FLUORESCENT COMPOUND, METHOD FOR PRODUCING FLUORESCENT COMPOUND, AND WATER TREATMENT COMPOSITION

Abstract

Provided are a water-soluble fluorescent compound having a novel structure, and a method for producing the fluorescent compound. The fluorescent compound is represented by formula (1).

Description

[Technical field]

[0001] The present invention relates to a fluorescent compound, a method for producing the fluorescent compound, and a water treatment composition using the fluorescent compound. [Background technology]

[0002] Fluorescent compounds that emit light when irradiated with light are used in a variety of applications, such as fluorescent dyes, fluorescent pigments, fluorescent lamps, fluorescent brightening agents, displays, etc. To date, various inorganic and organic compounds have been known as fluorescent compounds.

[0003] For example, Patent Document 1 describes a water-soluble fluorescent compound for use in industrial water systems.

[0004] As such water-soluble fluorescent compounds, fluorescent compounds having novel structures are desired.

[0005] In addition, in various water systems such as cooling water systems, paper pulp process water systems, dust collection water systems, scrubber water systems, and wastewater systems, water treatment agents having effects such as scale precipitation inhibition, corrosion prevention, and sterilization are usually used in order to realize safe, stable, and efficient operation of the equipment. In order to obtain the optimal effect of these water treatment agents, it is desirable to measure the concentration of the water treatment agent in the water system and control the amount of addition. As one of the methods, a method of adding a reference substance, so-called a tracer substance, for measuring the change over time of the water treatment agent is known.

[0006] Known examples of tracer substances include fluorescent substances, etc. Patent Documents 2 and 3 propose sulfonated pyrene compounds as fluorescent substances.

[0007] Patent Document 4 proposes a water treatment composition that is an aqueous solution containing at least one oxidizing agent selected from the group consisting of hypochlorite, hypobromite, N-bromosulfamate, N-chlorosulfamate, and chlorite, and at least one tracer selected from the group consisting of compounds and their salts that have a basic skeleton of a condensed polycyclic hydrocarbon composed of 2 to 6 benzene rings and have a hydrophilic group, and has a pH of 13 or more. The water treatment composition in Patent Document 4 lists a wide range of compounds as tracer substances, but specifically, only existing 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt hydrate and 1,5-naphthalenedisulfonate disodium are used. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 7-128324 [Patent Document 2] JP 2015-188813 A [Patent Document 3] JP 2015-188814 A [Patent Document 4] JP 2017-012989 A Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide a water-soluble fluorescent compound having a novel structure, a method for producing the fluorescent compound, and a water treatment agent composition using the fluorescent compound. [Means for solving the problem]

[0010] The present invention is a fluorescent compound represented by formula (1). [ka] (In formula (1), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 One or more and up to five groups selected from the following are sulfo groups or chemically acceptable salts thereof. When n is 2, multiple R 9 and R 12 may be the same or different, provided that X is an oxygen atom, n is 1, and R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 When all are hydrogen atoms, R 3 and R 10 cannot be a sulfo group or a chemically acceptable salt thereof. In addition, X is a nitrogen atom substituted with an alkyl group having one carbon atom, n is 0, and R 1、R 2 、R 4 、R 5 、R 6 、R 7 、R 8 、R 10 and R 11 are all hydrogen atoms, and R 3 is a sulfo group or a chemically acceptable salt thereof; and a compound in which X is a nitrogen atom, n is 0, and R 2 、R 4 、R 5 、R 6 、R 7 、R 8 、R 10 and R 11 are all hydrogen atoms, and R 1 is a hydroxyl group, and R 3 is a sulfo group or a chemically acceptable salt thereof; and a compound in which X is a nitrogen atom, n is 0, and R 1 、R 3 、R 5 、R 6 、R 7 、R 8 、R 10 and R 11 are all hydrogen atoms, and R 4 is a hydroxyl group, and R 2 is a sulfo group or a chemically acceptable salt thereof; and a compound in which X is a nitrogen atom, n is 1, and R 1 、R 2 、R 3 、R 5 、R 6 、R 7 、R 8 、R 10 、R 11 and R12 are all hydrogen atoms, and R 4 、R 9 is a Sr salt of a sulfo group. )

[0011] In the fluorescent compound, X is preferably an oxygen atom.

[0012] In the fluorescent compound, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is preferably a sulfo group or a chemically acceptable salt thereof, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is preferably 0 or 1.

[0013] In the fluorescent compound, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 It is preferable that one or more and four or less groups selected from the group consisting of are a sulfo group or a chemically acceptable salt thereof.

[0014] In the fluorescent compound, R 3 , R 5 , R 6 , R 8 and R 10 It is preferred that at least one group is a sulfo group or a chemically acceptable salt thereof.

[0015] In the fluorescent compound, R 3 , R 5 , R 6 , R 8and R 10 It is preferable that at least two groups selected from are a sulfo group or a chemically acceptable salt thereof.

[0016] The present invention is a method for producing a fluorescent compound represented by formula (1), which comprises sulfonating an aromatic compound represented by formula (2). [ka] (In formula (1), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 One or more and up to five groups selected from the following are sulfo groups or chemically acceptable salts thereof. When n is 2, multiple R 9 and R 12may be the same or different, provided that X is an oxygen atom, n is 1, and R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 When all are hydrogen atoms, R 3 and R 10 cannot be a sulfo group or a chemically acceptable salt thereof.) [ka] (In formula (2), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12Two or more groups selected from are hydrogen atoms. When n is 2, multiple A 9 and A 12 may be the same or different. 1 From A 12 Each group represented by the same number R 1 From R 12 When the group represented by R is a sulfo group or a chemically acceptable salt thereof, the corresponding group represented by A is a hydrogen atom.)

[0017] In the method for producing the fluorescent compound, it is preferable that the sulfonation is carried out using at least one of chlorosulfonic acid, sulfuric acid, and fuming sulfuric acid.

[0018] In the method for producing the fluorescent compound, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 an aromatic sulfonic acid compound or a salt thereof, in which two or less groups selected from the group consisting of sulfo groups, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 It is preferable to co-produce an aromatic sulfonic acid compound or a salt thereof in which three or more groups selected from the group consisting of the above are sulfo groups.

[0019] The present invention is a water treatment agent composition comprising a fluorescent compound represented by formula (1). [ka] (In formula (1), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 One or more and up to five groups selected from the following are sulfo groups or chemically acceptable salts thereof. When n is 2, multiple R 9 and R 12 may be the same or different, provided that X is an oxygen atom, n is 1, and R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 When all are hydrogen atoms, R 3 and R 10 cannot be a sulfo group or a chemically acceptable salt thereof.)

[0020] The water treatment composition preferably further contains at least one component selected from the group consisting of a water-soluble polymer, a bactericide, an anticorrosive agent, and a pH adjuster.

[0021] In the water treatment composition, the water-soluble polymer is at least one monovalent compound selected from the group consisting of carboxylic acids and salts thereof. Mer It is preferred that the .alpha.-alkyl group has units.

[0022] In the water treatment composition, the germicide is preferably at least one of a chlorine-based oxidizing agent, a bromine-based oxidizing agent, and a hypohalous acid stabilizing composition.

[0023] In the water treatment agent composition, the stabilized hypohalous acid composition is preferably a stabilized hypobromous acid composition containing a bromine-based oxidizing agent and a sulfamic acid compound.

[0024] In the water treatment composition, the corrosion inhibitor is preferably at least one of a nitrite, a molybdate, a polymerized phosphate, a phosphonate, a zinc salt, and an azole compound.

[0025] The water treatment agent composition preferably contains at least the bactericide and the corrosion inhibitor selected from the group consisting of the water-soluble polymer, the bactericide, the corrosion inhibitor, and the pH adjuster, and the corrosion inhibitor is an azole compound.

[0026] In the water treatment agent composition, the mass ratio of the azole compound to the fluorescent compound is preferably in the range of 7:1 to 100:1.

[0027] In the water treatment agent composition, the azole compound is preferably 1,2,3-benzotriazole.

[0028] The present invention is a method for treating water to be treated, which comprises adding the water treatment agent composition to the water to be treated.

[0029] The present invention relates to a method for measuring the concentration of a water treatment agent composition in water to be treated, which comprises measuring the concentration of the water treatment agent composition contained in the water to be treated by fluorescence measurement.

[0030] The present invention is a concentration control method for controlling the concentration of the water treatment agent composition added to the water to be treated, the concentration control method controlling the concentration of the water treatment agent composition added to the water to be treated by measuring the concentration of the fluorescent compound.

[0031] The present invention is a concentration control device that controls the concentration of the water treatment agent composition added to the water to be treated, and controls the concentration of the water treatment agent composition added to the water to be treated by measuring the concentration of the fluorescent compound. Effect of the Invention

[0032] According to the present invention, it is possible to provide a water-soluble fluorescent compound having a novel structure, a method for producing the fluorescent compound, and a water treatment agent composition using the fluorescent compound. [Brief description of the drawings]

[0033] [Figure 1] 13 is a graph showing the remaining rate (%) of the fluorescent compound versus the mass ratio of the azole compound to the fluorescent compound after storage at 50° C. for 14 days in Example 16. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following describes an embodiment of the present invention. The embodiment is merely an example of implementing the present invention, and the present invention is not limited to the embodiment.

[0035] <Fluorescent compounds> The fluorescent compound according to this embodiment is an aromatic sulfonic acid compound represented by formula (1) or a salt thereof. [ka] (In formula (1), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 One or more and up to five groups selected from the following are sulfo groups or chemically acceptable salts thereof. When n is 2, multiple R 9 and R 12 may be the same or different, provided that X is an oxygen atom, n is 1, and R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 When all are hydrogen atoms, R 3 and R 10 cannot be a sulfo group or a chemically acceptable salt thereof.)

[0036] The fluorescent compound according to the present embodiment is a water-soluble organic fluorescent compound having a novel structure. The fluorescent compound according to the present embodiment can be used in various applications, such as monitoring applications, paints, displays, wavelength conversion films, and bioimaging (biofluorescent probes).

[0037] The aromatic sulfonic acid compound represented by formula (1) or its salt will be described in detail below. Note that the "aromatic sulfonic acid compound represented by formula (1) or its salt" which is the fluorescent compound according to this embodiment may be referred to as "aromatic sulfonic acid compound or its salt (1)" below.

[0038] The definitions of the substituents in the aromatic sulfonic acid compound or a salt thereof (1) and preferred specific examples thereof are as follows.

[0039] [About X] X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group.

[0040] The methylene group, nitrogen atom, or silicon atom represented by X may be substituted with an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be any of linear, branched, and cyclic alkyl groups, and specific examples thereof include a methyl group, a cyclohexylmethyl group, an ethyl group, a 2-cyclopentylethyl group, a propyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a 3-cyclopropylpropyl group, an isopropyl group, a cyclopropyl group, a butyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2-butyl group, a 3-methylbutan-2-yl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 2-methylpentyl group, a 3-ethylpentyl group, a 2,4-dimethylpentyl group, a 2-pentyl group, a 2-methylpentan-2-yl group, a 4,4-dimethylpentan-2-yl group, a 3-pentyl group, a 3-ethylpentan- Examples of such groups include cyclohexyl, cyclopentyl, 2,5-dimethylcyclopentyl, 3-ethylcyclopentyl, hexyl, 2-methylhexyl, 3,3-dimethylhexyl, 4-ethylhexyl, 2-hexyl, 2-methylhexane-2-yl, 5,5-dimethylhexane-2-yl, 3-hexyl, 2,4-dimethylhexane-3-yl, cyclohexyl, 4-ethylcyclohexyl, 4,4-dimethylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, 4-heptyl, bicyclo[2.2.1]heptyl, octyl, 2-octyl, 3-octyl, 4-octyl, cyclooctyl, and bicyclo[2.2.2]octyl groups. As the alkyl group having 1 to 8 carbon atoms, a methyl group, an ethyl group, or a tert-butyl group is preferred, and a methyl group is more preferred, from the viewpoint of ease of synthesis of the aromatic sulfonic acid compound or a salt thereof (1).

[0041] In terms of ease of synthesis of the aromatic sulfonic acid compound or a salt thereof (1), X is preferably an oxygen atom, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a methylene group, or a carbonyl group, more preferably an oxygen atom, a nitrogen atom, or a methylene group, still more preferably an oxygen atom or a methylene group, and particularly preferably an oxygen atom.

[0042] [About n] n represents 0, 1 or 2. In terms of ease of synthesis of the aromatic sulfonic acid compound or a salt thereof (1), n ​​is preferably 0 or 1, and more preferably 1.

[0043] [R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 About R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 one or more and not more than five groups selected from the group consisting of a sulfo group or a chemically acceptable salt thereof.

[0044] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12The sulfo group represented by the formula (I) may form a salt, and the salt is not particularly limited as long as it is a chemically acceptable salt, and may be an inorganic salt or an organic salt. Specific examples of the salt include an alkali metal salt, an alkaline earth metal salt, and an ammonium salt. Examples of the alkali metal salt include a lithium salt, a sodium salt, and a potassium salt. Examples of the alkaline earth metal salt include a calcium salt and a magnesium salt. Examples of the ammonium salt include an ammonium salt of an aliphatic amine or an aromatic amine, and examples of the aliphatic amine include ammonia, methylamine, and the like. hmm, Examples of the aromatic amine include pyridine, lutidine, pyrrole, imidazole, benzimidazole, triazole, etc. As the salt, an alkali metal salt or an ammonium salt is preferable in terms of ease of synthesis of the aromatic sulfonic acid compound or its salt (1), and a sodium salt, a potassium salt, an alkyl ammonium salt or an ammonium (NH4 + ) salts are more preferred, sodium salts, potassium salts or ammonium (NH4 + ) salt is more preferred, sodium salt or ammonium (NH4 + ) salts are particularly preferred, with the sodium salts being especially preferred.

