Algal growth inhibitor composition

Abstract

To provide an algal growth inhibitor composition that maintains prolonged resistance to algae.SOLUTION: An algal growth inhibitor composition comprises an organosilicon compound represented by the following formula (1). (In the formula, R1 independently represents a hydrogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group; R2 independently represents a C1-C10 alkyl group or a C6-C10 aryl group; X represents a single bond, an oxyalkylene group, -O-, -S-, -NH-, -NHCO-, -NHCOO-, or -NHCONH-; Z represents a group having a nitrogen-containing heterocycle; m represents an integer of 1 to 20; and n represents an integer of 1 to 3).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an algae growth inhibitor composition, and more specifically, to an algae growth inhibitor composition containing an organosilicon compound. [Background technology]

[0002] In order to prevent deterioration of performance and appearance due to algae growth on surfaces that come into contact with water, such as cooling towers, ornamental fish tanks, water storage tanks, piping in bathtub circulation systems, and ship bottoms, a method has been proposed in which a composition containing octadecyldimethyl(3-trialkoxysilylpropyl)ammonium chloride as the main component is coated on the surfaces (Patent Document 1).

[0003] However, methods using such compositions may show a decrease in the durability of algae resistance over a long period of use, and therefore further improvement is desired. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2010-83830 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide an algae growth inhibitor composition which has excellent durability of algae resistance. [Means for solving the problem]

[0006] As a result of intensive research to achieve the above-mentioned object, the inventors discovered that an algae growth inhibitor composition containing a specific organosilicon compound can impart long-lasting algae resistance to articles such as glass, and thus completed the present invention.

[0007] That is, the present invention provides 1. An algae growth inhibitor composition comprising an organosilicon compound represented by the following formula (1): [ka] (In the formula, R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms; R 2 each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; X represents a single bond, an oxyalkylene group, -O-, -S-, -NH-, -NHCO-, -NHCOO-, or -NHCONH-; Z represents a group having a nitrogen-containing heterocycle; m is an integer of 1 to 20; and n is an integer of 1 to 3. 2. The algae growth inhibitor composition according to claim 1, wherein the nitrogen-containing heterocycle of Z is one or more rings selected from a triazine ring, an isothiazolidinone ring, an isothiazolinone ring, a benzimidazole ring, and derivatives thereof. 3. The algae growth inhibitor composition according to claim 1, further comprising an amino group-containing organosilicon compound other than the organosilicon compound represented by formula (1), wherein the mass ratio of the organosilicon compound represented by formula (1) to the other amino group-containing organosilicon compound is 99:1 to 10:90. 4. The algae growth inhibitor composition according to claim 1, further comprising water, an organic solvent or both as a solvent, and the content of the organosilicon compound represented by the formula (1) is 0.0001 to 40 mass% based on the total mass of the composition. 5. The algae growth inhibitor composition according to 4, wherein the water is adjusted to be acidic. 6. An article having any one of the algae growth inhibitor compositions 1 to 5 attached thereto. to provide. Effect of the Invention

[0008] The algae growth inhibitor composition of the present invention has excellent water resistance and can impart long-lasting algae resistance to articles such as glass. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention will be specifically described below. The algae growth inhibitor composition of the present invention contains an organosilicon compound represented by the following formula (1).

[0010] [ka]

[0011] In formula (1), R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R 1 The alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, and cyclohexyl groups. R 1 Specific examples of the aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, include a phenyl group and a tolyl group. Among these, R 1 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

[0012] R 2 each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms and the aryl group having 6 to 10 carbon atoms are each represented by R 1 Among these, a methyl group is more preferable.

[0013] X represents a single bond, an oxyalkylene group, -O-, -S-, -NH-, -NHCO-, -NHCOO-, or -NHCONH-. The oxyalkylene group of X includes those having 1 to 10 carbon atoms, and specific examples thereof include methyleneoxy, ethyleneoxy, trimethyleneoxy, and propyleneoxy groups. In addition, some of the hydrogen atoms of the oxyalkylene group may be substituted with hydroxy groups or amino groups.

