JP7497484B1 - Composition - Google Patents

Abstract

[Problem] To provide a composition having sustained release of a functional component. [Solution] The composition contains a photosensitizer (A), an amine compound (B), and a carboxylic acid compound (C), and at least a portion of the amine compound (B) and the carboxylic acid compound (C) form a salt. [Selected Figure] Figure 1

Description

The present invention relates to a composition, specifically a sustained release composition that sustains the release of a specific substance.

2. Description of the Related Art In order to sustain the effects of functional ingredients such as medicines, fragrances, agricultural chemicals, and fertilizers, sustained release materials that gradually release these functional ingredients have been investigated.
The sustained release material may be a microcapsule or a material having a porous substrate.
For example, Patent Document 1 describes specific sustained-release composite particles having core particles containing a polymer and a functional component, and micronized cellulose covering the core particles.
Patent Document 2 describes a microcapsule that includes a core containing an oil phase, a specific photosensitive polymer, and a photocatalyst, and a specific shell formed by interfacial polymerization, and describes that the oil phase is released by irradiation with light.
Furthermore, Patent Document 3 discloses a sustained release material containing specific metal oxide porous particles and a specific sustained release substance.

In addition, caged compounds are known as compounds that release specific compounds. Caged compounds are compounds in which a biologically active substance or the like is modified with a protecting group that can be deprotected by light, rendering it inactive. Caged compounds usually have a light-absorbing site in the molecule, and release the compound by irradiation with light.
Patent Document 4 discloses a method for releasing a compound by short-term light irradiation, in which a specific caged compound is irradiated with light in the presence of a photosensitizer.

International Publication No. 2019/208801 JP 2017-538815 A JP 2019-089976 A International Publication No. 2021/177343

The sustained-release materials in Patent Documents 1 to 3 require the synthesis of polymers and microcapsules and the production of porous particles, and sustained-release materials with superior productivity are in demand. In addition, there is a problem in that the polymers (microplastics) of the microcapsules and the porous particles remain after use, which can have an impact on the environment.

The present invention aims to provide a composition that provides sustained release of a functional ingredient.

The present invention provides a composition having the following configurations [1] to [14].
[1] A composition comprising a photosensitizer (A), an amine compound (B), and a carboxylic acid compound (C),
A composition in which the amine compound (B) and the carboxylic acid compound (C) at least partially form a salt.
[2] The composition according to the above [1], wherein the photosensitizer (A) includes a compound having a skeleton selected from isoalloxazine, alloxazine, phenothiazine, fluorescein, anthraquinone, and acridine.
[3] The composition according to the above [1] or [2], wherein the amine compound (B) includes a compound having an α-hydrogen of an amino group.
[4] The composition according to any one of the above [1] to [3], wherein the amine compound (B) includes a compound having an amino group and a hydrophilic group.
[5] The composition according to the above [4], wherein the hydrophilic group includes one or more selected from an amino group, a guanidino group, a carboxy group, and a hydroxy group.
[6] The composition according to any one of the above [1] to [5], wherein the amine compound (B) comprises one or more selected from the group consisting of alkanolamines, amino acids, and amino sugars.
[7] The composition according to any one of the above [1] to [6], wherein the carboxylic acid compound (C) includes one or more selected from fatty acids and cinnamic acids.
[8] The composition according to any one of the above [1] to [7], wherein a molar ratio of an amino group in the amine compound (B) to a carboxy group in the carboxylic acid compound (C) (amino group/carboxy group) is 1.0 or more.
[9] The composition according to any one of the above [1] to [8], further comprising a gelling agent.
[10] The composition according to any one of the above [1] to [9], which sustains release of the carboxylic acid compound (C).
[11] The composition according to any one of the above [1] to [10], which sustains release of the carboxylic acid compound (C) by light irradiation.
[12] The composition according to any one of the above [1] to [11], wherein the carboxylic acid compound (C) contains a fatty acid having 3 to 15 carbon atoms or a cinnamic acid, and has moss-removing properties.
[13] The composition according to any one of the above [1] to [12], wherein the carboxylic acid compound (C) contains a fatty acid having 3 to 15 carbon atoms and has antifungal properties.
[14] A composition comprising a photosensitizer (A), an amine compound (B), and a carboxylic acid compound (C),
the photosensitizer (A) contains a compound having a skeleton selected from isoalloxazine and alloxazine,
the amine compound (B) comprises a compound having an α hydrogen atom of an amino group,
The carboxylic acid compound (C) contains a fatty acid,
the amine compound (B) and the carboxylic acid compound (C) at least partially form a salt;
A sustained release composition which sustains the release of the carboxylic acid compound (C) by irradiation with light.