[0045] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12The alkyl group having 1 to 8 carbon atoms represented by the formula (I) may be any of a linear, branched, or cyclic alkyl group, and specific examples thereof include a methyl group, a cyclohexylmethyl group, an ethyl group, a 2-cyclopentylethyl group, a propyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a 3-cyclopropylpropyl group, an isopropyl group, a cyclopropyl group, a butyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2-butyl group, a 3-methylbutan-2-yl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 2-methylpentyl group, a 3-ethylpentyl group, a 2,4-dimethylpentyl group, a 2-pentyl group, a 2-methylpentan-2-yl group, a 4,4-dimethylpentan-2-yl group, a 3-pentyl group, a 3-ethyl Examples of the alkyl group include pentan-3-yl group, cyclopentyl group, 2,5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, hexyl group, 2-methylhexyl group, 3,3-dimethylhexyl group, 4-ethylhexyl group, 2-hexyl group, 2-methylhexane-2-yl group, 5,5-dimethylhexane-2-yl group, 3-hexyl group, 2,4-dimethylhexane-3-yl group, cyclohexyl group, 4-ethylcyclohexyl group, 4,4-dimethylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, bicyclo[2.2.1]heptyl group, octyl group, 2-octyl group, 3-octyl group, 4-octyl group, cyclooctyl group, and bicyclo[2.2.2]octyl group. As the alkyl group having 1 to 8 carbon atoms, from the viewpoint of ease of synthesis of the aromatic sulfonic acid compound or a salt thereof (1), an alkyl group having 1 to 4 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.

[0046] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12The alkoxy group having 1 to 8 carbon atoms represented by the formula (I) may be either a linear or branched alkoxy group, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, an isopropoxy group, a 2-methylpropyloxy group, a 2-butyloxy group, a tert-butoxy group, a 2-ethylhexyloxy group, etc. As the alkoxy group having 1 to 8 carbon atoms, a methoxy group is preferred in terms of ease of synthesis of the aromatic sulfonic acid compound or a salt thereof (1).

[0047] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12The haloalkyl group having 1 to 8 carbon atoms and represented by the formula (I) may be any of linear, branched, and cyclic haloalkyl groups, and specific examples thereof include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a perfluoropropyl group, a Isopropyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group perfluorocyclobutyl group, 2,2,3,3,4,4-hexafluorocyclobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2,2,3,3,3-hexafluoro-1-(perfluoroethyl)propyl group, 2,2,3,3,3-pentafluoro-1-(perfluoroethyl)propyl group, perfluoro Examples of the haloalkyl group having 1 to 8 carbon atoms include a fluorocyclopentyl group, a perfluorohexyl group, a 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, a 4,4,5,5,6,6,6-heptafluorohexyl group, a 5,5,6,6,6-pentafluorohexyl group, a 6,6,6-trifluorohexyl group, a perfluorocyclohexyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a 2-chloroethyl group, and a 3-bromopropyl group. As the haloalkyl group having 1 to 8 carbon atoms, a trifluoromethyl group is preferable in terms of ease of synthesis of the aromatic sulfonic acid compound or a salt thereof (1).

[0048] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 The aromatic group having 6 to 10 carbon atoms represented by the formula (1) is not particularly limited, and specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc. As the aromatic group having 6 to 10 carbon atoms, a phenyl group is preferred in terms of ease of synthesis of the aromatic sulfonic acid compound or a salt thereof (1).

[0049] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Specific examples of the halogen atom represented by the formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the halogen atom, a fluorine atom or a bromine atom is preferred, and a bromine atom is more preferred, in terms of ease of synthesis of the aromatic sulfonic acid compound or a salt thereof (1).

[0050] The aromatic sulfonic acid compound or its salt (1) is easily synthesized, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 or R 12are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

[0051] The aromatic sulfonic acid compound or its salt (1) is easy to synthesize, and R 3 , R 5 , R 6 , R 7 , R 8 and R 10 is preferably a sulfo group, 3 , R 5 , R 6 , R 8 and R 10 More preferably, either one of R is a sulfo group, 3 , R 5 , R 6 and R 10 It is more preferable that either of R is a sulfo group. 5 and R 6 It is particularly preferred that either of R 5 It is particularly preferable that is a sulfo group.

[0052] The aromatic sulfonic acid compound or its salt (1) has high solubility in water-soluble solvents such as water. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 or R 12 Preferably, two or more of these are sulfo groups or chemically acceptable salts thereof, more preferably, three or more of these are sulfo groups or chemically acceptable salts thereof, and even more preferably, four or more of these are sulfo groups or chemically acceptable salts thereof.

[0053] Aromatic sulfonic acid compounds or salts thereof (1) are preferred because of their high solubility in water and other water-soluble solvents. 1 , R 2 , R3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is preferably a sulfo group or a chemically acceptable salt thereof, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is preferably 0 or 1.

[0054] In the aromatic sulfonic acid compound or its salt (1), R 3 , R 5 , R 6 , R 7 , R 8 and R 10 At least one group of R is preferably a sulfo group or a chemically acceptable salt thereof. 3 , R 5 , R 6 , R 8 and R 10 More preferably, at least one group of R is a sulfo group or a chemically acceptable salt thereof, 5 , R 6 , R 8 and R 10 It is further preferred that at least one group of R is a sulfo group or a chemically acceptable salt thereof. 5 and R 10 It is particularly preferred that at least one group of R is a sulfo group or a chemically acceptable salt thereof. 5 is particularly preferably a sulfo group or a chemically acceptable salt thereof.

[0055] Aromatic sulfonic acid compounds or salts thereof (1) are preferred because of their high solubility in water and other water-soluble solvents. 3 , R 5 , R 6 , R 7 , R 8 and R 10At least two groups selected from R 3 , R 5 , R 6 , R 8 and R 10 More preferably, at least two groups of R are sulfo groups or chemically acceptable salts thereof, 5 , R 6 , R 8 and R 10 It is further preferred that at least two groups of R are sulfo groups or chemically acceptable salts thereof. 5 , R 6 and R 10 It is particularly preferred that at least two groups of R are sulfo groups or chemically acceptable salts thereof. 5 and R 10 is particularly preferably a sulfo group or a chemically acceptable salt thereof.

[0056] In the aromatic sulfonic acid compound or its salt (1), when n is 2, a plurality of R 9 and R 12 may be the same or different.

[0057] In the aromatic sulfonic acid compound or its salt (1), X is an oxygen atom, n is 1, and R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 When all are hydrogen atoms, R 3 and R 10 cannot be a sulfo group or a chemically acceptable salt thereof.

[0058] The aromatic sulfonic acid compound or a salt thereof (1) is not particularly limited, and specific examples thereof include the compounds having the structures shown in 1-1 to 1-1325 below.

[0059]

change

[0060]

change

[0061]

change

[0062]

change

[0063]

change

[0064]

change

[0065]

change

[0066]

change

[0067]

change

[0068]

change

[0069]

change

[0070]

change

[0071]

change

[0072]

change

[0073]

change

[0074]

change

[0075]

change

[0076]

change

[0077]

change

[0078]

change

[0079]

change

[0080]

change

[0081]

change

[0082]

change

[0083]

change

[0084]

change

[0085]

change

[0086]

change

[0087]

change

[0088]

change

[0089]

change

[0090]

change

[0091]

change

[0092]

change

[0093]

change

[0094]

change

[0095]

change

[0096]

change

[0097]

change

[0098]

change

[0099]

change

[0100]

change

[0101]

change

[0102]

change

[0103]

change

[0104]

change

[0105]

change

[0106]

change

[0107]

change

[0108]

change

[0109]

change

[0110]

change

[0111]

change

[0112] In this specification, SO3M represents a sulfonic acid or a chemically acceptable salt of a sulfonic acid.

[0113] Among the compounds represented by compounds 1-1 to 1-1325, the aromatic sulfonic acid compounds or salts thereof (1) are, in view of their high solubility in water-soluble solvents such as water, 1-1, 1-2, 1-4, 1-80, 1-83, 1-85, 1-90, 1-92, 1-132, 1-135, 1-171, 1-173, 1-324, 1-441, 1-508, 1-509, 1-526, 1-533, 1-693, 1-694, 1-696, 1-705, 1-708, 1-715, 1-717, 1-729, 1-1 134, 1-1136, 1-1145, 1-1196, 1-1197, 1-1199, 1-1128, 1-1299 or 1-1300 are preferred, 1-1, 1-2, 1-83, 1-85, 1-90, 1-135, 1-171, 1-173, 1-324, 1-441 or 1-693 are more preferred, 1-2, 1-83, 1-90, 1-171 or 1-173 are even more preferred, and 1-2, 1-90 or 1-171 are particularly preferred.

[0114] The aromatic sulfonic acid compound or a salt thereof (1) has, for example, a fluorescence wavelength in the range of 350 to 500 nm and an excitation wavelength in the range of 310 to 380 nm.

[0115] <Method of manufacturing fluorescent compounds> Next, a method for producing the aromatic sulfonic acid compound or its salt (1), which is a fluorescent compound according to an embodiment of the present invention, will be described.

[0116] The aromatic sulfonic acid compound or a salt thereof (1) can be produced, for example, by Step 1 shown in the following reaction scheme.

[0117] [ka] (In the formula, X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 Two or more groups selected from are hydrogen atoms. When n is 2, multiple A 9 and A 12 may be the same or different. 1 From A 12 Each group represented by the same number R 1 From R 12 When the group represented by R is a sulfo group or a chemically acceptable salt thereof, the corresponding group represented by A is a hydrogen atom. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11and R 12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 One or more and up to five groups selected from the following are sulfo groups or chemically acceptable salts thereof. When n is 2, multiple R 9 and R 12 may be the same or different, provided that X is an oxygen atom, n is 1, and R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 When all are hydrogen atoms, R 3 and R 10 cannot be a sulfo group or a chemically acceptable salt thereof.)

[0118] Step 1 is a step of producing an aromatic sulfonic acid compound or a salt thereof (1) by sulfonating an aromatic compound (2).

[0119] X and n in the aromatic compound (2) have the same meanings as X and n in the aromatic sulfonic acid compound and its salt (1), and examples of X include the same substituents.

[0120] In aromatic compounds (2) A 1 、 A 2 , A 3 , A4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 Chemically acceptable salts of the sulfo group are represented by R 1 ~R 12 Examples of the salts include the same chemically acceptable salts of the sulfo group as those exemplified above.

[0121] In aromatic compounds (2) A 1 、 A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 The alkyl group having 1 to 8 carbon atoms represented by the formula: 1 ~R 12 Examples of the substituent include the same alkyl groups having 1 to 8 carbon atoms as those exemplified in 1.

[0122] A in aromatic compounds (2) 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 The alkoxy group having 1 to 8 carbon atoms represented by the formula: 1 ~R 12 Examples of the substituents include the same as the alkoxy groups having 1 to 8 carbon atoms exemplified in 1.

[0123] A in aromatic compounds (2) 1 , A 2 , A 3 , A 4 , A5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 A haloalkyl group having 1 to 8 carbon atoms, represented by the formula: 1 ~R 12 Examples of the substituents include the same substituents as the haloalkyl groups having 1 to 8 carbon atoms exemplified in 1.

[0124] A in aromatic compounds (2) 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 The aromatic group having 6 to 10 carbon atoms is represented by R 1 ~R 12 Examples of the substituents include the same aromatic groups having 6 to 10 carbon atoms as those exemplified in 1.

[0125] A in aromatic compounds (2) 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 The halogen atom represented by R 1 ~R 12 Examples of the substituents include the same halogen atoms as those exemplified above.

[0126] A in aromatic compounds (2) 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A8 , A 9 , A 10 , A 11 and A 12 In terms of ease of synthesis of the aromatic compound (2), a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and a hydrogen atom is more preferred.

[0127] Examples of the aromatic compound (2) used in step 1 include compounds having the structures shown in 2-1 to 2-12 below.

[0128] [ka]

[0129] Among the compounds represented by 2-1 to 2-12, the compounds represented by 2-1, 2-2, 2-3, 2-4, 2-5 or 2-8 are preferred in terms of ease of synthesis of the aromatic compound (2), and the compounds represented by 2-1, 2-2 or 2-3 are more preferred. The aromatic compound (2) can be produced by a general method well known to those skilled in the art, and for example, the aromatic compound (2) can be obtained according to the method disclosed in Chin. J. Org. Chem. 2018, Vol. 38, pp. 1516-1524. In addition, a commercially available product may be used as the aromatic compound (2).

[0130] The sulfonation in step 1 can be carried out using a sulfonating agent. Specific examples of the sulfonating agent include sulfuric acid, fuming sulfuric acid, sulfur dioxide, sulfur trioxide, chlorosulfonic acid (sulfur chloride), and sulfuryl chloride, and these sulfonating agents may be used alone or in combination of two or more. In terms of ease of synthesis of the aromatic sulfonic acid compound (1), sulfuric acid, fuming sulfuric acid, sulfur trioxide, and chlorosulfonic acid are preferred, and sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid are more preferred.

[0131] There is no particular limitation on the molar ratio of the aromatic compound (2) and the sulfonating agent used in step 1, and in order to synthesize an aromatic sulfonic acid compound (1) substituted with one sulfo group, the molar ratio of the aromatic compound (2):sulfonating agent is preferably in the range of 10:1 to 1:10, more preferably in the range of 5:1 to 1:5, and even more preferably in the range of 2:1 to 1:2, in terms of good reaction yield. In order to synthesize an aromatic sulfonic acid compound (1) substituted with two sulfo groups, the molar ratio of the aromatic compound (2):sulfonating agent is preferably in the range of 1:1 to 1:50, more preferably in the range of 1:2 to 1:35, and even more preferably in the range of 1:2 to 1:20, in terms of good reaction yield. In order to synthesize an aromatic sulfonic acid compound (1) substituted with three sulfo groups, the molar ratio of aromatic compound (2):sulfonating agent is preferably in the range of 1:1 to 1:200, more preferably in the range of 1:3 to 1:100, and even more preferably in the range of 1:3 to 1:60, in terms of good reaction yield. In order to synthesize an aromatic sulfonic acid compound (1) substituted with four sulfo groups, the molar ratio of aromatic compound (2):sulfonating agent is preferably in the range of 1:4 to 1:300, more preferably in the range of 1:10 to 1:200, and even more preferably in the range of 1:20 to 1:100, in terms of good reaction yield.

