KR102197921B1 - Water treatment composition and water treatment method - Google Patents

Abstract

In the water treatment composition containing a bromine-based oxidizing agent, a sulfamic acid compound, and an azole compound, there is provided a stable water treatment composition in which the generation of precipitates is reduced even under conditions such as outdoor storage irradiated with light such as sunlight. A bromine-based oxidizing agent, a sulfamic acid compound, an azole compound, a surfactant, and a polymer containing an N-vinylpyrrolidone monomer, wherein the surfactant is an amphoteric surfactant, an anionic surfactant, and a nonionic interface It is a water treatment composition which is at least one type selected from active agents.

Description

Water treatment composition and water treatment method

The present invention relates to a water treatment composition and a water treatment method using the water treatment composition.

As a disinfectant for controlling bioadhesion in industrial water systems such as cooling water systems or paper making processes, inorganic slime control agents that have more oxidizing power than organic slime control agents, that is, have higher immediate effect, are increasingly being used. . As the inorganic slime control agent, hypochlorite such as sodium hypochlorite is mainly used, but in order to further enhance the effect, hypobromate such as sodium hypobromite may be used.

Sodium hypobromite, which has higher slime control performance than sodium hypochlorite, is unstable, and industrially, for example, bromide salts such as sodium bromide and hypochlorite such as sodium hypochlorite are mixed immediately before use. In addition, a method of producing sodium hypobromate in the system or a method of providing a stabilized hypobromite in which hypobromate is stabilized with sulfamic acid or the like are employed.

A water treatment composition in which these inorganic slime control agents and an azole compound corresponding to an anticorrosive agent for a copper-based metal such as a copper alloy are made into one formulation has been developed.

For example, Patent Document 1 discloses a water treatment composition in which a bromine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent, a sulfamic acid compound, and an azole compound are blended at a pH of 13.2 or higher.

In addition, Patent Document 2 discloses a composition for eradicating or inhibiting a biofilm containing a biocide and a biodispersant based on bromine stabilized with sulfamate. Patent Document 2 describes that as a bio-dispersant, it can be selected from various types of surfactants including anionic, nonionic, cationic and amphoteric surfactants.

JP 2015-044765 A JP (Special) 2005-505408 A

The water treatment composition containing a bromine-based oxidizing agent, a sulfamic acid compound, and an azole compound described in Patent Document 1 is mainly stored in an outdoor tank next to a cooling tower irradiated with direct sunlight. However, when the water treatment composition is stored outdoors, it has been found that there is a problem in that when light such as sunlight is irradiated, the azole compound is decomposed and precipitates are formed. Moreover, although many surfactants are illustrated as a bio-dispersing agent in patent document 2, it does not mention at all about what mix|blending an azole compound and what the azole compound decomposes and generates a precipitate.

An object of the present invention is to provide a water treatment composition containing a bromine-based oxidizing agent, a sulfamic acid compound, and an azole compound, in which the generation of precipitates is reduced even under conditions such as outdoor storage irradiated with light such as sunlight. It is in doing.

The present invention includes at least one of a bromine-based oxidizing agent, a sulfamic acid compound, an azole compound, a surfactant and a polymer containing an N-vinylpyrrolidone monomer, wherein the surfactant is an amphoteric surfactant and an anionic surfactant. And at least one type of water treatment composition selected from nonionic surfactants.

In the water treatment composition, it is preferable that the surfactant is at least one amphoteric surfactant selected from an alkylamino fatty acid type surfactant, an alkyl betaine type surfactant, and an alkylamine oxide type surfactant.

In the water treatment composition, it is preferable that the surfactant is an anionic surfactant or a nonionic surfactant having an alkyl ether structure.

In the water treatment composition, it is preferable that the bromine-based oxidizing agent is bromine.

In the water treatment composition, the blending amount of at least one of the surfactant and the N-vinylpyrrolidone monomer-containing polymer in the water treatment composition is 0.01% by weight or more and 30% by weight or less with respect to the total weight of the water treatment composition. desirable.

In the water treatment composition, it is preferable that the pH of the water treatment composition is 13.0 or more.

Further, the present invention is a water treatment method for treating water using the water treatment composition.