The present invention provides a composition that provides sustained release of a functional ingredient.

FIG. 2 is a schematic diagram for explaining a gas-phase antifungal property test. FIG. 2 is a schematic diagram for explaining a gas-phase antifungal property test of a gel composition. 1 is a graph showing the decomposition of an amine compound by light irradiation.

The composition according to the present invention will now be described.
In the present invention, the term "functional ingredient" refers to an ingredient that can exert a useful effect when released.
The term "to" indicating a range of numerical values includes the lower and upper limits, unless otherwise specified.

[Composition]
The composition contains a photosensitizer (A), an amine compound (B), and a carboxylic acid compound (C), and at least a portion of the amine compound (B) and the carboxylic acid compound (C) form a salt.
The composition has the above-mentioned constitution, and is a composition that slowly releases a carboxylic acid compound as a functional component. In the composition, the amine compound (B) and the carboxylic acid compound (C) form a salt (neutralization), and it is presumed that when light is irradiated, the amine compound (B) is decomposed by the action of the photosensitizer (A). As a result, the carboxylic acid compound (C) is gradually released. In the composition, the sustained release of the carboxylic acid compound (C) is photoresponsive, so it is also possible to control the amount of the carboxylic acid compound (C) released by irradiation with light. In addition, the composition can be easily prepared by the method described below, and is also excellent in productivity.

This composition contains at least a photosensitizer (A), an amine compound (B), and a carboxylic acid compound (C), and may further contain other components within the scope of the effects of the present invention. Each component that may be contained in this composition is described below.

<Photosensitizer (A)>
The photosensitizer (A) may be any one capable of decomposing the amine compound (B) by a photocatalytic reaction, 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 benzyl and camphorquinone; azo compounds, and organometallic 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 reactivity with the amine compound (B).

The photosensitizer (A) is preferably one having a tricyclic condensed ring (tricylic) from the viewpoint of obtaining an excellent photocatalytic action and being 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 which 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 from the viewpoint of photocatalytic performance by visible light (e.g., wavelength 400 to 600 nm).
Specific examples of compounds having a phenothiazine skeleton include perfeazine, chlorpromazine, acepromazine, phenothiazine, methylphenothiazine, methylene blue, etc., and from the viewpoint of sustained release of the composition, 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.

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). With these compounds, excellent photocatalytic effects can be obtained even when a light source with a relatively low output, such as a white LED, is used.

式（１）中、
Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々独立に、水素原子、ハロゲン原子、又は、置換基を有していてもよい炭化水素基であり、
Ｒ^５及びＲ^６は、各々独立に、水素原子、又は、置換基を有していてもよい炭化水素基であり、
式（２）中、
Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は、各々独立に、水素原子、ハロゲン原子、又は、置換基を有していてもよい炭化水素基であり、
Ｒ^１５及びＲ^１６は、各々独立に、水素原子、又は、置換基を有していてもよい炭化水素基である。

In formula (1),
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group which may have a substituent;
^R5 and ^R6 each independently represent 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 represent a hydrogen atom, a halogen atom or a hydrocarbon group which may have a substituent;
R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent.

Examples of the halogen atom in R ¹ to R ⁴ and R ¹¹ to R ¹⁴ include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group in R ¹ to R ⁴ and R ¹¹ to R ¹⁴ include a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group or an 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. Examples of the substituent that the hydrocarbon group in R ¹ to R ⁴ and R ¹¹ to R ¹⁴ may have include a hydroxy group, a carboxy group, and a halogen atom, and the hydroxy group and the carboxy group may be further esterified derivatives.
From the viewpoint of photocatalytic activity, it is preferable that R ¹ , R ⁴ , R ¹¹ and R ¹⁴ are each independently a hydrogen atom. Also, from the viewpoint of photocatalytic activity, it is preferable that R ² , R ³ , R ¹² and R ¹³ are each independently an unsubstituted linear or branched alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.

Examples of the hydrocarbon group in R ⁶ , R ¹⁵ and R ¹⁶ include the same as those in R ¹ , etc., and the preferred embodiments are also the same. From the viewpoint of photocatalytic activity, it is preferable that R ⁶ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom.

Examples of the hydrocarbon group in ^R5 include the same as those in ^R1 . Examples of the substituent that the hydrocarbon group in ^R5 may have include a hydroxyl group or an esterified product thereof. Among them, the substituent in ^R5 is preferably a ribityl group ( _-CH2 -CHOH-CHOH-CHOH- _CH2OH ) or an esterified product of the ribityl group.