[0132] The reaction in step 1 can also be carried out in a solvent. There is no particular limit to the solvent that can be used, as long as it does not inhibit the sulfonation reaction. Specific examples of such solvents include halogen-based solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and orthodichlorobenzene; ether-based solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; acids such as sulfuric acid and fuming sulfuric acid; nitromethane and nitrobenzene; and two or more of these may be mixed in any ratio. There is no particular limit to the amount of solvent used. Among these, dichloromethane, 1,4-dioxane, chlorobenzene, nitrobenzene, sulfuric acid, and fuming sulfuric acid are preferred in terms of the good reaction yield of the aromatic sulfonic acid compound (1), and dichloromethane, 1,4-dioxane, sulfuric acid, and fuming sulfuric acid are more preferred.

[0133] The reaction temperature when carrying out step 1 is not particularly limited, and the reaction can usually be carried out at a temperature appropriately selected from the range of, for example, -80°C to 160°C. In terms of a good reaction yield of aromatic sulfonic acid compound (1), it is preferable to carry out the reaction at a temperature appropriately selected from the range of -10°C to 100°C, and it is more preferable to carry out the reaction at a temperature appropriately selected from the range of 0°C to 80°C.

[0134] After completion of the reaction in step 1, the aromatic sulfonic acid in the aromatic sulfonic acid compound or its salt (1) can be obtained by carrying out a conventional post-treatment. If necessary, the product may be purified by a conventional purification method such as recrystallization, column chromatography, sublimation, salting out, or preparative high performance liquid chromatography (HPLC).

[0135] Step 2 may be carried out to convert the aromatic sulfonic acid obtained in step 1 into a sulfonate. A method for converting an aromatic sulfonic acid into a sulfonate may be, for example, a general neutralization reaction, for example, by reacting an aromatic sulfonic acid with an alkali metal hydroxide, an alkaline earth metal hydroxide, or an alkali metal alkoxide, and an alkali metal hydroxide or an alkali metal alkoxide is preferred in terms of a good reaction yield of the sulfonate, and sodium hydroxide or sodium methoxide is more preferred. The neutralization reaction may be carried out in an aqueous solution, but may also be carried out in the presence of an organic solvent that is miscible with water, for example, an alcoholic solvent or an ether solvent.

[0136] Ammonium salts can also be produced by reacting aromatic sulfonic acids with aliphatic amines or aromatic amines. This reaction can also be carried out in an organic solvent, and specific examples of the organic solvent include halogen-based solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and orthodichlorobenzene, ether-based solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane, nitromethane, and the like, and two or more of these may be mixed in any ratio.

[0137] The reaction in step 2 can give the target product in good yield by carrying out the reaction at a temperature appropriately selected from the range of, for example, −80° C. to 100° C. There is no particular limitation on the reaction time.

[0138] After the reaction is completed, the desired sulfonate can be obtained by a conventional method such as reprecipitation, recrystallization, salting out, etc. The sulfonate may be purified by a conventional purification method, if necessary.

[0139] In the method for producing an aromatic sulfonic acid compound or a salt thereof (1) according to the present embodiment, R 1 , R 2 , R 3, R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 an aromatic sulfonic acid compound or a salt thereof (1), in which two or less groups selected from the group consisting of 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 An aromatic sulfonic acid compound or a salt thereof (1) in which three or more groups selected from the group consisting of the above are sulfo groups may be produced concomitantly.

[0140] The sulfonation in step 1 may produce an aromatic sulfonic acid compound (1) as a mixture containing at least two of the aromatic sulfonic acid compound (1) substituted with one sulfo group, the aromatic sulfonic acid compound (1) substituted with two sulfo groups, the aromatic sulfonic acid compound (1) substituted with three sulfo groups, the aromatic sulfonic acid compound (1) substituted with four sulfo groups, and the aromatic sulfonic acid compound (1) substituted with five sulfo groups. The sulfonation in step 1 may also produce an aromatic sulfonic acid compound (1) as a mixture containing at least two aromatic sulfonic acid compounds (1) substituted with the same number of sulfo groups at different substitution positions. In these cases, the aromatic sulfonic acid compound or salt (1) of two or more kinds may be used for a specific purpose as a mixture, or the obtained aromatic sulfonic acid compound or salt (1) may be purified and used for a specific purpose as one type of aromatic sulfonic acid compound or salt (1).

[0141] <Water Treatment Agent Composition> The water treatment agent composition according to the embodiment of the present invention is a water treatment agent composition containing the fluorescent compound represented by the above formula (1).

[0142] The fluorescent compound contained in the water treatment composition may be mixed in a solvent such as water at a predetermined ratio. The ratio is not particularly limited, but the fluorescent compound represented by the above formula (1) may be mixed in a range of, for example, 0.001 to 1.0 wt %, preferably 0.01 to 0.8 wt %, based on the total weight of the water treatment composition. If the fluorescent compound is mixed in an amount exceeding 1.0 wt % based on the total weight of the water treatment composition, problems such as an increase in the cost of the fluorescent compound and precipitation of dissolved components may occur, and if it is less than 0.001 wt %, the fluorescence intensity is low and accurate measurement may be difficult.

[0143] The water treatment agent composition according to this embodiment may further contain, in addition to the fluorescent compound represented by formula (1) above, at least one component selected from the group consisting of a water-soluble polymer, a bactericide, an anticorrosive, and a pH adjuster.

[0144] The water-soluble polymer may be, for example, a monomer selected from the group consisting of carboxylic acid or a salt thereof, phosphonic acid or a salt thereof, and maleic acid or a salt thereof. Mer and polymers having a unit.

[0145] Examples of carboxylic acids include carboxylic acid homopolymers (polyacrylic acid and its salts, polymethacrylic acid and its salts, polymaleic acid and its salts), carboxylic acid copolymers (acrylic acid / 2-acrylamido-2-methylpropanesulfonic acid binary copolymer, acrylic acid / maleic acid binary copolymer, maleic acid / methyl vinyl ether binary copolymer, acrylic acid / hydroxypropyl acrylate binary copolymer, sulfonated styrene / maleic anhydride binary copolymer), carboxylic acid terpolymers (maleic acid / acrylic acid alkyl ester / vinyl acetate terpolymer, acrylic acid / sulfonic acid / sodium styrene sulfonate terpolymer, acrylic acid / sulfonic acid / substituted acrylamide terpolymer), phosphonocarboxylic acid polymers (tetrasodium phosphonoethane-1,2-dicarboxylate, hexasodium phosphonobutane-1,2,3,4-tetracarboxylate), and the like. From the viewpoint of inhibiting the decomposition of inorganic fungicides, polyacrylic acid and its salts, acrylic acid / 2-acrylamido-2-methylpropanesulfonic acid binary copolymers are preferred. Examples of the salt of the carboxylic acid include an alkali metal salt such as a sodium salt.

[0146] Examples of the salt of phosphonic acid include alkali metal salts such as sodium salts.

[0147] Examples of the salt of maleic acid include alkali metal salts such as sodium salt.

[0148] Examples of water-soluble polymers include polyacrylic acid, polymaleic acid, binary copolymers of acrylic acid / 2-acrylamido-2-methylpropanesulfonic acid, binary copolymers of acrylic acid / 2-acrylamido-2-methylpropanesulfonic acid, and ternary copolymers of acrylic acid / 2-acrylamido-2-methylpropanesulfonic acid / substituted acrylamide, such as terpolymers of acrylic acid / 2-acrylamido-2-methylpropanesulfonic acid / alkylacrylamide. From the viewpoint of inhibiting the decomposition of inorganic fungicides, polyacrylic acid and binary copolymers of acrylic acid / 2-acrylamido-2-methylpropanesulfonic acid are preferred.

[0149] The weight average molecular weight of the water-soluble polymer is not particularly limited, but is, for example, in the range of 500 to 100,000.

[0150] The concentration of the water-soluble polymer contained in the water treatment agent composition is preferably, for example, in the range of 1% by weight to 50% by weight based on the total amount of the water treatment agent composition. If the concentration of the water-soluble polymer is less than 1% by weight, the scale dispersion effect may be insufficient, and if it exceeds 50% by weight, precipitation may occur.

[0151] In the existing water treatment agent compositions described in the above prior art that contain fluorescent compounds such as 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt hydrate and 1,5-naphthalenedisulfonic acid disodium salt, when a water-soluble polymer is present, the fluorescent compound deteriorates unless the pH is acidic or alkaline, which imposes restrictions on the components that can be incorporated into the water treatment agent. The water treatment agent composition according to the embodiment of the present invention uses the fluorescent compound represented by the above formula (1) and can suppress the deterioration of the fluorescent compound without depending on the components that can be incorporated into the water treatment agent.

[0152] Examples of the disinfectant include organic disinfectants, chlorine-based oxidants, bromine-based oxidants, and hypohalous acid stabilized compositions.

[0153] Examples of organic fungicides include isothiazolinone compounds such as 2-methyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-octyl-4-isothiazolin-3-one, and 1,2-benzoisothiazolin-3-one, and hydrazine. One type may be used alone, or two or more types may be used in combination.

[0154] Examples of chlorine-based oxidizing agents include chlorine gas, chlorine dioxide, hypochlorous acid or its salt, chlorous acid or its salt, chloric acid or its salt, perchloric acid or its salt, and chlorinated isocyanuric acid or its salt. Among these, examples of salts include alkali metal hypochlorite such as sodium hypochlorite and potassium hypochlorite, alkaline earth metal hypochlorite such as calcium hypochlorite and barium hypochlorite, alkali metal chlorite such as sodium chlorite and potassium chlorite, alkaline earth metal chlorite such as barium chlorite, other metal chlorite such as nickel chlorite, alkali metal chlorate such as ammonium chlorate, sodium chlorate, and potassium chlorate, alkaline earth metal chlorate such as calcium chlorate and barium chlorate, and the like. These chlorine-based oxidizing agents may be used alone or in combination of two or more. As the chlorine-based oxidizing agent, it is preferable to use sodium hypochlorite from the viewpoint of handling and the like.

[0155] Examples of the bromine-based oxidizing agent include bromine (liquid bromine), bromine chloride, bromic acid, bromate, hypobromous acid, etc. Hypobromous acid may be produced by reacting a bromine compound such as sodium bromide with a chlorine-based oxidizing agent such as hypochlorous acid.

[0156] Examples of the bromine compound include sodium bromide, potassium bromide, lithium bromide, ammonium bromide, hydrobromic acid, etc. Among these, sodium bromide is preferred from the viewpoint of formulation costs, etc.

[0157] Examples of the hypohalous acid stabilized composition include a "hypochlorous acid stabilized composition" containing a chlorine-based oxidizing agent and a sulfamic acid compound, and a "hypobromous acid stabilized composition" containing a bromine-based oxidizing agent and a sulfamic acid compound.

[0158] "Containing a chlorine-based oxidizing agent and a sulfamic acid compound" may include a stabilized hypochlorous acid composition containing a mixture of a "chlorine-based oxidizing agent" and a "sulfamic acid compound", or may include a stabilized hypochlorous acid composition containing a "reaction product of a chlorine-based oxidizing agent and a sulfamic acid compound". "Containing a bromine-based oxidizing agent and a sulfamic acid compound" may include a stabilized hypobromous acid composition containing a mixture of a "bromine-based oxidizing agent" and a "sulfamic acid compound", or may include a stabilized hypobromous acid composition containing a "reaction product of a bromine-based oxidizing agent and a sulfamic acid compound".

[0159] Of these, a stabilized hypobromous acid composition containing a bromine-based oxidizing agent and a sulfamic acid compound is preferred, and a stabilized hypobromous acid composition containing "bromine and a sulfamic acid compound (a mixture of bromine and a sulfamic acid compound)" using bromine or a "reaction product of bromine and a sulfamic acid compound" is more preferred than a stabilized hypobromous acid composition of "bromine compound, hypochlorous acid, and sulfamic acid compound" and a stabilized hypochlorous acid composition containing "bromine chloride and sulfamic acid", because they are less likely to decompose coexisting fluorescent compounds, have high stability of effective bromine, and can suppress the by-production of bromic acid.

[0160] The sulfamic acid compound is a compound represented by the following general formula (3). R2NSO3H (3) (In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

[0161] Examples of sulfamic acid compounds that are considered to function as stabilizers for inorganic bactericides constituting the stabilized composition of hypochlorous acid or hypobromous acid include sulfamic acid (amidosulfuric acid) in which both of the two R groups are hydrogen atoms, as well as sulfamic acid compounds in which one of the two R groups is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms, such as N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, N-isopropylsulfamic acid, and N-butylsulfamic acid; Examples of sulfamic acid compounds include sulfamic acid compounds in which both of the two R groups are alkyl groups having 1 to 8 carbon atoms, such as N-dimethylsulfamic acid, N,N-diethylsulfamic acid, N,N-dipropylsulfamic acid, N,N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid, and N-methyl-N-propylsulfamic acid, and sulfamic acid compounds in which one of the two R groups is a hydrogen atom and the other is an aryl group having 6 to 10 carbon atoms, such as N-phenylsulfamic acid, and salts thereof. Examples of sulfamic acid salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts, strontium salts, and barium salts, other metal salts such as manganese salts, copper salts, zinc salts, iron salts, cobalt salts, and nickel salts, ammonium salts, and guanidine salts. The sulfamic acid compounds and their salts may be used alone or in combination of two or more. As the sulfamic acid compound, it is preferable to use sulfamic acid (amidosulfuric acid) from the viewpoint of environmental load and the like.

[0162] In the water treatment agent composition according to the present embodiment, the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" is preferably 1.0 or more, more preferably in the range of 1.0 to 2.0, and even more preferably in the range of 1.05 to 1.5. If the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" is less than 1.0, the bromine concentration may be significantly reduced, and if it exceeds 2.0, the production cost may increase.

[0163] In the water treatment agent composition, the bactericide is preferably at least one of a hypochlorite, a hypobromite, an isothiazolinone compound, and hydrazine.

[0164] The concentration of the bactericide contained in the water treatment composition is preferably, for example, in the range of 0.02 to 45% by weight based on the total amount of the water treatment composition. If the concentration of the bactericide is less than 0.02% by weight, the bactericidal effect may be insufficient, and if it exceeds 45% by weight, the production cost may be high. The concentration of the isothiazolinone compound contained in the water treatment composition is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.

