acid or a salt thereof, glycine or a salt thereof, thiamine lauryl sulfate or a salt thereof, chitosan or a salt thereof, dehydroacetic acid or a salt thereof, lysozyme, egg white lysozyme, allyl isothiocyanate, nisin, polylysine, yucca extract, licorice extract, hop extract, and milt protein. These 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).

[0055] <Method for preparing a light-sustained-release composition> The composition can be prepared by uniformly mixing the photosensitizer (A) and the compound (B), and specifically by adding the photosensitizer (A), the compound (B), and other optional additive components to a medium such as a water-containing solvent and / or a resin, and then mixing them. Alternatively, a highly concentrated composition may be prepared by the above method, and then diluted with a solvent such as water before use.

[0056] <Uses of the photo-sustained release composition> This photocatalytic composition is a composition that slowly releases a compound (C) having an aldehyde group upon irradiation with light, and because it can continuously produce this easily decomposed compound (C) over a long period of time, it can be used in any application where the compound (C) is used as a functional ingredient. Specifically, this composition can be used as an antifungal agent, herbicide, pest repellent, disinfectant, or fragrance. Furthermore, by selecting the photosensitizer (A), the photocomposition can provide excellent functionality such as antimicrobial properties even when using a light source with a relatively low output, such as a white LED. The present composition can be used in various forms. For example, it 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 also be impregnated into a porous substrate to form a sheet-like or particulate article. Examples of porous substrates include, but are not limited to, paper, fabric, and zeolite. Alternatively, the composition may be applied to the surface of an existing article and dried as necessary to form an antimicrobial layer. The resin-containing composition may be molded into a desired shape, such as a film, to form various articles with antimicrobial properties, etc. Alternatively, the composition may be applied to the surface of an existing article and, if necessary, dried or cured to form an antimicrobial layer. [Example]

[0057] 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. Note that hereinafter, "ppm" represents "μg / g" and "%" represents "% by mass."

[0058] [Confirmation test for generation of compound (C)] The generation of aldehyde from the light-controlled release composition of each example described below was confirmed by the following method. 5 mL of each composition was placed in a 500 mL Erlenmeyer flask and sealed with a rubber stopper. Next, light irradiation was performed for at least 2 hours using a blue LED (450 nm, 5500 lx) or white LED light (500 lx). After light irradiation, the composition was sampled and analyzed by gas chromatography-mass spectrometry (GC-MS), ion chromatography (IC), or liquid chromatography-mass spectrometry (LC-MS) under the following measurement conditions: ·GC-MS measurement conditions Column: InertCap624 (GL Science) 60 m x 0.32 mm x 1.8 μm 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 LC-MS measurement conditions Column: Inertsil ODS-2 (GL Sciences) 4.6 mm x 150 mm Mobile phase solvent: Gradient (acetonitrile / water = 9:1 to acetonitrile / THF / water = 7:2 / 1) Flow rate: 1.0ml / min Injection volume: 10.0μl Column temperature: 40℃ Ionization method: ESI

[0059] [Example Group 1: Evaluation of Durability of Vapor Phase Antifungal Effect] Example 1 A 0.1% by mass equivalent of sodium riboflavic acid ester and a 0.1% by mass equivalent of N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (ADEKACARPOL MD-100, manufactured by ADEKA Corporation, hereinafter also referred to as "MD-100") were mixed, and water was added to prepare a composition having the composition shown in Table 1.

[0060] <Examples 2 to 32 and Comparative Examples 1 to 7> Each compound and solvent were mixed to obtain the composition shown in Tables 1 to 3, and each composition was prepared in the same manner as in Example 1. In the tables, EDTA stands for ethylenediamine-N,N,N',N'-tetraacetic acid.

[0061] (Vapor phase antifungal test) 10 ml of potato dextrose agar medium 21 sterilized in an autoclave was poured into a deep sterilized petri dish 20 (depth 2 cm, diameter 90 mm) shown in Figure 1 and allowed to solidify. A suspension of black mold (NBRC9455) was applied in a single line onto the dish. Separately, 5 ml of the composition 11 of the above example or comparative example was poured into a sterilized petri dish 10 having a diameter of 60 mm. Also, as a blank test, 5 ml of water was poured into a sterilized petri dish 10. As shown in Figure 1, Petri dish 10 was placed on lid 30 corresponding to Petri dish 20, and Petri dish 20 was then placed on top of lid 30. The outer peripheries of Petri dish 20 and lid 30 were sealed with vinyl tape. Two of these were prepared for each composition, and one was cultured under the following light conditions and the other under the following dark conditions at 25°C for two days, and the mycelia that appeared on the medium were visually observed. Light conditions: Light was irradiated under the light irradiation conditions shown in Tables 1 to 3. Dark conditions: The petri dish was covered with aluminum foil and left undisturbed to avoid exposure to light. (Evaluation criteria) The width of the hyphae in the center of each sterilized petri dish 20 was measured, and the value of (hyphae width under light conditions Wb (cm)) / (hyphae width under dark conditions Wd (cm)) was calculated and evaluated. A: Wb / Wd was less than 0.1. B: Wb / Wd was 0.1 or more and less than 0.4. C: Wb / Wd was 0.4 or more and less than 0.6. D: Wb / Wd was 0.6 or more and less than 0.9. E:Wb / Wd was 0.9 or more.