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 can be suitably used, for example, in applications where the composition is dispersed in soil or air, or where it may be taken up by humans or other living organisms.
Specific examples of riboflavin derivatives include riboflavin tetrabutyrate, riboflavin tetraacetate, lumichrome (7,8-dimethylalloxazine), riboflavin phosphate and its salts (sodium salt, potassium salt, etc.), flavin adenine dinucleotide, and the like.

Among these, riboflavin, riboflavin tetrabutylate, lumichrome, and riboflavin sodium phosphate are preferred as the photosensitizer (A) in terms of photocatalytic activity, safety, and ease of industrial availability.

<Amine Compound (B)>
The amine compound (B) is a component which has at least one amino group in one molecule and can form a salt with the carboxylic acid compound (C), and which can be decomposed by the action of a photocatalyst.
The amino group in the amine compound (B) may be any of a primary amino group, a secondary amino group, and a tertiary amino group. From the viewpoint of decomposition by photocatalysis, it is preferable that the amine compound (B) has an α-hydrogen of the amino group, that is, the carbon atom adjacent to the nitrogen atom constituting the amino group has a hydrogen atom (the amine compound (B) has a structure of ">N-CH<").

In addition, when the present composition is used as an aqueous solution, it is preferable that the amine compound (B) has an amino group and a hydrophilic group in terms of the solubility of the salt formed by the amine compound (B) and the carboxylic acid compound (C). Examples of the hydrophilic group include an amino group, a guanidino group (-NHC(=NH)(-NH ₂ )), a carboxy group, and a hydroxy group. The hydrophilic group in the amine compound (B) may be one or more. When one molecule has two or more hydrophilic groups, the two or more hydrophilic groups may be the same or different. When the hydrophilic group is an amino group, the amine compound (B) has two or more amino groups. When the hydrophilic group is a carboxy group, it may also be included in the carboxylic acid compound (C) described later, but it is included in the amine compound (B) in consideration of its action in the present composition.

The amine compound (B) may be a low molecular weight compound or a high molecular weight compound. In the present invention, a low molecular weight compound refers to a compound having a molecular weight of 1,000 or less, and a high molecular weight compound refers to a compound having a molecular weight of more than 1,000.

Of the low molecular weight amine compounds (B), alkanolamines, amino acids, and amino sugars are preferred from the standpoints of decomposition by photocatalysis, solubility of salt-formed products, industrial availability, and the like.
Specific examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, dimethylethanolamine, N-ethylethanolamine, dimethylethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and tetrahydroxypropylethylenediamine.
Specific examples of amino acids include glycine, alanine, arginine, asparagine, aspartic acid, glutamine, glutamic acid, serine, cysteine, proline, and tyrosine. Among these, basic amino acids are preferred, and arginine is more preferred.
Specific examples of amino sugars include glucosamine, fructosamine, galactosamine, mannosamine, perosamine, sialic acid, muramic acid, and neuraminic acid, with glucosamine being preferred.

The molecular weight of the low molecular weight amine compound (B) is not particularly limited as long as it is 1,000 or less, but in order to suppress the proportion of the amine compound (B) in the composition, it is preferably 500 or less, and more preferably 300 or less. The lower limit of the molecular weight of the amine compound (B) is not particularly limited, but is usually 30 or more.

As the polymeric amine compound (B), chitosan or polyethyleneimine is preferred because it has a large number of amino groups per mass and is easy to form a salt with the carboxylic acid compound (C).

The chitosan is a compound having two or more structural units derived from glucosamine, and may have structural units derived from acetylglucosamine, and may further have other structures. It may also be a relatively low molecular weight compound that can be classified as a chitosan oligosaccharide. In terms of photocatalytic activity, the chitosan is preferably chitosan (poly-1,4-β-D-glucosamine) or chitosan oligosaccharide, which is polymerized by bonding the 1-position and the 4-position of multiple D-glucosamines. The chitosan may be a polyglucosamine consisting only of structural units derived from glucosamine, or may have structural units derived from N-acetylglucosamine.

The chitosan can be obtained by deacetylating, with an alkali, chitin obtained from, for example, the cell walls of shrimp, crab, mushroom, insect, fungus, etc. The degree of deacetylation of chitosan is preferably 50% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more, from the standpoint of the photocatalytic effect and the durability of the photocatalytic effect.
The degree of deacetylation of chitosan is expressed as {number of structural units derived from glucosamine/(number of structural units derived from glucosamine+number of structural units derived from acetylglucosamine)}×100 (%) and can be measured, for example, by colloid titration using potassium polyvinyl sulfate (PVSK).