[0165] Examples of the anticorrosive agent include azole compounds, which are anticorrosive agents for copper-based metals such as copper and copper alloys, and nitrites, molybdates, polymerized phosphates, phosphoric acid, organic phosphates (phosphonic acid, etc.), zinc salts, etc., which are anticorrosive agents for iron-based metals such as carbon steel. It is preferable to add an azole compound, from the viewpoints of having an ultraviolet absorbing effect and contributing to inhibiting the decomposition of the fluorescent compound, in addition to having an anticorrosive effect on copper-based metals.

[0166] The azole-based compound acts as an anticorrosive agent for copper-based metals such as copper and copper alloys. Examples of the azole-based compound include 1,2,3-benzotriazole, tolyltriazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 5-carboxybenzotriazole, and 5-nitrobenzotriazole. One type may be used alone, or two or more types may be used in combination. Among these, 1,2,3-benzotriazole and tolyltriazole are preferred from the viewpoint of production cost, and 1,2,3-benzotriazole is more preferred.

[0167] Examples of phosphonic acids include 2-phosphonobutane-1,2,4-tricarboxylic acid and its salts (PBTC), 1-hydroxyethylidene-1,1-diphosphonic acid and its salts (HEDP), and the like.

[0168] The concentration of the corrosion inhibitor for copper-based metals, etc., contained in the water treatment agent composition is preferably, for example, in the range of 0.1% by weight to 4% by weight based on the total amount of the water treatment agent composition. If the concentration of the corrosion inhibitor is less than 0.1% by weight, the corrosion inhibitor effect on copper-based metals, etc. and the ultraviolet ray absorbing effect may be insufficient, and if it exceeds 4% by weight, precipitation may occur.

[0169] In the water treatment agent composition according to the present embodiment, when the fluorescent compound represented by the above formula (1) and a bactericide are contained, it is preferable to further contain an azole-based compound, and more preferable to contain 1,2,3-benzotriazole. When the fluorescent compound represented by the above formula (1) and a bactericide are contained, if an azole-based compound is further contained, the stability of the fluorescent compound during high-temperature storage (e.g., storage at 50°C or higher) is improved. In this case, the azole-based compound acts as a stabilizer for the fluorescent compound, but also acts as an anticorrosive agent for copper-based metals such as copper and copper alloys.

[0170] In this case, the mass ratio of the azole compound to the fluorescent compound represented by the above formula (1) is preferably in the range of 7:1 to 100:1, and more preferably in the range of 7:1 to 67:1. If the mass ratio of the azole compound to the fluorescent compound represented by the above formula (1) is less than 7:1, the stability of the fluorescent substance during high-temperature storage may decrease, and if it is more than 100:1, precipitation may occur.

[0171] Examples of pH adjusters include acids such as hydrochloric acid, sulfuric acid, and nitric acid, and alkalis such as sodium hydroxide and potassium hydroxide. Of the acids, hydrochloric acid and sulfuric acid are preferred from the standpoint of cost, etc. Of the alkalis, sodium hydroxide and potassium hydroxide are preferred from the standpoint of cost, etc.

[0172] The concentration of the pH adjuster contained in the water treatment agent composition may be an amount capable of adjusting the pH of the water treatment agent composition to a predetermined pH. The pH of the water treatment agent composition is, for example, in the range of 0 to 14.

[0173] The water treatment composition containing a fluorescent compound may be a pure liquid of the fluorescent compound that contains only the fluorescent compound, without containing a water-soluble polymer, an azole compound, a bactericide, or a pH adjuster, or may contain a pH buffer to suppress changes in pH.

[0174] Examples of pH buffers include inorganic acids such as phosphoric acid, sodium carbonate, and sodium bicarbonate, and organic acids such as citric acid. From the viewpoint of inhibiting slime generation, inorganic acids such as phosphoric acid, sodium carbonate, and sodium bicarbonate are preferred.

[0175] <Method of producing stabilized hypohalous acid composition> The stabilized hypohalous acid composition can be obtained, for example, by mixing a bromine-based or chlorine-based oxidizing agent and a sulfamic acid compound in water, and an alkali may also be mixed therein.

[0176] The method for producing a stabilized hypobromous acid composition containing bromine and a sulfamic acid compound preferably includes a step of adding bromine to a mixed solution containing water, an alkali, and a sulfamic acid compound under an inert gas atmosphere to cause a reaction, or a step of adding bromine to a mixed solution containing water, an alkali, and a sulfamic acid compound under an inert gas atmosphere. By adding and reacting under an inert gas atmosphere or by adding under an inert gas atmosphere, the bromate ion concentration in the stabilized hypobromous acid composition is reduced.

[0177] The inert gas to be used is not limited, but from the viewpoint of production etc., at least one of nitrogen and argon is preferable, and from the viewpoint of production cost etc., nitrogen is particularly preferable.

[0178] The oxygen concentration in the reactor during the addition of bromine is preferably 6% or less, more preferably 4% or less, even more preferably 2% or less, and particularly preferably 1% or less. If the oxygen concentration in the reactor during the reaction of bromine exceeds 6%, the amount of bromic acid produced in the reaction system may increase.

[0179] The addition rate of bromine is preferably 25% by weight or less, more preferably 1% by weight or more and 22.5% by weight or less, based on the total amount of the stabilized hypobromous acid composition. If the addition rate of bromine exceeds 25% by weight based on the total amount of the stabilized hypobromous acid composition, the amount of bromic acid produced in the reaction system may increase. If it is less than 1% by weight, the sterilizing power may be poor.

[0180] The reaction temperature during the addition of bromine is preferably controlled in the range of 0° C. to 25° C., but from the viewpoint of production costs, etc., it is more preferable to control it in the range of 0° C. to 15° C. If the reaction temperature during the addition of bromine exceeds 25° C., the amount of bromic acid produced in the reaction system may increase, and if it is below 0° C., freezing may occur.

[0181] <Method of producing water treatment composition> The water treatment composition can be obtained, for example, by mixing the fluorescent compound represented by the above formula (1) with water, and may further include at least one component selected from the group consisting of a water-soluble polymer, a bactericide, an anticorrosive, and a pH adjuster, a pH buffer, etc.

[0182] <Treatment method for untreated water> The method for treating water to be treated according to the embodiment of the present invention is a treatment method in which the above-mentioned water treatment agent composition is added to the water to be treated.

[0183] In the method for treating water to be treated according to this embodiment, the water treatment agent composition may be added to the water to be treated to a concentration of, for example, 1 to 1000 mg / L, though this is not particularly limited.

[0184] The water to be treated is not particularly limited, and may be, for example, industrial water, tap water, city water, well water, pure water, ultrapure water, wastewater, sewage, etc., or water that has been treated by a biological treatment device, a physicochemical treatment device, etc. In many cases, a bactericide such as sodium hypochlorite is added to the water to be treated beforehand depending on the purpose.

[0185] As the disinfectant contained in the water to be treated, examples of the chlorine-based oxidizing agent include chlorine gas, chlorine dioxide, hypochlorous acid or its salt, chlorous acid or its salt, chloric acid or its salt, perchloric acid or its salt, chlorinated isocyanuric acid or its salt, and a stabilized hypochlorous acid composition. Examples of the bromine-based oxidizing agent include bromine (liquid bromine), bromine chloride, bromic acid, bromate, hypobromous acid, and a stabilized hypobromous acid composition. The hypobromous acid may be generated by reacting a bromide such as sodium bromide with a chlorine-based oxidizing agent such as hypochlorous acid. These oxidizing agents may be contained alone or in combination of two or more.

[0186] The concentration of oxidizing agents such as chlorine-based oxidizing agents and bromine-based oxidizing agents contained in the water to be treated is generally 0.01 mg / L or more and 100 mg / L or less in terms of free chlorine concentration or total chlorine concentration. As a means for measuring the concentration of these oxidizing agents, a known method used for measuring free chlorine concentration or total chlorine concentration can be applied, and examples of the measuring methods include the diethyl-p-phenylenediamine (DPD) colorimetric method, diethyl-p-phenylenediamine (DPD) spectrophotometric method, amperometric titration method, diethyl-p-phenylenediamine (DPD) titration method, iodometric titration method, polarographic method, orthotolidine method, etc.

[0187] Water treatment chemicals added in cooling towers and the like often come into contact with the heat exchangers of the facilities, and the contact with the heat exchanger is under high temperature conditions (e.g., 50°C or higher) in the dark. The water treatment agent composition according to the present embodiment has high stability of the fluorescent compound even when used under high temperature conditions, and therefore can be suitably used in water systems having heating devices such as heat exchangers, and in ultraviolet ray irradiation environments such as outdoors.

[0188] <Method for measuring concentration of water treatment agent composition in water to be treated> The method for measuring the concentration of a water treatment agent composition in water to be treated according to an embodiment of the present invention is a method for measuring the concentration of the water treatment agent composition contained in the water to be treated by fluorescence measurement.

[0189] The fluorescence may be measured, for example, by measuring the fluorescence intensity using a fluorometer or the like.

[0190] <Concentration control method and concentration control device> The concentration control method according to an embodiment of the present invention is a method for controlling the concentration of a water treatment agent composition added to water to be treated by measuring the concentration of the fluorescent compound represented by the above formula (1).

[0191] For example, the concentration of the fluorescent compound represented by the above formula (1) in the water to be treated may be determined by measuring the fluorescence intensity using a fluorometer or the like.

[0192] The concentration control device according to the embodiment of the present invention is a device for controlling the concentration of a water treatment agent composition added to water to be treated by measuring the concentration of the fluorescent compound represented by the above formula (1).

[0193] For example, the concentration of the fluorescent compound represented by the above formula (1) in the water to be treated may be measured using a fluorometer or the like.

[0194] This specification includes the following embodiments. [1] A fluorescent compound represented by formula (1). [ka] (In formula (1), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 One or more and up to five groups selected from the following are sulfo groups or chemically acceptable salts thereof. When n is 2, multiple R 9 and R 12 may be the same or different, provided that X is an oxygen atom, n is 1, and R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 When all are hydrogen atoms, R 3 and R 10 cannot be a sulfo group or a chemically acceptable salt thereof.)

[0195] [2] The fluorescent compound according to [1], X is an oxygen atom;

[0196] [3] The fluorescent compound according to [1] or [2], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12is a sulfo group or a chemically acceptable salt thereof, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is 0 or 1.

[0197] [4] The fluorescent compound according to [3], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 wherein one or more and four or less groups selected from the following are sulfo groups or chemically acceptable salts thereof.

[0198] [5] The fluorescent compound according to any one of [1] to [4], R 3 , R 5 , R 6 , R 8 and R 10 at least one group of is a sulfo group or a chemically acceptable salt thereof.

[0199] [6] The fluorescent compound according to any one of [1] to [4], R 3 , R 5 , R 6 , R 8 and R 10 and wherein at least two groups selected from the group consisting of a sulfo group or a chemically acceptable salt thereof.

[0200] [7] A method for producing a fluorescent compound represented by formula (1), comprising sulfonating an aromatic compound represented by formula (2). [ka] (In formula (1), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 One or more and up to five groups selected from the following are sulfo groups or chemically acceptable salts thereof. When n is 2, multiple R 9 and R 12 may be the same or different, provided that X is an oxygen atom, n is 1, and R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 When all are hydrogen atoms, R 3 and R 10 cannot be a sulfo group or a chemically acceptable salt thereof.) [ka] (In formula (2), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 Two or more groups selected from are hydrogen atoms. When n is 2, multiple A 9 and A 12 may be the same or different. 1 From A 12 Each group represented by the same number R 1 From R 12 When the group represented by R is a sulfo group or a chemically acceptable salt thereof, the corresponding group represented by A is a hydrogen atom.)

[0201] [8] A method for producing the fluorescent compound according to [7], A method for producing a fluorescent compound, comprising sulfonating the compound with at least one of chlorosulfonic acid, sulfuric acid, and oleum.

[0202] [9] A method for producing the fluorescent compound according to [8], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 an aromatic sulfonic acid compound or a salt thereof, in which two or less groups selected from the group consisting of sulfo groups, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 The method for producing a fluorescent compound also includes the co-production of an aromatic sulfonic acid compound or a salt thereof, in which three or more groups selected from the above are sulfo groups.

[0203]

[10] A water treatment agent composition comprising a fluorescent compound represented by formula (1): [ka] (In formula (1), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 One or more and up to five groups selected from the following are sulfo groups or chemically acceptable salts thereof. When n is 2, multiple R 9 and R 12 may be the same or different, provided that X is an oxygen atom, n is 1, and R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 When all are hydrogen atoms, R 3 and R 10 cannot be a sulfo group or a chemically acceptable salt thereof.)

[0204]

[11]

[10] The water treatment agent composition according to the present invention, The water treatment composition further comprises at least one component selected from the group consisting of a water-soluble polymer, a bactericide, a corrosion inhibitor, and a pH adjuster.

[0205]

[12] The water treatment composition according to

[11] , The water-soluble polymer is a polymer having at least one monomer selected from the group consisting of a carboxylic acid and a salt thereof. Mer A water treatment composition having a unit.

[0206]

[13] The water treatment composition according to

[11] or

[12] , The water treatment composition, wherein the disinfectant is at least one of a chlorine-based oxidant, a bromine-based oxidant, and a hypohalous acid-stabilized composition.

[0207]

[14] The water treatment composition according to

[13] , The water treatment agent composition, wherein the stabilized hypohalous acid composition is a stabilized hypobromous acid composition containing a bromine-based oxidizing agent and a sulfamic acid compound.

[0208]

[15] The water treatment agent composition according to any one of

[11] to

[14] , The water treatment composition, wherein the corrosion inhibitor is at least one of a nitrite, a molybdate, a polymeric phosphate, a phosphonate, a zinc salt, and an azole compound.

[0209]

[16] The water treatment agent composition according to any one of

[11] to

[15] , A water treatment agent composition comprising at least the bactericide and the corrosion inhibitor selected from the group consisting of the water-soluble polymer, the bactericide, the corrosion inhibitor, and the pH adjuster, wherein the corrosion inhibitor is an azole compound.

[0210]

[17]

[16] The water treatment composition according to the present invention, A water treatment agent composition, wherein a mass ratio of the azole compound to the fluorescent compound is in the range of 7:1 to 100:1.