[0014] Z represents a group having a nitrogen-containing heterocycle, which may be a heteroaromatic ring or a heterocycle that is partially or completely saturated, and may have either a monocyclic structure or a polycyclic structure (including a spirocyclic structure). The nitrogen-containing heterocycle may further contain an oxygen atom and / or a sulfur atom in the ring. Specific examples of the heteroaromatic ring include pyrrole, maleimide, imidazole, pyrazole, pyrazolone, triazole, tetrazole, pyridine, pyridone, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, azepine, diazepine, oxazole, isoxazole, thiazole, thiazolinone, isothiazole, isothiazolinone, furazan, oxadiazole, oxazine, oxadiazine, oxazepine, oxadiazepine, thiadiazole, thiazine, thiadiazine, thiazepine, thiadiazepine, indole, isoindole, indolizine, indazole, pyrindine, quinoline, isoquinoline, quinolizine, purine, phthalazine, pteridine, naphthyridine, quinoxaline, quinazoline, cinnoline, benzoxazole, benzothiazole, benzimidazole, benzofurazan, benzothiadiazole, and benzotriazole rings.

[0015] Specific examples of partially or fully saturated nitrogen-containing heterocycles include pyrroline, pyrrolidone, pyrrolidine, pyrrolizidine, succinimide, imidazoline, imidazolidine, imidazolidone, triazoline, triazolidine, tetrazoline, tetrazolidine, pyrazoline, pyrazolidine, pyrazolidone, dihydropyridine, tetrahydropyridine, piperidine, piperidone, dihydropyrazine, tetrahydropyrazine, piperazine, dihydropyrimidine, tetrahydropyrimidine, perhydropyrimidine, dihydropyridazine, tetrahydropyridazine, and perhydropyrimidine. -hydropyridazine, triazinane, triazinanetrione (isocyanuric acid), dihydroazepine, tetrahydroazepine, perhydroazepine, dihydrodiazepine, tetrahydrodiazepine, perhydrodiazepine, dihydrooxazole, tetrahydrooxazole (oxazolidine), dihydroisoxazole, tetrahydroisoxazole (isoxazolidine), dihydrothiazole (thiazoline), tetrahydrothiazole (thiazolidine), thiazolidinone, dihydroisothiazole (isothiazoline), tetrahydroisothiazo dihydrooxadiazole, tetrahydrooxadiazole (oxadiazolidine), dihydrooxazine, tetrahydrooxazine, dihydrooxadiazine, tetrahydrooxadiazine, dihydrooxazepine, tetrahydrooxazepine, perhydrooxazepine, dihydrooxadiazepine, tetrahydrooxadiazepine, perhydrooxadiazepine, dihydrothiadiazole, tetrahydrothiadiazole (thiadiazolidine), dihydrothiazolidine Azine, tetrahydrothiazine, dihydrothiadiazine, tetrahydrothiazepine, tetrahydrothiazepine, perhydrothiazepine, dihydrothiadiazepine, tetrahydrothiadiazepine, perhydrothiadiazepine, morpholine, thiomorpholine, indoline, isoindoline, dihydroindazole, perhydroindazole, dihydroquinoline, tetrahydroquinoline, perhydroquinoline, dihydroisoquinoline, tetrahydroisoquinoline, perhydroisoquinoline, dihydrophthalazine, tetrahydrophthalazine,Perhydrophthalazine, dihydronaphthyridine, tetrahydronaphthyridine, perhydronaphthyridine, dihydroquinoxaline, tetrahydroquinoxaline, perhydroquinoxaline, dihydroquinazoline, tetrahydroquinazoline, perhydroquinazoline, dihydrosinnoline, tetrahydrosinnoline, perhydrosinnoline, dihydrobenzoxazine, dihydrobenzothiazine, pyrazinomorpholine, dihydrobenzoxazole, perhydrobenzoxazole, dihydrobenzothiazole, perhydrobenzothiazole, dihydrobenzimidazole, perhydrobenzimidazole rings and the like can be mentioned.

[0016] Specific examples of the spiro-bonded bicyclic nitrogen-containing heterocyclic ring and the bridged bicyclic nitrogen-containing heterocyclic ring include azaspiro[4.4]nonane, oxazaspiro[4.4]nonane, azaspiro[4.5]decane, oxazaspiro[4.5]decane, azabicyclo[2.2.1]heptane, azabicyclo[3.1.1]heptane, azabicyclo[3.2.1]octane, azabicyclo[2.2.2]octane, azabicyclo[2.2.2]octane ring and the like.