Chitosan may also contain a chitosan derivative, such as hydroxyalkylene chitosan, e.g., hydroxyethyl chitosan, which is obtained by reacting the chitosan with an alkylene oxide, e.g., ethylene oxide, propylene oxide, etc.;
a carboxymethylated chitosan obtained by reacting the chitosan with (1) monochloroacetic acid or (2) reductive amination of glyoxalic acid;
Examples of the chitosan include chitosan having a crosslinked structure obtained by reacting the above chitosan with a dichloride such as adipic acid dichloride.

The molecular weight of chitosan is preferably 5,000 or more, more preferably 30,000 or more, and even more preferably 40,000 or more. On the other hand, in order to suppress the viscosity of the solution, the molecular weight of chitosan is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less.
In the present invention, the molecular weight of a polymer compound is the peak top molecular weight (Mp) determined as a standard pullulan equivalent value by aqueous gel filtration chromatography (Chromaster (registered trademark), manufactured by Hitachi High-Tech Science Corporation).

Polyethyleneimine is a compound having two or more types of structural units selected from the structural unit represented by -CH ₂ -CH ₂ -NH- and the structural unit represented by -CH ₂ -CH ₂ -N< in one molecule, and may be linear or branched, or may be a dendrimer type. Polyethyleneimine may have other structural units and may contain a polyethyleneimine derivative.
Examples of the polyethyleneimine derivatives include hydroxyalkylene polyethyleneimines such as hydroxyethyl polyethyleneimine obtained by reacting the above-mentioned polyethyleneimine with an alkylene oxide such as ethylene oxide or propylene oxide;
A carboxymethylated polyethyleneimine obtained by reacting the polyethyleneimine with (1) monochloroacetic acid or (2) reductive amination of glyoxalic acid;
Examples of the polyethyleneimine include polyethyleneimine having a crosslinked structure obtained by reacting the above-mentioned polyethyleneimine with a dichloride such as adipic acid dichloride.

The peak top molecular weight (Mp) of polyethyleneimine is preferably 10,000 or more, and more preferably 25,000 or more. On the other hand, from the viewpoint of ease of synthesis, the molecular weight of polyethyleneimine is preferably 1,000,000 or less, more preferably 800,000 or less, and even more preferably 500,000 or less.

Polyethyleneimine can be synthesized, for example, by ring-opening polymerization of aziridine. Alternatively, commercially available polyethyleneimine may be used.

The amine compound (B) may be used alone or in combination of two or more types, for example, a low molecular weight amine compound (B) may be combined with a high molecular weight amine compound (B).

<Carboxylic Acid Compound (C)>
The carboxylic acid compound (C) is a compound having at least one carboxy group in one molecule. In the present composition, the carboxylic acid compound (C) is a component that forms a salt with the amine compound (B) and is released by irradiation with light. The carboxylic acid compound (C) may have a substituent other than a carboxy group, but those having an amino group are included in the amine compound (B).

In the present composition, the carboxylic acid compound (C) is a functional component that is sustained-released, and may be appropriately selected depending on the application of the present composition. From the viewpoint of ease of controlling sustained release, monovalent carboxylic acids are preferred. Examples of such monovalent carboxylic acids include fatty acids and cinnamic acids.

The hydrocarbon group of the fatty acid may be linear or branched, and may be saturated or unsaturated.
Specific examples of fatty acids include acetic acid, propionic acid, butyric acid, hexanoic acid, caprylic acid, isononanoic acid, pelargonic acid, capric acid, neodecanoic acid, undecenoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, palmitoleic acid, oleic acid, elaidic acid, paccenic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, etc., and one type may be used alone or two or more types may be used in combination. In addition, linseed oil fatty acid, tung oil fatty acid, castor oil fatty acid, soybean oil fatty acid, tall oil fatty acid, rice bran oil fatty acid, palm oil fatty acid, coconut oil fatty acid, etc. may also be used.

Cinnamic acids include cinnamic acid and its derivatives. In the present invention, "cinnamic acid" includes the E form ((2E)-3-phenyl-prop-2-enoic acid) and the Z form ((2Z)-3-phenyl-prop-2-enoic acid; allocinnamic acid).

Examples of cinnamic acid and its derivatives include the compound represented by the following formula (11).

式（１１）中、
Ｒ^２１～Ｒ^２５は、各々独立に、水素原子、ハロゲン原子、水酸基、炭素数１～６のアルキル基、又は、炭素数１～６のアルコキシ基である。

In formula (11),
R ²¹ to R ²⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

The halogen atoms include fluorine, chlorine, and bromine atoms. The alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. The alkoxy groups include methoxy, ethoxy, propoxy, and butoxy groups.