[0211]

[18] The water treatment composition according to

[16] or

[17] , The water treatment composition, wherein the azole compound is 1,2,3-benzotriazole.

[0212]

[19] A method for treating water to be treated, comprising adding the water treatment agent composition according to any one of

[10] to

[18] to the water to be treated.

[0213]

[20] A method for measuring the concentration of a water treatment agent composition in water to be treated, comprising measuring the concentration of the water treatment agent composition according to any one of

[10] to

[18] contained in the water to be treated by fluorescence measurement.

[0214]

[21] A concentration control method for controlling the concentration of a water treatment agent composition according to any one of

[10] to

[18] added to water to be treated, comprising: The concentration of the fluorescent compound is measured to thereby control the concentration of the water treatment agent composition added to the water to be treated.

[0215]

[22] A concentration control device for controlling the concentration of a water treatment agent composition according to any one of

[10] to

[18] added to water to be treated, comprising: a concentration control device for controlling the concentration of the water treatment agent composition added to the water to be treated by measuring the concentration of the fluorescent compound. EXAMPLES

[0216] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0217] [ 1 H-NMR measurement] 1 H-NMR measurements were performed using a Bruker AVANCE III 400 or AVANCE III HD 400 NMR. 1 H-NMR was measured using a deuterated solvent as the measurement solvent and tetramethylsilane (TMS) as the internal standard.

[0218] [ESI-MS - measurement] ESI-MS - The measurement was performed using a Waters micromass ZQ.

[0219] <Example 1> [ka]

[0220] Under an argon atmosphere, dinaphtho[2,1-b:1',2'-d]furan (0.32 g, 1.2 mmol) was dissolved in dichloromethane (15 mL). 0.143 g, 1.2 mmol) was added and stirred at room temperature (20±5°C) for 3 hours. Chloroform and hexane were then added to this solution, and the mixture was allowed to stand, and the supernatant was removed. The solvent was distilled off under reduced pressure, and the resulting solid was washed with hexane to give dinaphtho[2,1-b:1',2'-d]furan-5-sulfonic acid as a white solid (0.20 g, 78% yield).

[0221] 1 H-NMR(400MHz,DMSO-d6)δ(ppm):9.18(dd,J=8.7,1.1Hz,1H),9.09(d,J=8.4Hz,2H),8.37(s,1H),8.23 (brd,J=8.1Hz,1H),8.17(d,J=8.9Hz,1H),8.06(d,J=8.9Hz,1H),7.87-7.81(m,2H),7.69-7.64(m,2H). ESI-MS - (MeOH) m / z: 347 (MH) -

[0222] <Example 2> [ka]

[0223] Under an argon atmosphere, dinaphtho[2,1-b:1',2'-d]furan (2.05g, 7.6mmol) was dissolved in dichloromethane (25mL). To this solution, sulfuric acid chloride (1.78g, 15mmol) was added and stirred at room temperature for 2 hours. Hexane was then added to the solution, which was then filtered. The solid obtained was washed with hexane to obtain a black-purple solid (3.51g, crude yield quant.). When this solid was analyzed by NMR, it was found to contain dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonic acid.

[0224] 1 H-NMR(400MHz,DMSO-d6)δ(ppm):9.16(dd,J=8.6,1.3Hz,1.2H),9.10-9.05(m,1.2H),9.02(d,J=8.7Hz,0.3H),8.44(s,0.3H),8.36(s,1.0H), 8.23(d,J=8.6Hz,0.4H),8.17(d,J=8.9Hz,0.2H),8.07(d,J=8.8Hz,0.5 H),8.03(d,J=8.9Hz,0.3H),7.88-7.80(m,1.3H),7.69-7.64(m,1.3H). ESI-MS - (MeOH) m / z: 427 (MH) -

[0225] <Example 3> [ka]

[0226] Under an argon atmosphere, dinaphtho[2,1-b:1',2'-d]furan (671 mg, 2.5 mmol) was dissolved in dichloromethane (8.5 mL). To this solution, sulfonic acid chloride (0.59 g, 5.1 mmol) was added and stirred at room temperature for 4 hours. Water was then slowly added to this solution, and the aqueous layer was extracted, followed by the addition of 5M aqueous sodium hydroxide solution (2.0 mL, 10 mmol), and the low boiling point fraction was removed under reduced pressure. Ethanol (50 mL) was added to the resulting solid, which was heated to 80°C and stirred for 30 minutes. After cooling to room temperature, filtration was performed, and the resulting solid was washed with ethanol to obtain sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate as a pale yellow solid (806 mg).

[0227] 1H-NMR(400MHz,DMSO-d6)δ(ppm):9.16(brd,J=8.6Hz,1H),9.08(brd,J=8.3Hz,1H),9.02(brd,J=8.8Hz,1H),8.43(d,J=1.7Hz,1H),8.35( s,1H),8.23(d,J=8.9Hz,1H),8.06(d,J=8.9Hz,1H),8.02(dd,J=8.8,1.7Hz,1H),7.83(dd,J=8.3,8.3Hz,1H),7.66(dd,J=8.3,8.3Hz,1H). ESI-MS - (MeOH) m / z: 449 (M-Na) -

[0228] <Example 4> [ka]

[0229] Dinaphtho[2,1-b:1',2'-d]furan (503mg, 1.9mmol) was added with 95% (mass%) sulfuric acid (3mL, 52mmol), and the solution was heated and stirred at 50°C for 9 hours. The solution was then cooled to 0°C, and water (30mL) and 5M aqueous sodium hydroxide solution (22mL, 110mmol) were slowly added, and the low boiling fraction was removed under reduced pressure. Methanol (30mL) was then added and stirred overnight, followed by filtration, and the low boiling fraction was removed under reduced pressure. Ethanol (50mL) was added to the obtained solid, and the mixture was heated to 80°C and stirred for 1 hour. After cooling to room temperature, filtration was performed, and the obtained solid was washed with ethanol to obtain a yellow solid (887mg). Analysis of this solid by NMR revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate and sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate in integral amounts of 47% and 14%, respectively.

[0230] 1H-NMR(400MHz,DMSO-d6)δ(ppm):9.49-9.45(m,0.93H),9.22-8.94(m,2.37H),8.46-8.37(m,1.59H),8.26-7.96(m,3.14H),7.91-7.65(m,0.97H). ESI-MS - (MeOH) m / z: 551 (M-Na) -

[0231] <Example 5> [ka]

[0232] 95% sulfuric acid (2 mL, 35 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (210 mg, 0.78 mmol), and the solution was heated and stirred at 100 °C for 5.5 hours. After cooling to room temperature, it was cooled to 0 °C and then 6 M aqueous sodium hydroxide solution (11 mL, 66 mmol) was slowly added to neutralize the sulfuric acid, and the low boiling point fraction was removed under reduced pressure. Then, methanol (50 mL) was added and stirred overnight, followed by filtration, and the low boiling point fraction was removed under reduced pressure. Ethanol (80 mL) was added to the obtained solid, heated to 80 °C, and stirred for 1 hour. After cooling to room temperature, filtration was performed, and the obtained solid was washed with ethanol to obtain an orange solid (287 mg, crude yield 54%). This solid was analyzed by ESI-MS - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,9,11-tetrasulfonate. ESI-MS - (MeOH) m / z: 653 (M-Na) -

[0233] <Example 6> [ka]

[0234] Under an argon atmosphere, 3,3'-dimethyl-[1,1'-binaphthalene]-2,2'-diol (432 mg, 1.4 mmol) and para-toluenesulfonic acid (559 mg, 2.9 mmol) were suspended in toluene (15 mL) and stirred at 135°C for 29 hours. After cooling to room temperature, chloroform and water were added to the reaction mixture, and the organic layer was extracted. Sodium sulfate was added to the organic layer and stirred, followed by filtration and removal of low boiling fractions under reduced pressure. The resulting solid was purified by column chromatography (hexane:chloroform = 100:0 to 95:5) to obtain 6,8-dimethyldinaphtho[2,1-b:1',2'-d]furan as a milky white solid (365 mg, yield 90%).

[0235] 1 H-NMR(400MHz,CDCl3)δ(ppm):9.13(d,J=8.4Hz,2H),7.99(dd,J=8.1,1.0Hz,2H),7.74( s,2H),7.68(ddd,J=8.4,6.9,1.3Hz,2H),7.55(ddd,J=8.0,6.9,1.2Hz,2H),2.81(s,6H).

[0236] [ka]

[0237] Under an argon atmosphere, 6,8-dimethyldinaphtho[2,1-b:1',2'-d]furan (151 mg, 0.51 mmol) was dissolved in dichloromethane (5 mL). To this solution, sulfuric acid chloride (62.4 mg, 0.53 mmol) was added and stirred at room temperature for 1.5 hours. Hexane was then added to the solution, which was then filtered. The resulting solid was washed with hexane to give a crude gray solid (144 mg, crude yield 75%). This solid was analyzed by ESI-MS. - Analysis revealed that it contained 6,8-dimethyldinaphtho[2,1-b:1',2'-d]furan-3-sulfonic acid. ESI-MS - (MeOH) m / z: 375 (MH) -

[0238] <Example 7> [ka]

[0239] Under an argon atmosphere, 6,8-dimethyldinaphtho[2,1-b:1',2'-d]furan (104 mg, 0.35 mmol) was dissolved in dichloromethane (3.5 mL). To this solution, sulfuric acid chloride (85.6 mg, 0.73 mmol) was added and stirred at room temperature for 6 hours. Hexane was then added to the solution, which was then filtered. The resulting solid was washed with hexane to obtain a black-purple solid (157 mg, crude yield 99%). This solid was analyzed by ESI-MS. - Analysis revealed that it contained a structural isomer of 6,8-dimethyldinaphtho[2,1-b:1',2'-d]furan-disulfonic acid. ESI-MS - (MeOH) m / z: 455 (MH) -

[0240] <Example 8> [ka]

[0241] Under an argon atmosphere, 7H-dibenzo[c,g]carbazole (252 mg, 0.9 mmol) was dissolved in dichloromethane (5 mL). To this solution, sulfonic acid chloride (112 mg, 1.0 mmol) was added and stirred at room temperature for 1 hour. Hexane was then added to the solution, followed by filtration. The solid obtained was washed with hexane to obtain 7H-dibenzo[c,g]carbazole-5-sulfonic acid as a red-purple solid (286 mg, 87% yield).

[0242] 1H-NMR(400MHz,DMSO-d6)δ(ppm):12.35(s,1H),9.07(ddd,J=8.6,7.5,1.1Hz,3H),8.33(s,1H),8.10(dd ,J=8.1,1.2Hz,1H),7.94(d,J=8.7Hz,1H),7.82(d,J=8.7Hz,1H),7.71-7.64(m,2H),7.53-7.47(m,2H). ESI-MS - (MeOH) m / z: 346 (MH) -

[0243] <Example 9> [ka]

[0244] Benzo[b]naphtho[1,2-d]furan (218 mg, 1.0 mmol) was dissolved in dichloromethane (10 mL) under an argon atmosphere. Sulfonic acid chloride (120 mg, 1.0 mmol) was added to the solution, and the mixture was stirred at room temperature for 2.5 hours. Hexane was then added to the solution, followed by filtration. The resulting solid was washed with hexane to obtain a white solid (188 mg, crude yield 63%). This solid was analyzed by ESI-MS. - Analysis revealed that it contained benzo[b]naphtho[1,2-d]furan-5-sulfonic acid. ESI-MS - (MeOH) m / z: 297(MH) -

[0245] <Example 10> [ka]

[0246] Dinaphtho[2,1-b:1',2'-d]furan (597mg, 2.2mmol) was added with 95% sulfuric acid (2.8mL, 49mmol), and the solution was heated and stirred at 100°C for 24 hours. After cooling to room temperature, the solution was cooled to 0°C, and then 5M aqueous potassium hydroxide solution (21mL, 105mmol) was slowly added to neutralize the sulfuric acid, and the low boiling point fraction was removed under reduced pressure. Methanol (250mL) was then added and stirred for 2 days, followed by filtration, and the low boiling point fraction was removed under reduced pressure. The resulting solid was washed with hexane to obtain an orange solid (1.83g, crude yield quant.). This solid was analyzed by ESI-MS - Analysis revealed that the solution contained potassium dinaphtho[2,1-b:1',2'-d]furan-3,5,9,11-tetrasulfonate. ESI-MS - (MeOH) m / z: 701 (MK) -

[0247] <Example 11> [ka]

[0248] Under an argon atmosphere, 7H-benzo[c]fluorene (207 mg, 1.0 mmol) was dissolved in dichloromethane (10 mL). To this solution, sulfonic acid chloride (116 mg, 1.0 mmol) was added and stirred at room temperature for 2.5 hours. Hexane was then added to the solution, followed by filtration. The resulting solid was washed with hexane to obtain a white solid (219 mg, crude yield 78%). When this solid was analyzed by NMR, it was found to contain 7H-benzo[c]fluorene-5-sulfonic acid and 7H-benzo[c]fluorene-6-sulfonic acid in integral ratios of 77% and 33%, respectively.

[0249] 1H-NMR(400MHz,DMSO-d6)δ(ppm):9.04(dd,J=8.7,1.0Hz,1.0H),8.82(d,J=8.4Hz,1.3H),8.49(d,J =7.9Hz,1.0H),8.42(d,J=8.2Hz,0.3H),8.23(s,1.0H),8.07(d,J=7.8Hz,0.3H),7.94(d,J=8.3Hz,0 .3H),7.89(s,0.3H),7.79(d,J=8.3Hz,0.3H),7.75(brd,J=7.8Hz,0.3H),7.72-7.65(m,2.3H),7.6 0-7.55(m,1.3H),7.50(brd,J=7.4,6.8Hz,1.0H),7.39(ddd,J=7.4,6.6,0.8Hz,1.0H),4.08(s,3H). ESI-MS - (MeOH) m / z: 295 (MH) -

[0250] [Fluorescence wavelength measurement] Each of the fluorescent substances in Examples 1 to 11, sodium 2-naphthalenesulfonate (CAS number 532-02-5, manufactured by Kanto Chemical) as Reference Example 1, and pyrene-1,3,6,8-tetrasodium sulfonate (abbreviated as PTSA, CAS number 59572-10-0, manufactured by Acros Organics), a type of sulfonated pyrene, as Reference Example 2, were dissolved in pure water to a concentration of 1000 μg / L, and the fluorescence wavelength at which the strongest fluorescence intensity was observed and the optimal excitation wavelength at that time were obtained using a spectrofluorophotometer (FP-8350DS, manufactured by JASCO). The results are shown in Table 1.