[0017] Among these, a triazine ring, an isothiazolidinone ring, an isothiazolinone ring, and a benzimidazole ring are preferable.

[0018] In addition, in the group having a nitrogen-containing heterocyclic ring of Z, a hydrogen atom bonded to a carbon atom of the above nitrogen-containing heterocyclic ring and / or a hydrogen atom bonded to a nitrogen atom may be substituted with a halogen atom or a monovalent organic group. The monovalent organic group may be linear, branched, or cyclic, and includes an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, a hydroxy group, a carboxy group, -NR 3 2 represented groups (R 3 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group.) and the like. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, and icosyl groups. Examples of the cycloalkyl group include cyclopentyl and cyclohexyl groups. Specific examples of the aryl group include phenyl and naphthyl groups. Specific examples of the aralkyl group include benzyl and phenylethyl groups. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, -NR 3 2 Specific examples of the group represented by the formula (I) include an amino group, a methylamino group, a dimethylamino group, a cyclopropylamino group, a phenylamino group, a vinylamino group, a divinylamino group, an allylamino group, and a diallylamino group.

[0019] Specific examples of Z are shown below, but are not limited to these. Among these, the groups represented by (Z1) to (Z5) are preferable.

[0020] [ka] (In the formula, the wavy line represents a bond.)

[0021] m is an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 8, and even more preferably 3. n is an integer from 1 to 3.

[0022] Specific examples of the organosilicon compound represented by the above formula (1) are shown below, but are not limited to these. Among these, those represented by (1-1) to (1-5) are preferred. In the following chemical formulas, Me represents a methyl group.

[0023] [ka]

[0024] The organosilicon compound represented by the above formula (1) can be obtained, for example, by reacting (A) an isocyanato group-containing organosilicon compound (hereinafter referred to as compound (A)) with (B) a nitrogen-containing heterocyclic compound having an amino group, a hydroxyl group, or a mercapto group (hereinafter referred to as compound (B)) in the air or in an inert gas such as nitrogen.

[0025] Specific examples of the compound (A) include those represented by the following structural formulas, and the compound represented by (A-1) is preferred.

[0026] [ka]

[0027] Specific examples of the compound (B) include those represented by the following structural formulas, and the compounds represented by (B-1) and (B-2) are preferred.

[0028] [ka]

[0029] The reaction between the compound (A) and the compound (B) can be carried out without a solvent, but can also be carried out in an alcohol solvent such as methanol or ethanol, if necessary. The reaction temperature is preferably 0 to 150° C., more preferably 10 to 80° C. The reaction time is preferably 1 to 30 hours, more preferably 6 to 24 hours. The ratio (A) / (B) (molar ratio) of compound (A) to compound (B) used in the reaction is preferably 0.7 to 1.3.

[0030] The organosilicon compound represented by the above formula (1) can also be obtained by reacting (C) a mercapto group-containing organosilicon compound (hereinafter referred to as compound (C)) with (D) a nitrogen-containing heterocyclic compound having a Michael addition donor site (hereinafter referred to as compound (D)) in the atmosphere or in an inert gas such as nitrogen.

[0031] Specific examples of the compound (C) include those represented by the following structural formulas, and the compound represented by (C-1) is preferred. [ka]

[0032] Specific examples of the compound (D) include those represented by the following structural formulas, and the compound represented by (D-1) is preferred.

[0033] [ka]

[0034] The reaction between the compound (C) and the compound (D) can be carried out without a solvent, but can also be carried out in an alcohol solvent such as methanol or ethanol, if necessary. The reaction temperature is preferably 0 to 150° C., more preferably 10 to 80° C. The reaction time is preferably 1 to 30 hours, more preferably 6 to 24 hours. The ratio (C) / (D) (molar ratio) of compound (C) to compound (D) used in the reaction is preferably 0.7 to 1.3.