Of the cinnamic acid and its derivatives, cinnamic acid, ferulic acid, caffeic acid, coumaric acid, sinapic acid, etc. are preferred, with cinnamic acid and ferulic acid being more preferred.

The carboxylic acid compound (C) can be used alone or in combination of two or more types.

Examples of applications in which the carboxylic acid compound (C) is used as a functional component include moss removers, antifungal agents, and spreaders for agricultural chemicals.
When the present composition is used as a moss-removing agent, the carboxylic acid compound (C) is preferably a fatty acid having 3 to 15 carbon atoms or a cinnamic acid, and among these, a fatty acid having 6 to 15 carbon atoms or a cinnamic acid is more preferred.
When the present composition is used as an antifungal agent, the carboxylic acid compound (C) is preferably a fatty acid having 3 to 15 carbon atoms, and among these, a fatty acid having 6 to 15 carbon atoms is more preferred.
Furthermore, when the present composition is used as a spreader for agricultural chemicals, the carboxylic acid compound (C) is preferably a fatty acid, more preferably a fatty acid having 8 or more carbon atoms, and even more preferably a fatty acid having 12 to 24 carbon atoms. By using a fatty acid having 8 or more carbon atoms, the difference in HLB value between the salt of the amine compound (B) and the carboxylic acid compound (C) and the simple carboxylic acid compound (C) after release becomes large, making it easier to attach the chemical to the surfaces of plants and pests.

The composition may contain other acidic compounds in place of or in combination with the carboxylic acid compound (C). The other acidic compounds may be any compounds capable of forming a salt with the amine compound (B), and examples of such compounds include sulfonic acid compounds and acidic phosphate esters.
The sulfonic acid compound is a compound having at least one sulfo group in one molecule, and is preferably an organic acid.Specific examples of the sulfonic acid compound include alkyl sulfonic acids such as octanesulfonic acid, dodecanesulfonic acid, and hexadecanesulfonic acid; alkyl benzene sulfonic acids such as decyl benzene sulfonic acid, dodecyl benzene sulfonic acid, and tridecyl benzene sulfonic acid; alkyl sulfates such as dodecyl sulfate and lauryl sulfate; alkyl ether sulfates such as polyoxyethylene lauryl ether sulfate and polyoxyethylene isotridecyl sulfate.
An acidic phosphate ester is a compound having a P-OH and a phosphate ester structure in the molecule. Specific examples of acidic phosphate esters include alkyl phosphate esters such as isotridecyl acid phosphate and oleyl acid phosphate, and ethylene glycol acid phosphate. These acidic compounds can be suitably used as the spreading agent.

(Content of each component)
The content ratio of the photosensitizer (A), the amine compound (B) and the carboxylic acid compound (C) in the present composition may be appropriately adjusted depending on the application.
The proportion of the photosensitizer (A) can be appropriately adjusted, for example, within a range of 0.1 × 10-5% by mass to ⁴⁰ % by mass relative to 100% by mass, which is the total mass of the photosensitizer (A), the amine compound (B), and the carboxylic acid compound (C), taking into consideration the amount of functional component generated relative to the amount of light irradiation and the duration of the effect.
From the viewpoint of the durability of the effect of the present composition and the viewpoint of the cost merit of the present composition, the ratio of the photosensitizer (A) to the total mass is preferably 40 mass% or less, more preferably 30 mass% or less, even more preferably 10 mass% or less, particularly preferably 5 mass% or less, and extremely preferably 0.5 mass% or less. Even if the present composition has a relatively high concentration of the photosensitizer (A) (e.g., 30 mass% or more), the effect of the functional component can be sustained when exposed to sunlight without releasing the carboxylic acid compound (C) all at once.
From the viewpoint of making the present composition a sustained-release composition having excellent photoresponsiveness, the ratio of the photosensitizer (A) is preferably 0.1× ^10-5 % by mass or more, more preferably 0.2× ^10-4 % by mass or more, and even more preferably 0.1× ^10-3 % by mass or more.

The molar ratio (amino group/carboxy group) of the amino group of the amine compound (B) and the carboxy group of the carboxylic acid compound (C) contained in this composition is preferably 1.0 or more, more preferably 1.2 or more, and even more preferably 1.5 or more. If the molar ratio is 1.0 or more, most of the carboxylic acid compound (C) in the composition is in salt form, so the effect of the functional component can be maintained for a long period of time. The upper limit of the molar ratio is not particularly limited, but for example, 3.0 or less is sufficient, preferably 2.5 or less, and more preferably 2.0 or less.
The molar ratio of the amine compound (B) to the carboxylic acid compound (C) (amine compound (B)/carboxylic acid compound (C)) is preferably from 1.0 to 3.0, more preferably from 1.2 to 2.5, and even more preferably from 1.5 to 2.0. The molar ratio of amino groups to carboxy groups in the composition can be determined from the amine value and acid value of the composition.