[0251] [Table 1]

[0252] As is clear from Table 1, water-soluble fluorescent substances having various fluorescence wavelengths and excitation wavelengths could be obtained.

[0253] [Measurement of fluorescence intensity] Each of the fluorescent substances of Examples 1 and 2, and tetrasodium pyrene-1,3,6,8-tetrasulfonate as Reference Example 2 was dissolved in pure water to a concentration of 1000 μg / L, and the fluorescence wavelength at which the strongest fluorescence intensity was observed and the fluorescence intensity at that time were obtained using a spectrofluorophotometer (JASCO FP-8350DS). The results are shown in Table 2.

[0254] [Table 2]

[0255] As is clear from Table 2, a fluorescent substance having a higher fluorescence intensity than the existing fluorescent substance PTSA of Reference Example 2 was obtained. Therefore, when used as a fluorescent material, the amount of fluorescent substance to be blended can be reduced, and blending costs can be reduced.

[0256] As described above, the examples enable the production of water-soluble fluorescent compounds having novel structures.

[0257] <Examples 12 to 15> [Preparation of water treatment composition] The formulations were prepared with the blending compositions (mass%) shown in Tables 3 to 6. In a PTFE (polytetrafluoroethylene) container, each agent was added while stirring with a stirrer to prepare a water treatment agent composition with the composition shown in Tables 3 to 6 as a one-agent chemical. The fluorescent compound used was the fluorescent compound obtained in Example 4 (containing sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate and sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate in integral values ​​of 47% and 14%, respectively).

[0258] As the water-soluble polymer, acrylic acid homopolymer (weight average molecular weight 4,500), acrylic acid binary copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (weight average molecular weight 4,500), acrylic acid ternary copolymer of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and alkylacrylamide (weight average molecular weight 4,500), and polymaleic acid (weight average molecular weight 500) were used. As the bactericide, an isothiazolinone bactericide (a mixture containing about 10% by mass of 5-chloro-2-methyl-4-isothiazolin-3-one and about 3% by mass of 2-methyl-4-isothiazolin-3-one), a stabilized hypobromous acid composition (see below), sodium hypochlorite, and hydrazine monohydrate were used. The corrosion inhibitors used were 1,2,3-benzotriazole as an azole compound, zinc chloride, phosphoric acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and its salt (PBTC) as a phosphonic acid, and sodium molybdate dihydrate as a molybdate salt. The acid used was hydrochloric acid, and the alkali used was sodium hydroxide.

[0259] A stabilized hypobromous acid composition was prepared as follows.

[0260] [Preparation of stabilized hypobromous acid composition] In order to maintain the oxygen concentration in the reaction vessel at 1%, the flow rate of nitrogen gas was controlled by a mass flow controller, and 1436 g of water and 361 g of sodium hydroxide were added and mixed in a 2 L four-neck flask sealed by continuous injection. Then, 300 g of sulfamic acid was added and mixed, and 473 g of liquid bromine was added while maintaining cooling so that the temperature of the reaction liquid was 0 to 15 ° C., and 230 g of 48% potassium hydroxide solution was further added, and the target stabilized hypobromous acid composition was obtained, which has a weight ratio of 10.7% sulfamic acid, 16.9% bromine, and an equivalent ratio of sulfamic acid to bromine equivalent of 1.04 in terms of the weight ratio to the total amount of the composition. The pH of the resulting solution was 14 when measured by the glass electrode method. The bromine content of the resulting solution was 16.9% when measured by a method of converting bromine to iodine with potassium iodide and then performing oxidation-reduction titration using sodium thiosulfate, which was 100.0% of the theoretical content (16.9%). In addition, the oxygen concentration in the reaction vessel during the bromine reaction was measured using an oxygen monitor JKO-02 LJDII manufactured by JIKO Co., Ltd. The bromate concentration was less than 5 mg / kg.

[0261] The pH was measured under the following conditions. Electrode type: Glass electrode type pH meter: DKK Toa, IOL-30 Calibration of the electrode: Two-point calibration was performed using Kanto Chemical's neutral phosphate pH (6.86) standard solution (type 2) and the same company's borate pH (9.18) standard solution (type 2). Measurement temperature: 25℃ Measurement value: Immerse the electrode in the measurement solution, and the value after stabilization is the measurement value, which is the average of three measurements.

[0262] The obtained water treatment composition was placed in a polystyrene container and stored sealed at room temperature (25°C), 50°C, and -5°C, respectively, and the residual rate (%) of the fluorescent substance was measured after 14 days. The residual rate of the fluorescent substance was calculated from the measured value after 14 days, with the measured value immediately after formulation being set at 100%. For the formulation, a rating of 0 was given if no cloudiness or precipitation occurred. The results are shown in Tables 3 to 6.

[0263] [Table 3]

[0264] [Table 4]

[0265] [Table 5]

[0266] [Table 6]

[0267] As is clear from Tables 3 to 6, the fluorescence intensity was 95% or more in all samples compared to immediately after preparation.

[0268] <Example 16> In a PTFE (polytetrafluoroethylene) container, each agent was added while stirring with a stirrer in the blending composition (mass%) shown in Table 7, and a water treatment composition was prepared as a one-component chemical. The stabilized hypobromous acid composition (40 mass%), the fluorescent compound obtained in Example 4 (0.06 mass%), and 1,2,3-benzotriazole (0 to 6 mass%) were used as a bactericide. The prepared water treatment composition was placed in a polystyrene container and sealed, and the residual rate (%) of the fluorescent compound after storage at 50°C for 14 days was measured. The results are shown in Table 7. The residual rate (%) of the fluorescent compound relative to the mass ratio (BTA / fluorescent compound) of the azole compound after storage at 50°C for 14 days is shown in FIG. 1.

[0269] [Table 7]

[0270] Compared to immediately after preparation, the residual rate of the fluorescent compound was 70% or more in samples with mass ratios of azole compound to fluorescent compound ranging from 7:1 to 100:1. Under the conditions of fluorescent compound + fungicide in the examples, the addition of benzotriazole improved the stability of the fluorescent compound when stored at high temperatures.

[0271] <Example 17, Comparative Example 1> Water treatment compositions were prepared using the fluorescent compound of Example 4 or PTSA (1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt hydrate) as the fluorescent substance in the blending composition (mass%) shown in Table 8. The prepared water treatment composition was added to the water to be treated (cooling tower cooling water) in a polystyrene container so that the fluorescent compound or PTSA was 100 ppb, and after sealing, the container was stored for 14 days under a light-shielded condition at 50°C or outdoors (2-week average temperature 16.5°C, maximum temperature 28°C) under a light-shielded condition. The remaining rate (%) of the fluorescent compound after 14 days was measured. The results are shown in Table 9.

[0272] [Table 8]

[0273] [Table 9]

[0274] As shown in Table 9, the residual rate of the fluorescent compound in Example 4 was higher. The water treatment chemicals added in the cooling tower often come into contact with the heat exchanger of the facility, and contact with the heat exchanger occurs under high-temperature conditions in the dark. It was found that there is a possibility that the fluorescent chemicals will disappear if PTSA is used as the fluorescent substance.

[0275] <Example 18> [ka] 95% sulfuric acid (1 mL, 17 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (501 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 3 hours. The solution was then cooled to 0°C, and water (10 mL) and 5M aqueous sodium hydroxide solution (7 mL, 35 mmol) were slowly added and stirred, and then water (10 mL) was added again and filtered, and the low boiling point fraction was removed under reduced pressure. Methanol (18 mL) was then added and stirred at 50°C for 2 hours, followed by filtration. The filtrate was concentrated, and the precipitated solid was filtered to obtain a whitish yellow solid (311 mg). This solid was analyzed by ESI-MS - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate.

[0276] <Example 19> 95% sulfuric acid (3 mL, 52 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (501 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 2 hours. The solution was then cooled to 0°C, and water (50 mL) and 5M aqueous sodium hydroxide solution (21 mL, 105 mmol) were slowly added, filtered, insoluble matter was removed, and the low boiling point fraction was removed under reduced pressure. Methanol (50 mL) was then added, and the mixture was stirred at room temperature overnight, followed by filtration, and the low boiling point fraction was removed under reduced pressure. Ethanol (50 mL) was added to the obtained solid, and the mixture was heated to 80°C and stirred for 2 hours. After cooling to room temperature, filtration was performed, and the obtained solid was washed with ethanol to obtain a yellowish white solid (967 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate.

[0277] <Example 20> 95% sulfuric acid (1 mL, 17 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (501 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 9 hours. The solution was then cooled to 0°C, and water (50 mL) and 5M aqueous sodium hydroxide solution (7 mL, 35 mmol) were slowly added, and the low boiling fraction was removed under reduced pressure. Methanol (40 mL) was then added and stirred overnight at room temperature, followed by filtration, and the low boiling fraction was removed under reduced pressure. Ethanol (50 mL) was added to the resulting solid, which was heated to 80°C and stirred for 30 minutes. After cooling to room temperature, filtration was performed, and the resulting solid was washed with ethanol to obtain a yellow-white solid (818 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate.

[0278] <Example 21> 95% sulfuric acid (1 mL, 17 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (501 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (30 mL) and 5M aqueous sodium hydroxide solution (7 mL, 35 mmol) were slowly added, and the low boiling fraction was removed under reduced pressure. Methanol (50 mL) was then added, and the mixture was stirred overnight at 50°C, followed by filtration, and the low boiling fraction was removed under reduced pressure. Ethanol (50 mL) was added to the resulting solid, which was heated to 80°C and stirred for 30 minutes. After cooling to room temperature, filtration was performed, and the resulting solid was washed with ethanol to obtain a yellow-white solid (851 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate.

[0279] <Example 22> 95% sulfuric acid (1 mL, 17 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (500 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (30 mL) and 5M aqueous sodium hydroxide solution (7 mL, 35 mmol) were slowly added, filtered, insoluble matter was removed, and the low boiling point fraction was removed under reduced pressure. Methanol (50 mL) was then added, and the mixture was stirred overnight at 50°C, followed by filtration, and the low boiling point fraction was removed under reduced pressure. Ethanol (45 mL) was added to the resulting solid, and filtered to obtain a yellow-white solid (962 mg). This solid was analyzed by ESI-MS. - Analysis by NMR revealed that the solid contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate. Analysis by NMR revealed that the solid contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate and sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate in the proportions of 17% and 51%, respectively, calculated as integral values.

[0280] <Example 23> The same procedure as in Example 22 was carried out except that ethanol (45 mL) was replaced with isopropanol (70 mL), and a yellowish white solid was obtained (1038 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate.

[0281] <Example 24> The same procedure as in Example 22 was carried out except that the reaction temperature was changed to 40° C., and a yellowish white solid was obtained (988 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate.

[0282] <Example 25> The same procedure as in Example 22 was carried out except that the heating and stirring at 50°C for 6 hours was changed to heating and stirring at 60°C for 7 hours and ethanol (45 mL) was changed to isopropanol (50 mL), to obtain a yellowish white solid (1115 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate.

[0283] <Example 26> Working Example 19 The procedure was changed from 2 hours of heating and stirring at 50°C to 6 hours of heating and stirring at 50°C, water (50mL) was changed to water (10mL), 5M aqueous sodium hydroxide solution (21mL, 105mmol) was changed to 5M aqueous sodium hydroxide solution (7mL, 35mmol), ethanol (50mL) was changed to isopropanol (50mL), heating to 80°C and stirring for 2 hours was changed to heating to 80°C and stirring for 1 hour, and washing with ethanol was changed to washing with isopropanol. A yellowish white solid (986mg) was obtained by carrying out the same operations. This solid was analyzed by ESI-MS - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate.

[0284] <Example 27> 95% sulfuric acid (4 mL, 69.8 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (2.0 g, 7.5 mmol), and the solution was heated and stirred at 50 ° C for 6 hours. Then, the solution was cooled to 0 ° C, and water (14 mL) and 25% (mass%) sodium methoxide methanol solution (33 mL, 144.2 mmol) were slowly added. Then, water (24 mL) and methanol (56 mL) were added, and the mixture was heated and stirred overnight under reflux, filtered while hot, and the low boiling point fraction was concentrated under reduced pressure. Isopropanol (120 mL) was added thereto, concentrated under reduced pressure, and isopropanol (100 mL) was added again, and filtered to obtain a yellowish white solid (4.04 g). This solid was analyzed by ESI-MS - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate.