[0035] The organosilicon compound represented by the above formula (1) can also be obtained by reacting (E) an amino group-containing organosilicon compound (hereinafter referred to as compound (E)) with (F) a halogen-substituted nitrogen-containing heterocyclic compound (hereinafter referred to as compound (F)) in the air or in an inert gas such as nitrogen.

[0036] Specific examples of the compound (E) include those represented by the following structural formulas, and the compound represented by (E-1) is preferred.

[0037] [ka]

[0038] Specific examples of the compound (F) include those represented by the following structural formulas, and the compound represented by (F-1) is preferred.

[0039] [ka]

[0040] The reaction between the compound (E) and the compound (F) can be carried out without a solvent, but can also be carried out in a solvent, if necessary, within a range that does not inhibit the reaction. The reaction temperature is preferably 80 to 150° C., more preferably 100 to 130° C. The reaction time is preferably 1 to 30 hours, more preferably 6 to 24 hours. The ratio (E) / (F) (molar ratio) of compound (E) to compound (F) used during the reaction is preferably 0.7 to 1.3.

[0041] The organosilicon compound represented by the above formula (1) can also be obtained by reacting (G) an organosilicon compound containing a halogen-substituted alkyl group (hereinafter referred to as compound (G)) with (H) a nitrogen-containing heterocyclic compound having an amino group or a hydroxy group (hereinafter referred to as compound (H)) in the air or in an inert gas such as nitrogen.

[0042] Specific examples of the compound (G) include those represented by the following structural formulas, and the compound represented by (G-1) is preferred.

[0043] [ka]

[0044] Specific examples of the compound (H) include those represented by the following structural formulas, and the compound represented by (H-1) is preferred.

[0045] [ka]

[0046] The reaction between the compound (G) and the compound (H) can be carried out without a solvent, but can also be carried out in a solvent, if necessary, within a range that does not inhibit the reaction. The reaction temperature is preferably 80 to 150° C., more preferably 100 to 130° C. The reaction time is preferably 1 to 30 hours, more preferably 6 to 24 hours. The ratio (G) / (H) (molar ratio) of compound (G) to compound (H) used in the reaction is preferably 0.7 to 1.3.

[0047] The algae growth inhibitor composition of the present invention may further contain other organosilicon compounds. Other organosilicon compounds include amino group-containing organosilicon compounds, epoxy group-containing organosilicon compounds, and isocyanuric acid structure-containing organosilicon compounds. Among these, amino group-containing organosilicon compounds are preferred from the viewpoint of water resistance and algae resistance.

[0048] The amino group-containing organosilicon compound may be a compound having at least one of a primary amino group, a secondary amino group, and a tertiary amino group, and an alkoxysilyl group. Specific examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 8-aminooctyltrimethoxysilane, 8-aminooctyldimethoxysilane, 8-aminooctyltriethoxysilane, 8-aminooctylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxy ... Examples of the silane derivatives include N-(β-aminoethyl)-γ-aminopropyl methyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyldiethoxysilane, N-(β-aminoethyl)-γ-aminooctyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyldiethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, and N-phenyl-3-aminopropyl methyldimethoxysilane.

[0049] Examples of the epoxy group-containing organosilicon compound include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0050] An example of the organosilicon compound containing an isocyanuric acid structure is tris(trimethoxysilylpropyl)isocyanurate.

[0051] In the composition of the present invention, the mass ratio of the organosilicon compound (1) to the other organosilicon compounds is preferably from 99:1 to 10:90, and more preferably from 95:5 to 20:80. By ensuring that the content of the organosilicon compound (1) in the total organosilicon compounds contained in the composition is 10% by mass or more, algae resistance can be imparted, and by ensuring that the content of other organosilicon compounds is 1% by mass or more, the durability of the algae resistance can be improved.