<Optional ingredients>
The composition may contain other components within the range in which the effects of the present invention are achieved, such as solvents and various additives such as surfactants, gelling agents, antifoaming agents, preservatives, and pH adjusters.

The solvent can be appropriately selected from those that 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 content of 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 is preferably a solvent consisting essentially of water, since it can be used for various purposes.
For example, the present composition containing water can be in a form in which the carboxylic acid compound (C) dissolves when the amine compound (B) forms a salt, and the carboxylic acid compound (C) precipitates when the amine compound (B) is decomposed. The present composition containing a solvent is also easy to handle, for example, when it is sprayed on soil or applied to a wall surface.

Surfactants are used for purposes such as imparting wettability to substrates, and can be appropriately selected from known surfactants such as anionic surfactants, nonionic surfactants, and cationic surfactants depending on the application.

The composition may also contain a gelling agent and be used in the form of a gel. As gelling agents, gelatin, thickening polysaccharides, or crosslinked products thereof are preferred, as they are also used in food applications and reduce the environmental impact. When a gelling agent is used, it is preferred that the composition contains water. Even if the gelling agent has a carboxy group, it is not included in the above carboxylic acid compound (C) in consideration of functionality.

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.

<Method of preparing the composition>
The method for preparing the present composition may be any method as long as the amine compound (B) and the carboxylic acid compound (C) are mixed so that at least a part of them forms a salt. Specific examples of the method include (I) a method in which the amine compound (B) and the carboxylic acid compound (C) are added to water and/or a water-soluble solvent and mixed to form a salt, and then the photosensitizer (A) and other components used as necessary are added; and (II) a method in which the photosensitizer (A), the amine compound (B), the carboxylic acid compound (C), and other components used as necessary are added to water and/or a water-soluble solvent and mixed to prepare a composition while forming a salt between the amine compound (B) and the carboxylic acid compound (C).
Alternatively, a highly concentrated composition may be prepared by the above method, and then diluted with a solvent such as water when in use.
When the present composition is used as a spreading agent, a known emulsifiable concentrate and a chemical such as an agricultural chemical can be added to the composition after the above preparation.

This composition can be suitably used as a sustained release composition that releases the carboxylic acid compound (C) by light irradiation. By adjusting the content of the photosensitizer (A), the composition can be made to have sustained release properties without releasing the carboxylic acid compound (C) all at once even under direct sunlight irradiation. In addition, by selecting the photosensitizer (A), excellent sustained release 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 applied to known applications in which a carboxylic acid compound is a functional component, and can be suitably used, for example, as a moss remover for outdoors, etc.; a moss growth inhibitor used as a circulating fluid for a cooling tower or added to the circulating fluid; and a mold inhibitor for the surface of an article or in the gas phase.

The present invention will be specifically explained 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."

[Photosensitizer (A)]
The following (A1) to (A7) were used as photosensitizers.
(A1): Riboflavin (A2): Riboflavin phosphate sodium (A3): Lumichrome (A4): Rose Bengal (A5): Eosin Y
(A6): Acridine orange (A7): Sodium 2-anthraquinonesulfonate

[Amine compound (B)]
As the amine compounds, the following (B1) to (B6) were used.
(B1): L-arginine (B2): monoisopropanolamine (B3): diethanolamine (B4): triethanolamine (B5): triisopropanolamine (B6): tetrahydroxypropylethylenediamine

[Carboxylic Acid Compound (C)]
As the carboxylic acid compounds, the following (C1) to (C11) were used.
(C1): Hexanoic acid, (C2): Caprylic acid, (C3): Isononanoic acid, (C4): Pelargonic acid, (C5): Capric acid, (C6): Neodecanoic acid, (C7): Undecenoic acid, (C8): Lauric acid, (C9): Myristic acid, (C10): Coconut oil fatty acid (containing fatty acids with 8 to 12 carbon atoms)
(C11): Ferulic acid

Example 1: Preparation of composition
Riboflavin (5 ppm equivalent), tetrahydroxypropylethylenediamine (2.3 mass %), and hexanoic acid (1.3 mass %) were mixed, and water was added to prepare the composition shown in Table 1, to obtain the composition of Example 1. In Tables 1 to 3, the numerical value of the photosensitizer (A) represents ppm, and the numerical values of the other components represent mass %.