[0285] <Example 28> [ka] Dinaphtho[2,1-b:1',2'-d]furan (1.01g, 3.8mmol) was added with 95% sulfuric acid (5mL, 88mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and 6M aqueous sodium hydroxide solution (30mL, 180mmol) was slowly added, and the low boiling fraction was removed under reduced pressure. Methanol (120mL) was then added, and the mixture was stirred overnight, followed by filtration, and the low boiling fraction was removed under reduced pressure. Hexane was added to the resulting solid, and filtration was performed to obtain a yellow-white solid (2.97g). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0286] <Example 29> 95% sulfuric acid (2 mL, 35 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (349 mg, 1.3 mmol), and the solution was heated and stirred at 80°C for 6 hours. The solution was then cooled to 0°C, and water (15 mL) and 5M aqueous sodium hydroxide solution (14 mL, 70 mmol) were slowly added, filtered, insoluble matter was removed, and the low boiling point fraction was removed under reduced pressure. Methanol (50 mL) was then added, and the mixture was stirred overnight at 50°C, followed by filtration, and the low boiling point fraction was removed under reduced pressure. Ethanol (50 mL) was added to the obtained solid, and filtered to obtain a yellowish white solid (788 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0287] <Example 30> 95% sulfuric acid (3 mL, 52 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (501 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (30 mL) and 5M aqueous sodium hydroxide solution (22 mL, 110 mmol) were slowly added, filtered, insoluble matter was removed, and the low boiling point fraction was removed under reduced pressure. Methanol (50 mL) was then added, and the mixture was stirred overnight at 50°C, followed by filtration, and the low boiling point fraction was removed under reduced pressure. Isopropanol (70 mL) was added to the resulting solid, and filtered to obtain a yellow solid (1.17 g). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0288] <Example 31> A yellow solid was obtained by carrying out the same procedure as in Example 30, except that 95% sulfuric acid (3 mL, 52 mmol) was changed to 2 mL, 35 mmol, 5 M aqueous sodium hydroxide solution (22 mL, 110 mmol) was changed to 14 mL, 70 mmol, and isopropanol (70 mL) was changed to 50 mL. This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0289] <Example 32> 95% sulfuric acid (3 mL, 52 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (500 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (10 mL) and 5M aqueous sodium hydroxide solution (22 mL, 110 mmol) were slowly added, filtered, insoluble matter was removed, and the low boiling point fraction was removed under reduced pressure. Methanol (50 mL) was then added, and the mixture was stirred overnight at room temperature, followed by filtration, and the low boiling point fraction was removed under reduced pressure. Isopropanol was added to the resulting solid, and the mixture was filtered to obtain a yellow solid (1.19 g). This solid was analyzed by ESI-MS. -Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0290] <Example 33> The same procedure as in Example 32 was carried out except that the reaction temperature was 60° C., and a yellow solid was obtained (1.00 g). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0291] <Example 34> The same procedure as in Example 32 was carried out except that the reaction temperature was 70° C., and a yellow solid was obtained (1.03 g). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0292] <Example 35> Dinaphtho[2,1-b:1',2'-d]furan (1000mg, 3.7mmol) was added with 95% sulfuric acid (6mL, 105mmol), and the solution was heated and stirred at 55°C for 6 hours. The solution was then cooled to 0°C, and water (50mL) and 5M aqueous sodium hydroxide solution (42mL, 210mmol) were slowly added, filtered, insoluble matter was removed, and the low boiling point fraction was removed under reduced pressure. Methanol (100mL) was then added, and the mixture was stirred overnight at room temperature, followed by filtration, and the low boiling point fraction was removed under reduced pressure. Isopropanol was added to the resulting solid, and the mixture was filtered to obtain a yellow solid (1.56g). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0293] <Example 36> 95% sulfuric acid (3 mL, 52 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (500 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (30 mL) and 5M aqueous sodium hydroxide solution (22 mL, 110 mmol) were slowly added, filtered, insoluble matter was removed, and the low boiling fraction was removed under reduced pressure. Methanol (50 mL) was then added, and the mixture was stirred overnight at room temperature, followed by filtration, and the low boiling fraction was removed under reduced pressure. Isopropanol (50 mL) was added to the obtained solid, and the mixture was heated to 80°C and stirred for 1 hour. After cooling to room temperature, filtration was performed, and the obtained solid was washed with isopropanol to obtain a yellow solid (1.14 g). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0294] <Example 37> A yellow solid (825 mg) was obtained by carrying out the same procedure as in Example 36, except that 95% sulfuric acid (3 mL, 52 mmol) was changed to 10 mL, 175 mmol, water (30 mL) was changed to 50 mL, 5 M aqueous sodium hydroxide solution (22 mL, 110 mmol) was changed to 70 mL, 350 mmol, and methanol (50 mL) was changed to 100 mL. This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0295] <Example 38> 95% sulfuric acid (42 mL, 733 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (7.00 g, 26.1 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (50 mL) and 10 M aqueous sodium hydroxide solution (150 mL, 1500 mmol) were slowly added, filtered, and insoluble matter was removed, followed by vacuum removal of the low boiling fraction. Methanol (300 mL) was then added, and the mixture was stirred overnight at room temperature, followed by filtration, and the low boiling fraction was removed under reduced pressure. Isopropanol (450 mL) was added to the resulting solid, and filtered to obtain a yellow solid (16.3 g). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0296] <Example 39> Dinaphtho[2,1-b:1',2'-d]furan (504 mg, 1.9 mmol) was added with 95% sulfuric acid (3 mL, 52.4 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (100 mL) and a 25% sodium methoxide methanol solution (25 mL, 109 mmol) were slowly added, and the low boiling fraction was removed under reduced pressure. Methanol (100 mL) was then added, and the mixture was stirred overnight at room temperature, followed by filtration, and the low boiling fraction was removed under reduced pressure. Isopropanol was added to the resulting solid, and filtration was performed to obtain a yellow solid (1.14 g). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0297] <Example 40> The same procedure as in Example 39 was carried out except that the amount of water (100 mL) was changed to 25 mL, and a yellow solid was obtained (1.15 g). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0298] <Example 41> The same procedure as in Example 39 was carried out except that the amount of water (100 mL) was changed to 16.6 mL, and a yellow solid was obtained (925 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0299] <Example 42> The same procedure as in Example 39 was carried out except that the amount of water (100 mL) was changed to 11 mL and the amount of methanol (100 mL) was changed to 50 mL, to obtain a yellow solid (993 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0300] <Example 43> The same procedure as in Example 39 was carried out except that the amount of water (100 mL) was changed to 6.4 mL and the amount of methanol (100 mL) was changed to 90 mL, to obtain a yellowish white solid (656 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0301] <Example 44> The same procedure as in Example 39 was carried out except that the amount of water (100 mL) was changed to 2.8 mL, and a yellowish white solid was obtained (354 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0302] <Example 45> 95% sulfuric acid (3 mL, 52.4 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (503 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and methanol (50 mL) and 25% sodium methoxide methanol solution (25 mL, 109 mmol) were slowly added. After stirring at room temperature for 1 hour, filtration was performed, and methanol (100 mL) was added again to the obtained solid, which was stirred at room temperature overnight, followed by filtration, and the low boiling point fraction of the filtrate was removed under reduced pressure. In addition, methanol (100 mL) was added again to the solid obtained as the filtrate, which was stirred at room temperature overnight, followed by filtration, and the solid obtained by previously removing the low boiling point fraction was added to this solution, followed by removing the low boiling point fraction under reduced pressure. Isopropanol was added to the obtained solid, and filtration was performed to obtain a yellow solid (1.08 g). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0303] <Example 46> Dinaphtho[2,1-b:1',2'-d]furan (501 mg, 1.9 mmol) was added with 95% sulfuric acid (3 mL, 52.4 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (11 mL) and a 25% sodium methoxide methanol solution (25 mL, 109 mmol) were slowly added, and the low boiling point fraction was removed under reduced pressure. Soxhlet extraction was then performed overnight under reflux, and the low boiling point fraction was removed under reduced pressure. Isopropanol was added to the resulting solid, and the mixture was filtered to obtain a white solid (1122 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0304] <Example 47> The same procedure as in Example 46 was carried out, except that the low boiling point fraction was concentrated under reduced pressure after the Soxhlet extraction, to obtain a yellowish white solid (1.14 g). -Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0305] <Example 48> The same procedure as in Example 46 was carried out except that the amount of water (11 mL) was changed to 6.4 mL, and a yellowish white solid was obtained (994 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0306] <Example 49> The same procedure as in Example 46 was carried out except that the amount of water (11 mL) was changed to 2.8 mL, and a yellowish white solid was obtained (705 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0307] <Example 50> The same procedure as in Example 46 was carried out except that water (11 mL) was replaced with methanol (15 mL), and a white solid was obtained (1.39 g). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0308] <Example 51> Dinaphtho[2,1-b:1',2'-d]furan (503mg, 1.9mmol) was added with 95% sulfuric acid (3mL, 52.4mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and methanol (60mL) and 25% sodium methoxide methanol solution (25mL, 109mmol) were slowly added, stirred at room temperature for 1 hour, and filtered. The resulting solid was then subjected to Soxhlet extraction with methanol overnight under reflux, and the low boiling point fraction was removed under reduced pressure. Isopropanol was added to the resulting solid, and the solid was filtered to obtain a white solid (835mg). This solid was analyzed by ESI-MS. -Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0309] <Example 52> 95% sulfuric acid (3 mL, 52.4 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (502 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (11 mL) and a 25% solution of sodium methoxide in methanol (25 mL, 109 mmol) were slowly added, followed by addition of methanol (100 mL) and stirring at room temperature overnight. The solution was then filtered, and the low boiling point fraction was concentrated under reduced pressure. Isopropanol was added, and a yellowish white solid was obtained by filtration (484 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0310] <Example 53> Dinaphtho[2,1-b:1',2'-d]furan (502mg, 1.9mmol) was added with 95% sulfuric acid (3mL, 52.4mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (11mL) and 25% sodium methoxide methanol solution (25mL, 109mmol) were slowly added, followed by addition of methanol (100mL) and stirring at room temperature overnight. It was then filtered, and the low boiling point fraction was concentrated under reduced pressure. Isopropanol was added to this, and the low boiling point fraction was concentrated under reduced pressure, and isopropanol was added again, and the mixture was filtered to obtain a yellowish white solid (572mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0311] <Example 54> Dinaphtho[2,1-b:1',2'-d]furan (502 mg, 1.9 mmol) was added with 95% sulfuric acid (3 mL, 52.4 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (11 mL) and a 25% sodium methoxide methanol solution (25 mL, 109 mmol) were slowly added, and the low boiling fraction was removed under reduced pressure. Methanol (100 mL) was then added, and the mixture was stirred overnight at room temperature, followed by filtration, and the low boiling fraction was concentrated under reduced pressure. Isopropanol was added to the mixture, and the low boiling fraction was concentrated under reduced pressure. Isopropanol was then added again, and the mixture was filtered, yielding a yellow-white solid (934 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0312] <Example 55> Dinaphtho[2,1-b:1',2'-d]furan (501 mg, 1.9 mmol) was added with 95% sulfuric acid (3 mL, 52.4 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (11 mL) and a 25% solution of sodium methoxide in methanol (25 mL, 109 mmol) were slowly added, followed by addition of methanol (100 mL) and stirring at room temperature overnight. The solution was then filtered, and the low boiling fraction was removed under reduced pressure. Isopropanol was added to the resulting solid, and the mixture was filtered to obtain a yellow-white solid (649 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0313] <Example 56> Dinaphtho[2,1-b:1',2'-d]furan (501 mg, 1.9 mmol) was added with 95% sulfuric acid (3 mL, 52.4 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (11 mL) and a 25% sodium methoxide methanol solution (25 mL, 109 mmol) were slowly added, and the low boiling point fraction was concentrated under reduced pressure. Methanol (100 mL) was then added, and the mixture was stirred overnight at room temperature, filtered, and the low boiling point fraction was removed under reduced pressure. Isopropanol was added to the resulting solid, and the mixture was filtered to obtain a yellow-white solid (676 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0314] <Example 57> 95% sulfuric acid (3 mL, 52.4 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (501 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (11 mL) and a 25% sodium methoxide methanol solution (25 mL, 109 mmol) were slowly added, and the low boiling point fraction was concentrated under reduced pressure. Methanol (110 mL) was then added, and the mixture was stirred overnight at room temperature and filtered. Methanol (100 mL) was added again to the obtained solid, and the mixture was stirred overnight at room temperature and filtered, and the low boiling point fraction was concentrated under reduced pressure. Isopropanol was added to the mixture, and the mixture was concentrated under reduced pressure, and isopropanol was added again, and the mixture was filtered to obtain a yellowish white solid (362 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0315] <Example 58> 95% sulfuric acid (3 mL, 52.4 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (502 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (11 mL), 25% sodium methoxide methanol solution (25 mL, 109 mmol), and isopropanol (70 mL) were slowly added, and the low boiling point fraction was concentrated under reduced pressure. Isopropanol was then added again, and the mixture was filtered. Methanol (100 mL) was added to the obtained solid, and the mixture was stirred overnight at room temperature, filtered, and the low boiling point fraction was concentrated under reduced pressure. Isopropanol was added to the solid, and the mixture was concentrated under reduced pressure, and isopropanol was added again, and the mixture was filtered, to obtain a yellowish white solid (614 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0316] <Example 59> 95% sulfuric acid (3 mL, 52.4 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (501 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (11 mL) and a 25% sodium methoxide methanol solution (25 mL, 109 mmol) were slowly added, and the low boiling fraction was removed under reduced pressure. Methanol (100 mL) was then added, and the mixture was heated and stirred overnight under reflux, filtered while hot, and the low boiling fraction was concentrated under reduced pressure. Isopropanol was added to the mixture, and filtered to obtain a yellow-white solid (997 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0317] <Example 60> The same procedure as in Example 59 was carried out, except that the procedure of removing the low boiling fraction under reduced pressure after slowly adding 25% sodium methoxide in methanol (25 mL, 109 mmol) was omitted, to obtain a yellowish white solid (535 mg). -Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0318] <Example 61> The same procedure as in Example 59 was carried out except that the amount of water (11 mL) was changed to 2.8 mL, and a yellowish white solid was obtained (537 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0319] <Example 62> 95% sulfuric acid (3 mL, 52.4 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (502 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and 25% sodium methoxide methanol solution (25 mL, 109 mmol) was slowly added, stirred at room temperature for 1 hour, and filtered. Methanol (100 mL) was added to the resulting solid, and the mixture was heated and stirred overnight under reflux, filtered while hot, and the low boiling point fraction was concentrated under reduced pressure. Isopropanol was added to the mixture, and filtered to obtain a yellowish-white solid (312 mg). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0320] <Example 63> 95% sulfuric acid (3 mL, 52.4 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (500 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (11 mL) and 25% sodium methoxide methanol solution (25 mL, 109 mmol) were slowly added. Water (30 mL) and methanol (70 mL) were then added, and the mixture was heated and stirred overnight under reflux, filtered while hot, and the low boiling point fraction was concentrated under reduced pressure. Isopropanol was added to the mixture, concentrated under reduced pressure, and isopropanol was added again, followed by filtration to obtain a yellow solid (1.23 g). This solid was analyzed by ESI-MS.- Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0321] <Example 64> Slowly add 25% sodium methoxide in methanol (25 mL, 109 mmol) and then add water ( 30 6 mL) and methanol ( 70 The same procedure as in Example 63 was carried out except that the amount of ethanol (mL) was changed to 14 mL, and a yellow solid was obtained (1.08 g). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0322] <Example 65> Slowly add 25% sodium methoxide in methanol (25 mL, 109 mmol) and then add water ( 30 mL) and 3 mL of methanol ( 70 The same procedure as in Example 63 was carried out except that the amount of ethanol (mL) was changed to 7 mL, and a yellowish white solid was obtained (915 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0323] <Example 66> The same procedure as in Example 63 was carried out except that 25% sodium methoxide methanol solution (25 mL, 109 mmol) was slowly added, and then water and methanol were not added, to obtain a yellowish white solid (818 mg). - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0324] <Example 67> 95% sulfuric acid (42 mL, 733 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (7.00 g, 26.1 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (154 mL) and 25% sodium methoxide methanol solution (340 mL, 1486 mmol) were slowly added. Water (90 mL) and methanol (196 mL) were then added, and the mixture was heated and stirred overnight under reflux, filtered while hot, and the low boiling point fraction was concentrated under reduced pressure. Isopropanol (300 mL) was added to the mixture, concentrated under reduced pressure, and isopropanol (300 mL) was added again, and filtered to obtain a yellow solid (14.7 g). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0325] <Example 68> In Example 67, the dinaphtho[2,1-b:1',2'-d]furan (7.00g, 26.1mmol) was changed to 500mg, 1.9mmol, 95% sulfuric acid (42mL, 733mmol) was changed to 3mL, 52.4mmol, water (154mL) was changed to 11mL, 25% sodium methoxide methanol solution (340mL, 1486mmol) was changed to 25mL, 109mmol, water (90mL) added after neutralization was changed to 6mL, methanol (196mL) was changed to 14mL, isopropanol (300mL) added in the first time was changed to 60mL, and isopropanol (300mL) added in the second time was changed to 30mL, but the same operation was performed to obtain a yellow solid (995mg). This solid was analyzed by ESI-MS - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0326] <Example 69> 95% sulfuric acid (8 mL, 139.6 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (2.0 g, 7.5 mmol), and the solution was heated and stirred at 50°C for 6 hours. The solution was then cooled to 0°C, and water (28 mL) and 25% sodium methoxide methanol solution (65 mL, 284.1 mmol) were slowly added. Water (24 mL) and methanol (56 mL) were then added, and the mixture was heated and stirred overnight under reflux, filtered while hot, and the low boiling point fraction was concentrated under reduced pressure. Isopropanol (120 mL) was added to the mixture, concentrated under reduced pressure, and isopropanol (100 mL) was added again, and filtered to obtain a yellowish white solid (3.85 g). This solid was analyzed by ESI-MS - Analysis by FT-IR spectroscopy revealed that the solution contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate and sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0327] <Example 70> In Example 69, the 95% sulfuric acid (8 mL, 139.6 mmol) was changed to 12 mL, 209.4 mmol, the reaction temperature was changed from 50° C. to 65° C., the reaction time was changed from 6 hours to 3 hours, the water (28 mL) was changed to 42 mL, the 25% sodium methoxide methanol solution (65 mL, 284.1 mmol) was changed to 96 mL, 419.5 mmol, and the first isopropanol (120 mL) was changed to 160 mL. The same procedure was carried out to obtain a yellow solid (4.09 g). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0328] <Example 71> In Example 69, the 95% sulfuric acid (8 mL, 139.6 mmol) was changed to 6 mL, 104.7 mmol, the reaction temperature was changed from 50°C to 80°C, the water (28 mL) was changed to 21 mL, the 25% sodium methoxide methanol solution (65 mL, 284.1 mmol) was changed to 49 mL, 214.1 mmol, and the first isopropanol (120 mL) was changed to 200 mL. The same procedure was carried out to obtain a yellow solid (4.18 g). This solid was analyzed by ESI-MS. - Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0329] <Example 72> A yellowish white solid was obtained by carrying out the same procedure as in Example 69, except that 95% sulfuric acid (8 mL, 139.6 mmol) was changed to 6 mL, 104.7 mmol, water (28 mL) was changed to 21 mL, and 25% sodium methoxide methanol solution (65 mL, 284.1 mmol) was changed to 49 mL, 214.1 mmol. This solid was analyzed by ESI-MS. - Analysis by FT-IR spectroscopy revealed that the solution contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate and sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0330] <Example 73> 95% sulfuric acid (3 mL, 52.4 mmol) was added to dinaphtho[2,1-b:1',2'-d]furan (500 mg, 1.9 mmol), and the solution was heated and stirred at 50°C for 6 hours. Water (10 mL) and 1-octanol (11 mL) were then added to the solution to extract the organic layer. A 2.5 M aqueous solution of sodium hydroxide (2.5 mL, 6.25 mmol) was added to the collected organic layer to extract the aqueous layer, and the aqueous solvent was concentrated under reduced pressure. Isopropanol (120 mL) was added to the mixture, concentrated under reduced pressure, and isopropanol (100 mL) was added again and filtered to obtain an orange solid (1.23 g). This solid was analyzed by ESI-MS. -Analysis revealed that it contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0331] <Example 74> In Example 73, the 2.5 M aqueous sodium hydroxide solution (2.5 mL, 6.25 mmol) was changed to 3 mL, 7.5 mmol, and the first isopropanol (120 mL) was changed to 60 mL, but the same procedure was carried out to obtain an orange solid (871 mg). - Analysis by FT-IR spectroscopy revealed that the solution contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate and sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0332] <Example 75> In Example 73, the reaction temperature was changed from 50°C to 65°C, the reaction time was changed from 6 hours to 3 hours, 1-octanol (11 mL) was changed to 10 mL, 2.5 M aqueous sodium hydroxide solution (2.5 mL, 6.25 mmol) was changed to 3.4 mL, 8.5 mmol, and isopropanol (120 mL) was changed to 100 mL, but the same procedure was performed to obtain an orange solid (1.33 mg). This solid was analyzed by ESI-MS - Analysis by FT-IR revealed that the solution contained sodium dinaphtho[2,1-b:1',2'-d]furan-3,9-disulfonate and sodium dinaphtho[2,1-b:1',2'-d]furan-3,5,11-trisulfonate.