[0052] The algae growth inhibitor composition of the present invention may further contain water, an organic solvent, or both as a solvent. As the water, it is preferable to use water adjusted to be acidic from the viewpoint of the stability of the composition. Examples of acids for adjusting the acidity include organic acids such as formic acid, acetic acid, and citric acid; and inorganic acids such as hydrochloric acid. When an acid is used, the amount of the acid added is preferably 0.001 to 0.5 mass % of the total composition, and more preferably 0.01 to 0.2 mass %. When an acid is used, the water may be adjusted to be acidic by mixing the acid and water in advance, or the acid may be added to the composition of the present invention to adjust the acidity. The organic solvent is not particularly limited, but is preferably an organic solvent having excellent compatibility with water, and examples thereof include alcohols such as methanol, ethanol, isopropanol, etc.; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, etc.; esters such as ethyl acetate, etc.; ketones such as acetone, methyl ethyl ketone, etc.; and amides such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, etc. These may be used alone or in combination of two or more.

[0053] The content of the organosilicon compound represented by the above formula (1) contained in the algae growth inhibitor composition of the present invention is preferably 0.0001 to 40 mass %, more preferably 0.001 to 10 mass %, based on the total mass of the composition, from the viewpoint of algae resistance.

[0054] The algae growth inhibitor composition of the present invention can impart algae resistance to various materials, articles and the like by adhering to them. Specific examples of the above materials and articles include inorganic materials such as glass, titanium, ceramics, cement, and mortar; synthetic resin materials such as polyvinyl chloride resin, acrylic resin, phenolic resin, epoxy resin, polycarbonate resin, and polybutylene terephthalate resin; and various metals such as iron, stainless steel, aluminum, nickel, zinc, and copper. EXAMPLES

[0055] The present invention will be described in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0056] [1] Manufacturing of organosilicon compounds [Synthesis Example 1-1] In a nitrogen-purged 100 mL reaction vessel, 15.4 g of 3-isocyanatopropyltrimethoxysilane represented by the following formula (A-1) and 15.5 g of a compound represented by the following formula (B-1) were placed and reacted for 20 hours at 25° C. After the reaction, the mixture was filtered to obtain 28 g of an organosilicon compound represented by the following formula (1-1).

[0057] [ka]

[0058] [Synthesis Example 1-2] In a nitrogen-purged 100 mL reaction vessel, 14.7 g of 3-mercaptopropyltrimethoxysilane represented by the following formula (C-1) and 16.0 g of a compound represented by the following formula (D-1) were placed and reacted for 20 hours at 25° C. After the reaction, the mixture was filtered to obtain 28 g of an organosilicon compound represented by the following formula (1-2).

[0059] [ka]

[0060] [Synthesis Example 1-3] In a nitrogen-purged 100 mL reaction vessel, 13.5 g of 3-aminopropyltrimethoxysilane represented by the following formula (E-1) and 11.2 g of a compound represented by the following formula (F-1) were placed and reacted for 20 hours at 120° C. After the reaction, the mixture was filtered to obtain 20 g of an organosilicon compound represented by the following formula (1-3).

[0061] [ka]

[0062] [Synthesis Example 1-4] In a nitrogen-purged 100 mL reaction vessel, 14.9 g of 3-chloropropyltrimethoxysilane represented by the following formula (G-1) and 8.86 g of benzimidazole represented by the following formula (H-1) were placed and reacted for 20 hours at 120° C. After the reaction, the mixture was filtered to obtain 20 g of an organosilicon compound represented by the following formula (1-4).

[0063] [ka]

[0064] [Synthesis Example 1-5] In a nitrogen-purged 100 mL reaction vessel, 15.4 g of 3-isocyanatopropyltrimethoxysilane represented by the following formula (A-1) and 9.99 g of a compound represented by the following formula (B-2) were placed and reacted for 20 hours at 25° C. After the reaction, the mixture was filtered to obtain 22 g of an organosilicon compound represented by the following formula (1-5). [ka]

[0065] [Comparative Synthesis Example 1-1] 39.7 g of 3-chloropropyltrimethoxysilane, 59.6 g of octadecyldimethylamine, and 99.3 g of methanol were placed in a nitrogen-purged 300 mL pressure reaction vessel and reacted for 20 hours at 120° C. After the reaction, the mixture was filtered to obtain 190 g of a methanol solution of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride (solid content concentration: 50% by mass).