[Examples 2 to 31 and Comparative Examples 1 to 9: Preparation of Compositions]
Each composition was prepared in the same manner as in Example 1, except that the components and their amounts were changed so as to obtain the compositions shown in Tables 1 to 3.

[evaluation]
<Moss removal>
A moss growing naturally on concrete was surrounded by masking tape to provide sections of 10 cm x 10 cm each. 5 mL of the composition of Example 1 was sprayed onto one section. The composition of Example 1 was sprayed onto the other section in the same manner.
One of the sections sprayed was kept under the dark conditions described below, and the other was kept under the light conditions described below for four days, and the ratio of the area of the concrete surface exposed (exposed area) was evaluated on a five-point scale according to the following evaluation criteria. In addition, the ratio of the exposed area under light conditions to the exposed area under dark conditions (exposed concrete area ratio) was calculated. The compositions of Examples 2 to 23 and Comparative Examples 1 to 5 were also subjected to the same test. The results are shown in Tables 1 and 2.
Dark conditions: The surface was covered with aluminum foil to block light.
Light condition: The sample was exposed to sunlight without being covered with aluminum foil.
(Evaluation criteria)
◎: 100% concrete exposed. ◯: 80% or more but less than 100% concrete exposed. △: 50% or more but less than 80% concrete exposed. ▲: 30% or more but less than 50% concrete exposed. ×: Less than 30% concrete exposed.

<Vapor phase mold resistance>
The gas-phase antifungal test method will be described with reference to Fig. 1. The mold used was black mold (NBRC9455). A medium 21 (Czapek-Dox agar medium, CDA medium) 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 turbid liquid of the mold was applied in a line using a platinum loop.
On the other hand, 5 mL of composition 11 of Example 24 was dispensed into another sterilized petri dish 10 (diameter 60 mm).
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 covered, and the outer periphery of the petri dish 20 and the lid 30 were sealed with vinyl tape. Two sets of this were created. One was cultured under the dark conditions described below and the other was cultured under the light conditions described below at 20°C for 5 days, and the mycelium on the medium was visually observed. Examples 25 to 31 and Comparative Examples 5 to 9 were also evaluated in the same manner. The results are shown in Table 3.
Dark conditions: Cultured in the dark.
Light conditions: A white LED was used, and light was irradiated at an intensity of 1,000 lx for 16 hours per day.
(Evaluation criteria)
⊚: Mold growth was sufficiently inhibited.
◯: Mold growth was inhibited to some extent.
×: Mold growth could not be inhibited.

[Summary of results]
The composition of Comparative Example 3, which contains an amine compound (B) and a carboxylic acid compound (C) but does not contain a photosensitizer (A), had the same moss removal properties under light and dark conditions. Comparative Example 4, which has a composition in which thymol, a known antibacterial agent, was added to the composition of Comparative Example 3, also had the same moss removal properties under light and dark conditions. In contrast, the compositions of Examples 1 to 23, which contain a photosensitizer (A), an amine compound (B), and a carboxylic acid compound (C), all had a concrete exposed area ratio of 1.1 or more, indicating that the moss removal properties were improved under light irradiation. As shown in Comparative Example 1, this effect was not obtained when potassium hydroxide was used instead of the amine compound (B).
With regard to the gas-phase antifungal effect, the effect was more remarkable, and it is presumed that in the compositions of Examples 24 to 31 containing a photosensitizer (A), an amine compound (B) and a carboxylic acid compound (C), the carboxylic acid generated by irradiation with light was vaporized and reached the medium, inhibiting the growth of mold.

[Example 32: Production of vapor phase antifungal gel]
5 ppm of riboflavin, 1.5% by mass of tetrahydroxypropylethylenediamine, 0.8% by mass of caprylic acid, and 0.8% by mass of a gelling agent (Ina Food Industry Co., Ltd.'s "Calicolican" (agar)) were mixed together, and water was added to obtain the gel composition of Example 32.
The vapor-phase antifungal activity test method will be described with reference to Fig. 2. 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 line on the medium.
The above-mentioned petri dish 20 and 9 g of the gel composition 11 were placed in a container having a volume of (200 mm x 170 mm x 30 mm) and covered with a lid. Two sets of these were prepared. In addition, a set containing only the petri dish 20 and no gel composition was also prepared.
One of the cultures was cultured under the dark conditions described below, and the other and the one not containing the gel composition were cultured under the light conditions described below at 20° C. for 7 days, and the mycelium on the medium was visually observed.
Dark conditions: Cultured in the dark.
Light conditions: A white LED was used, and light was irradiated at an intensity of 500 lx for 16 hours per day.
As a result of the above test, it was confirmed that mold growth occurred under dark conditions and in the case where the gel composition was not placed, whereas it was confirmed that mold growth was sufficiently inhibited under light conditions.
As described above, the effectiveness of the present composition has been confirmed even when made into a gel. For example, by storing the composition in a container together with food, it can have the effect of maintaining the freshness of the food.