[0333] <Example 76> [ka] Under an argon atmosphere, dinaphtho[2,1-b:1',2'-d]furan (1.01g, 3.8mmol) was dissolved in dichloromethane (15mL). To this solution, sulfonic acid chloride (0.45g, 3.8mmol) was added and stirred at room temperature for 1.5 hours. Water was then slowly added to this solution, and the aqueous layer was extracted, followed by the addition of 5M aqueous sodium hydroxide (2.0mL, 10mmol) and isopropanol (50mL), and the low boiling point fraction was removed under reduced pressure. Ethanol (50mL) was added to the resulting solid, which was then filtered and washed with ethanol to obtain sodium dinaphtho[2,1-b:1',2'-d]furan-5-sulfonate as a white solid (943mg).

[0334] 1 H-NMR(400MHz,DMSO-d6)δ(ppm):9.18(dd,J=8.6,1.1Hz,1H),9.10(d,J=8.4Hz,2H),8.37(s,1H),8.23 (brd,J=8.3Hz,1H),8.18(d,J=8.9Hz,1H),8.07(d,J=8.9Hz,1H),7.88-7.82(m,2H),7.70-7.65(m,2H). ESI-MS - (MeOH) m / z: 347 (M- Na ) -

[0335] In this way, a water treatment composition using a water-soluble fluorescent compound having a novel structure was obtained. In addition, a water treatment composition capable of suppressing deterioration of the fluorescent compound without depending on ingredients that can be blended in the water treatment agent was obtained.

Claims

1. A fluorescent compound represented by formula (1): 【Chemistry 1】 (In formula (1), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ When n is 2, a plurality of R ９ and R １２ may be the same or different, provided that X is an oxygen atom, n is 1, and R １ , R ２ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １１ and R １２ are all hydrogen atoms, R ３ and R １０ cannot be a sulfo group or a chemically acceptable salt thereof. Further, a compound in which X is a nitrogen atom substituted with an alkyl group having 1 carbon atom, n is 0, R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 are all hydrogen atoms, and R 3 is a sulfo group or a chemically acceptable salt thereof; a compound in which X is a nitrogen atom, n is 0, R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 are all hydrogen atoms, R 1 is a hydroxyl group, and R 3 is a sulfo group or a chemically acceptable salt thereof; and a compound in which X is a nitrogen atom, n is 0, R 1 , R 3 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 are all hydrogen atoms, R 4 is a hydroxyl group, and R 2 is a sulfo group or a chemically acceptable salt thereof. is a sulfo group or a chemically acceptable salt thereof, and a compound in which X is a nitrogen atom, n is 1, R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 and R 12 are all hydrogen atoms, and R 4 and R 9 are Sr salts of a sulfo group.

2. 2. The fluorescent compound according to claim 1 , A fluorescent compound, wherein X is an oxygen atom.

3. 3. A fluorescent compound according to claim 1 or 2, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ is a sulfo group or a chemically acceptable salt thereof, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and n is 0 or 1.

4. 4. The fluorescent compound according to claim 3, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ 1. A fluorescent compound, characterized in that one or more and four or less groups selected from the following are sulfo groups or chemically acceptable salts thereof.

5. 3. A fluorescent compound according to claim 1 or 2, R ３ , R ５ , R ６ , R ８ and R １０ 1. A fluorescent compound, wherein at least one group of the formula (I) is a sulfo group or a chemically acceptable salt thereof.

6. 3. A fluorescent compound according to claim 1 or 2, R ３ , R ５ , R ６ , R ８ and R １０ 1. A fluorescent compound, characterized in that at least two groups selected from the following are sulfo groups or chemically acceptable salts thereof.

7. A method for producing a fluorescent compound represented by formula (1), comprising sulfonating an aromatic compound represented by formula (2). 【Chemistry 2】 (In formula (1), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ When n is 2, a plurality of R ９ and R １２ may be the same or different, provided that X is an oxygen atom, n is 1, and R １ , R ２ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １１ and R １２ are all hydrogen atoms, R ３ and R １０ cannot be a sulfo group or a chemically acceptable salt thereof.) 【Chemistry 3】 (In formula (2), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. A １ , A ２ , A ３ , A ４ , A ５ , A ６ , A ７ , A ８ , A ９ , A １０ , A １１ and A １２ each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; A １ , A ２ , A ３ , A ４ , A ５ , A ６ , A ７ , A ８ , A ９ , A １０ , A １１ and A １２ Two or more groups selected from are hydrogen atoms. ９ and A １２ may be the same or different. １ From A １２ Each group represented by the same number R １ From R １２ and when the group represented by R is a sulfo group or a chemically acceptable salt thereof, the corresponding group represented by A is a hydrogen atom.

8. A method for producing the fluorescent compound according to claim 7, comprising the steps of: A method for producing a fluorescent compound, comprising sulfonating the compound with at least one of chlorosulfonic acid, sulfuric acid, and fuming sulfuric acid.

9. A method for producing the fluorescent compound according to claim 8, comprising the steps of: R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ an aromatic sulfonic acid compound or a salt thereof, in which two or less groups selected from the group consisting of sulfo groups, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ 4. A method for producing a fluorescent compound, comprising simultaneously producing an aromatic sulfonic acid compound or a salt thereof, in which three or more groups selected from the group consisting of

10. A water treatment agent composition comprising a fluorescent compound represented by formula (1): 【Chemistry 4】 (In formula (1), X represents an oxygen atom, a selenium atom, a methylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms, a nitrogen atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, a silicon atom which may be substituted with an alkyl group having 1 to 8 carbon atoms, or a carbonyl group. n represents 0, 1 or 2. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ each independently represents a sulfo group or a chemically acceptable salt thereof, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a halogen atom, or a hydroxyl group; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ When n is 2, a plurality of R ９ and R １２ may be the same or different, provided that X is an oxygen atom, n is 1, and R １ , R ２ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １１ and R １２ are all hydrogen atoms, R ３ and R １０ cannot be a sulfo group or a chemically acceptable salt thereof.)

11. The water treatment composition according to claim 10, A water treatment composition further comprising at least one component selected from the group consisting of a water-soluble polymer, a bactericide, an anticorrosive agent, and a pH adjuster.

12. The water treatment composition according to claim 11, The water-treatment agent composition, wherein the water-soluble polymer has at least one monomer unit of a carboxylic acid or a salt thereof.

13. The water treatment composition according to claim 11, The water treatment composition, wherein the disinfectant is at least one of a chlorine-based oxidizing agent, a bromine-based oxidizing agent, and a hypohalous acid stabilizing composition.

14. The water treatment composition according to claim 13, 1. A water treatment agent composition, wherein the stabilized hypohalous acid composition is a stabilized hypobromous acid composition containing a bromine-based oxidizing agent and a sulfamic acid compound.

15. The water treatment composition according to claim 11, The water treatment composition, wherein the corrosion inhibitor is at least one of a nitrite, a molybdate, a polymeric phosphate, a phosphonate, a zinc salt, and an azole compound.

16. The water treatment composition according to claim 11, A water treatment agent composition comprising at least the bactericide and the corrosion inhibitor selected from the group consisting of the water-soluble polymer, the bactericide, the corrosion inhibitor, and the pH adjuster, wherein the corrosion inhibitor is an azole compound.

17. The water treatment composition according to claim 16, A water treatment agent composition, characterized in that a mass ratio of the azole compound to the fluorescent compound is in the range of 7:1 to 100:

1.

18. The water treatment composition according to claim 16 or 17, The water treatment composition, wherein the azole compound is 1,2,3-benzotriazole.

19. A method for treating water to be treated, comprising adding the water treating agent composition according to claim 10 or 11 to the water to be treated.

20. A method for measuring the concentration of the water treating agent composition according to claim 10 or 11 in water to be treated, comprising measuring the concentration of the water treating agent composition according to claim 10 or 11 in the water to be treated by fluorescence measurement.

21. A method for controlling the concentration of the water treatment agent composition according to claim 10 or 11 added to water to be treated, comprising: A concentration control method, comprising: controlling the concentration of the water treatment agent composition added to the water to be treated by measuring the concentration of the fluorescent compound.

22. A concentration control device for controlling the concentration of the water treatment agent composition according to claim 10 or 11 added to water to be treated, A concentration control device for controlling the concentration of the water treatment agent composition added to the water to be treated by measuring the concentration of the fluorescent compound.

Images