[0066] [Comparative Synthesis Example 1-2] 48.2 g of 3-chloropropyltriethoxysilane, 59.6 g of octadecyldimethylamine, and 107.8 g of ethanol were placed in a nitrogen-purged 300 mL pressure reaction vessel and reacted for 20 hours at 120° C. After the reaction, the mixture was filtered to obtain 210 g of an ethanol solution of octadecyldimethyl(3-triethoxysilylpropyl)ammonium chloride (solid content concentration: 50% by mass).

[0067] [2] Production of algae growth inhibitor composition [Example 2-1] In a nitrogen-purged 200 mL mixing vessel, 0.5 g of the organosilicon compound (1-1) obtained in Synthesis Example 1-1, 99.5 g of N-methyl-2-pyrrolidone, 0.1 g of ion-exchanged water, and 0.1 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid.

[0068] [Example 2-2] In a nitrogen-purged 200 mL mixing vessel, 0.5 g of the organosilicon compound (1-2) obtained in Synthesis Example 1-2, 80.0 g of methanol, 19.5 g of ion-exchanged water, and 0.1 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid.

[0069] [Example 2-3] In a nitrogen-purged 200 mL mixing vessel, 0.5 g of the organosilicon compound (1-3) obtained in Synthesis Example 1-3, 50.0 g of methanol, 49.5 g of ion-exchanged water, and 0.1 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid.

[0070] [Example 2-4] In a nitrogen-purged 200 mL mixing vessel, 0.5 g of the organosilicon compound (1-4) obtained in Synthesis Example 1-4, 50.0 g of methanol, 49.5 g of ion-exchanged water, and 0.1 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid.

[0071] [Example 2-5] In a nitrogen-purged 200 mL mixing vessel, 0.5 g of the organosilicon compound (1-5) obtained in Synthesis Example 1-5, 50.0 g of methanol, 49.5 g of ion-exchanged water, and 0.1 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid.

[0072] [Example 2-6] Into a 200 mL mixing vessel purged with nitrogen, 0.5 g of the organosilicon compound (1-1) obtained in Synthesis Example 1-1, 0.25 g of 3-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 99.5 g of N-methyl-2-pyrrolidone, 0.1 g of ion-exchanged water, and 0.1 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid.

[0073] [Example 2-7] Into a 200 mL mixing vessel purged with nitrogen, 0.5 g of the organosilicon compound (1-2) obtained in Synthesis Example 1-2, 0.25 g of 3-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 80.0 g of methanol, 19.5 g of ion-exchanged water, and 0.1 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid.

[0074] [Example 2-8] Into a 200 mL mixing vessel purged with nitrogen, 0.5 g of the organosilicon compound (1-3) obtained in Synthesis Example 1-3, 0.25 g of 3-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 50.0 g of methanol, 49.5 g of ion-exchanged water, and 0.1 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid.

[0075] [Example 2-9] In a nitrogen-substituted 200 mL mixing vessel, 0.5 g of the organosilicon compound (1-4) obtained in Synthesis Example 1-4, 0.25 g of 3-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 50.0 g of methanol, 49.5 g of ion-exchanged water, and 0.1 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid.

[0076] [Example 2-10] Into a 200 mL mixing vessel purged with nitrogen, 0.5 g of the organosilicon compound (1-5) obtained in Synthesis Example 1-5, 0.25 g of 3-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 50.0 g of methanol, 49.5 g of ion-exchanged water, and 0.1 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid.

[0077] [Comparative Example 2-1] In a 200 mL mixing vessel purged with nitrogen, 2 g of the methanol solution of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride obtained in Comparative Example 1-1, 98 g of ion-exchanged water, and 0.1 g of citric acid were placed and stirred at 25°C for 1 hour to obtain a colorless, transparent liquid.

[0078] [Comparative Example 2-2] In a 200 mL mixing vessel purged with nitrogen, 2 g of the methanol solution of octadecyldimethyl(3-triethoxysilylpropyl)ammonium chloride obtained in Comparative Example 1-2, 98 g of ion-exchanged water, and 0.1 g of citric acid were placed and stirred at 25°C for 1 hour to obtain a colorless, transparent liquid.