[Test Example 1: Decomposition of amine by light irradiation]
A test solution was prepared by adding 50 ppm of riboflavin to a 1% aqueous solution of triethanolamine. The test solution was irradiated with a blue LED at 5,500 lx, and the amount of triethanol was measured by ion chromatography. As a control experiment, a 1% aqueous solution of triethanolamine without added riboflavin was also irradiated with light in the same manner. The results are shown in Figure 3.
As shown in FIG. 3, the amine compound (B) is decomposed by irradiating a composition containing a photosensitizer (A) and an amine compound (B) with light.

[Test Example 2: Generation of Carboxylic Acid Compounds by Irradiation with Light]
A test solution was prepared by mixing 20 ppm equivalent of riboflavin, 1.77 mass % equivalent of triisopropanolamine, 0.8 mass % equivalent of isononanoic acid, and water. 5 mL of the test solution was placed in a vial and irradiated with light under the following conditions. The gas phase of the vial before and after irradiation was measured by headspace gas chromatography analysis.
The area of the peak assigned to isononanoic acid after light irradiation was 1.32 times that before light irradiation.
<Light irradiation conditions>
The white LED was irradiated at 500 lx for 5 hours.
<Gas chromatography conditions>
Headspace sampler: Agilent Technologies 7697A
Column: HP-5MS (inner diameter 0.25 mm, 30 m, film thickness 0.25 μm)
Carrier gas: Helium (2.0 ml/min)

From the results of Test Examples 1 and 2, it is presumed that when a composition containing a photosensitizer (A), an amine compound (B), and a carboxylic acid compound (C) is irradiated with light, the decomposition of the amine compound (B) that forms a salt with the carboxylic acid compound (C) is promoted, resulting in the release of the carboxylic acid compound (C).
From the above, it has been demonstrated that the composition of the present invention, which contains a photosensitizer (A), an amine compound (B), and a carboxylic acid compound (C), in which at least a part of the amine compound (B) and the carboxylic acid compound (C) form a salt, gradually releases the carboxylic acid compound (C) by light irradiation.

The composition according to the present invention slowly releases a carboxylic acid compound (C) when irradiated with light, and can be suitably used as a moss remover, antifungal material, antibacterial agent, fragrance, etc., in which it is desirable to use a carboxylic acid compound as a functional component and to prolong its effect.

10: Petri dish, 11: composition, 12: gel composition, 20: petri dish, 21: culture medium, 30: lid, 40: container.

Claims (9)

Contains a photosensitizer (A), an amine compound (B), and a carboxylic acid compound (C),
the photosensitizer (A) contains a compound having a skeleton selected from isoalloxazine and alloxazine,
the amine compound (B) contains one or more selected from alkanolamines and amino acids,
the carboxylic acid compound (C) contains a fatty acid having 3 to 15 carbon atoms or a cinnamic acid,
A composition in which the amine compound (B) and the carboxylic acid compound (C) at least partially form a salt. The composition according to claim 1, wherein the amine compound (B) includes a compound having an alpha hydrogen of an amino group. The composition according to claim 1, wherein the molar ratio (amino group/carboxy group) of the amino group of the amine compound (B) to the carboxy group of the carboxylic acid compound (C) is 1.0 or more. The composition according to claim 1, further comprising a gelling agent. The composition according to claim 1, which sustains release of the carboxylic acid compound (C). The composition according to claim 5 , which sustains release of the carboxylic acid compound (C) by irradiation with light. The composition according to claim 1 or 5 , wherein the carboxylic acid compound (C) has moss- removing properties. The composition according to claim 1 or 5 , wherein the carboxylic acid compound (C) contains a fatty acid having 3 to 15 carbon atoms and has antifungal properties. Contains a photosensitizer (A), an amine compound (B), and a carboxylic acid compound (C),
the photosensitizer (A) contains a compound having a skeleton selected from isoalloxazine and alloxazine,
the amine compound (B) contains one or more selected from alkanolamines and amino acids having an α hydrogen atom of an amino group,
The carboxylic acid compound (C) contains a fatty acid,
the amine compound (B) and the carboxylic acid compound (C) at least partially form a salt;
A sustained release composition which sustains the release of the carboxylic acid compound (C) by irradiation with light.

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