[0062] [Table 1]

[0063] [Table 2]

[0064] [Table 3]

[0065] [Summary of Tables 1 to 3] The compositions of Comparative Examples 1 and 2 were control tests, and it was confirmed that when only either the photosensitizer (A) or the compound (B) was used, no aldehyde was generated even when irradiated with light. In the composition of Comparative Example 3, which used Basic Blue 1 as the photosensitizer (A), no generation of aldehyde was confirmed, and no vapor-phase antifungal effect was obtained. In the composition of Comparative Example 4, which used an ester instead of compound (B), no generation of aldehyde was confirmed, and no vapor-phase antifungal effect was obtained. In addition, in the composition of Comparative Example 5, which used sunflower oil equivalent to compound (B) but no water, no generation of aldehyde was confirmed, and no vapor-phase antifungal effect was obtained. In contrast, the compositions of Examples 1 to 32, which contain a photosensitizer (A1) having a tricyclic fused ring, a compound (B), and water, all generate aldehyde under light irradiation, and are shown to have a gas-phase anti-mold effect.

[0066] [Example Group 2: Herbicidal Evaluation] <Examples 41 to 42, Comparative Examples 11 to 12> As shown in Table 4, each composition was prepared by mixing each compound and a solvent.

[0067] (Leaf wither test) The leaves were collected and placed in a sterilized petri dish, and 1 mL of the composition of the example was applied to the entire surface. Two such dishes were prepared for each composition, and one was left standing for 3 days under the following light conditions and the other under the following dark conditions. Light conditions: Placed near a window exposed to sunlight. Dark conditions: The petri dish was covered with aluminum foil and left undisturbed to avoid exposure to light. (Evaluation criteria) The percentage of discolored area when the leaf area was set to 1 was visually observed, and the evaluation was performed by calculating (Ad-Ab) / Ad from the percentage of discolored area under light conditions, Ab, and the percentage of discolored area under dark conditions, Ad. A: (Ad-Ab) / Ad was 0.8 or more. B: (Ad-Ab) / Ad was 0.5 or more and less than 0.8. C: (Ad-Ab) / Ad was 0.3 or more and less than 0.5. D: (Ad-Ab) / Ad was 0.1 or more and less than 0.3. E: (Ad-Ab) / Ad was less than 0.1.

[0068] [Table 4]

[0069] [Example Group 3: Pest repellency evaluation] <Example 51, Comparative Examples 21 and 22> Each composition was prepared by mixing each compound and a solvent as shown in Table 5. In Comparative Example 22, water was used instead of the composition.

[0070] (Pest repellency test) 2 mL of the above composition and 30 ant baits were placed in a container. The container was then closed and exposed to sunlight outdoors for 10 minutes. After leaving it for 1 hour near a tree or bush, the number of ant baits remaining was counted. The greater the number of baits remaining, the better the pest repellency was evaluated. Table 5 shows the average values ​​obtained by conducting two tests for each Example and Comparative Example.

[0071] [Table 5]

[0072] As shown in Examples 41 to 42 and Example 51, the light-controlled release composition of this embodiment was shown to exhibit excellent effects as a herbicide and insect repellent. [Industrial Applicability]

[0073] The light-controlled release composition of the present disclosure can be used as an antifungal composition for food by applying it to, for example, food utensils, containers, packaging, etc. Furthermore, for example, the present composition containing a solvent can also be used as a circulating fluid for cooling towers and chillers.

[0074] The present invention is not limited to the above-described embodiment, and can be modified as appropriate within the scope of the invention. [Explanation of symbols]

[0075] 10... Petri dish, 11... composition, 20... Petri dish, 21... culture medium, 30... lid.

Claims

1. Contains a photosensitizer (A), a compound (B), and water, the photosensitizer (A) contains a photosensitizer (A1) having a tricyclic fused ring, The compound (B) is a compound that satisfies at least one of the following (B1) to (B3): (B1) A heteroatom and a carbon atom at the alpha position of the heteroatom, the carbon atom being bonded to one or more hydrogen atoms; (B2) a carboxyl group or a salt thereof and a carbon atom at the α-position of the carboxyl group or the salt thereof, the carbon atom being bonded to one or more hydrogen atoms; (B3) An aryl group and a carbon atom at the α-position of the aryl group, the carbon atom being bonded to one or more hydrogen atoms.

2. The light-sustained release composition according to claim 1, wherein the compound (B) is represented by the following formula (1): 【Chemical 1】 however, R ａ is an aryl group which may have a substituent, and X ａ is a hydrogen atom, or Or, R ａ is a hydrocarbon group which may have a substituent, and X ａ But, -NR １ R ２ , -NR １ C(=O)R １１ , -NR １ C(=O)NR ２ R ３ , —OH, —OR １ , -SH, -SR １ , a carboxyl group, or a carboxylate; R １ , R ２ and R ３ are each independently a hydrogen atom, a hydrocarbon group which may have a substituent, or -R １２ -X １ (CH ２ R ａ ) ｍ and R １１ represents a hydrogen atom, a hydrocarbon group which may have a substituent, or -R １２ -X １ (CH ２ R ａ ) ｍ and R １２ is an alkylene group having 1 to 12 carbon atoms, X １ is N, O or S, m is X １ is 2 when N, and X １ is 0 or S, then it is 1.

3. Due to the action of light, R ａ The light-sustained-release composition according to claim 2, which generates CHO.

4. The light-sustained-release composition according to claim 1, further comprising a gelling agent.

5. The light-sustained-release composition according to claim 1, further comprising a resin.

6. The light-controlled release composition according to any one of claims 1 to 5, which is used as an antifungal agent, a herbicide, or a pest repellent.

7. An article comprising a porous substrate impregnated with the light-releasing composition according to any one of claims 1 to 5.

8. An article comprising a molded product of the light-sustained-release composition according to claim 5.

Images