[0079] [3] Manufacturing of articles having an algae growth inhibitor composition attached thereto [Examples 3-1 to 3-10, Comparative Examples 3-1 and 3-2] 0.1 g of each of the algae growth inhibitor compositions obtained in Examples 2-1 to 2-10 and Comparative Examples 2-1 and 2-2 was dropped onto the surface of a glass plate measuring 5.0 cm in length, 15 cm in width, and 1.5 mm in thickness, and the entire surface was evenly spread using a nonwoven fabric. The glass plate was then dried at 105°C for 10 minutes to produce a glass plate with the algae growth inhibitor composition adhered thereto.

[0080] [4] Evaluation of algae resistance [Preparation of Dettmel plate medium] 1.0 g of calcium nitrate, 0.25 g of potassium chloride, 0.25 g of magnesium sulfate heptahydrate, 0.25 g of potassium dihydrogen phosphate, 0.002 g of iron (III) chloride, and 20 g of agar were dissolved in 1000 ml of distilled water, sterilized in an autoclave at 121°C (equivalent to a pressure of 103 kPa) for 20 minutes, and approximately 20 ml of the solution was poured into a petri dish and allowed to solidify. [Preparation of Dettmel medium (medium for growing algae)] 1.0 g of calcium nitrate, 0.25 g of potassium chloride, 0.25 g of magnesium sulfate heptahydrate, 0.25 g of potassium dihydrogen phosphate, 0.002 g of iron (III) chloride, and 20 g of agar were dissolved in 1000 ml of distilled water and sterilized in an autoclave at 121°C (equivalent to a pressure of 103 kPa) for 20 minutes. [Preparation of algae test solution] Chlorella vulgaris (NIES-641) was transplanted onto Dettmel medium and cultured for one month in a sunny window while aerating with sterile air. [Algae resistance evaluation] The obtained glass plate was cut into a length of 5 cm and a width of 5 cm to be used as a test specimen. This test specimen was placed in the center of a Dettmel plate medium, and 1 ml of the algae test liquid was evenly sprinkled onto the medium and the test specimen, and the specimen was cultured for 20 weeks in a sunny window. During the culture, 1 ml of the algae test liquid was added to the medium and the test specimen every 4 weeks. After 4 weeks, 10 weeks, and 20 weeks from the start of culture, the algae resistance was judged based on the criteria in Table 1 below. The results are shown in Table 2.

[0081] [Table 1]

[0082] [Table 2]

[0083] As shown in Table 2, the glass plates to which the algae growth inhibitor compositions of Examples 3-1 to 3-5 were attached exhibited excellent durability of algae resistance. In particular, when the algae growth inhibitor compositions of Examples 2-6 to 2-10 to which an amino group-containing organosilicon compound was added were used (Examples 3-6 to 3-10), the durability of algae resistance was particularly excellent. On the other hand, in Comparative Examples 3-1 and 3-2, the algae resistance was lost after 10 weeks, indicating that the durability of the algae resistance was poor.

Claims

1. An algae growth inhibitor composition comprising an organosilicon compound represented by the following formula (1): 【Chemistry 1】 (In the formula, R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms; R 2 each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; X represents a single bond, an oxyalkylene group, -O-, -S-, -NH-, -NHCO-, -NHCOO-, or -NHCONH-; Z represents a group having a nitrogen-containing heterocycle; m is an integer of 1 to 20; and n is an integer of 1 to 3.

2. 2. The algae growth inhibitor composition according to claim 1, wherein the nitrogen-containing heterocycle of Z is one or more rings selected from the group consisting of a triazine ring, an isothiazolidinone ring, an isothiazolinone ring, a benzimidazole ring and derivatives thereof.

3. The algae growth inhibitor composition according to claim 1, further comprising an amino group-containing organosilicon compound other than the organosilicon compound represented by formula (1), wherein the mass ratio of the organosilicon compound represented by formula (1) to the other amino group-containing organosilicon compound is 99:1 to 10:

90.

4. The algae growth inhibitor composition according to claim 1, further comprising water, an organic solvent or both as a solvent, and the content of the organosilicon compound represented by formula (1) is 0.0001 to 40 mass% based on the total mass of the composition.

5. 5. The algae growth inhibitor composition according to claim 4, wherein the water is adjusted to be acidic.

6. An article having the algae growth inhibitor composition according to any one of claims 1 to 5 attached thereto.

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