In the present invention, in the water treatment composition containing a bromine-based oxidizing agent, a sulfamic acid compound, and an azole compound, at least one surfactant selected from amphoteric surfactants, anionic surfactants and nonionic surfactants, and N-vinylpi By blending at least one of the rolidone monomer-containing polymers, it is possible to provide a stable water treatment composition in which the generation of precipitates is reduced even under conditions such as outdoor storage irradiated with light such as sunlight.

Embodiments of the present invention will be described below. This embodiment is an example of carrying out the present invention, and the present invention is not limited to this embodiment.

<Water treatment composition>

As a result of intensive examination by the present inventors, a hypobromic acid stabilizing composition (hypobromic acid stabilizing composition) formed from a ``bromine-based oxidizing agent'' and a ``sulfamic acid compound'', a ``azole compound'', and a ``positive surfactant, anionic By mixing at least one surfactant selected from surfactants and nonionic surfactants” and at least one of “N-vinylpyrrolidone monomer-containing polymer”, under conditions such as outdoor storage irradiated with sunlight or other light It has been found that it becomes possible to provide a stable liquid water treatment composition having a higher quality, in which the generation of road precipitates is reduced.

The water treatment agent composition according to the present embodiment is at least one selected from ``bromine-based oxidizing agent'', ``sulfamic acid compound'', ``azole compound'', and ``amphoteric surfactant, anionic surfactant, and nonionic surfactant. A hypobromic acid stabilizing composition formed of a ``bromine-based oxidizing agent'' and a ``sulfamic acid compound'', but containing at least one of ``a polymer containing N-vinylpyrrolidone monomer'' and a ``azole compound'', It may contain at least one of “at least one surfactant selected from amphoteric surfactants, anionic surfactants and nonionic surfactants” and “N-vinylpyrrolidone monomer-containing polymer”.

The ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" is preferably 1 or more. When the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" is less than 1, the amount of bromic acid produced in the reaction system may increase.

Bromo seeds the amount included in the water treatment agent composition according to the present embodiment, as an effective halogen concentration of chlorine conversion, water treatment chemicals with respect to the amount of the total composition, and preferably less than 0.1% by weight (calculated as Cl _2), 0.5% by weight (calculated as Cl ₂ ) To 20% by weight (as Cl ₂ ), more preferably in the range of 1.1% by weight (as Cl ₂ ) to 20% by weight (as Cl ₂ ). If the amount of bromine is less than 1.1% by weight (as Cl ₂ ) of the total amount of the water treatment composition as an effective halogen concentration, the slime control performance of the water treatment composition may slightly decrease, and exceeds 20% by weight (as Cl ₂ ). If so, the amount of bromic acid produced may increase. When the amount of bromine is less than 0.5% by weight (as Cl ₂ ) relative to the total amount of the water treatment composition as an effective halogen concentration, the slime control performance of the water treatment composition may decrease.

The bromine constituting the hypobromic acid stabilizing composition needs to be supplied as active bromine by some means, and bromine (liquid bromine) may be used as a bromine-based oxidizing agent, or a chlorine-based bromine compound and hypochlorite Activated bromine generated by reacting an oxidizing agent may be used, or as a bromine-based oxidizing agent, activated bromine via bromine chloride, bromate, or the like may be used. Among these, the most preferable one is to use bromine (liquid bromine).

Examples of the bromine-based oxidizing agent include bromine (liquid bromine), bromine chloride, bromic acid, bromate, hypobromic acid, and the like. As described above, the "reaction product of a bromine compound and a chlorine-based oxidizing agent" obtained by reacting a bromine compound with a chlorine-based oxidizing agent such as hypochlorite is also included in the bromine-based oxidizing agent. Among these, the composition containing "bromine and sulfamic acid compound (a mixture of bromine and sulfamic acid compound)" or "reaction product of bromine and sulfamic acid compound" using bromine is "hypochlorous acid and bromine compound. Compared to a composition containing "persulfamic acid" and a composition containing "bromine chloride and sulfamic acid", the stability of the effective bromine is high and the by-product of bromic acid can be suppressed, so it is more preferable.

Examples of the bromine compound include sodium bromide, potassium bromide, lithium bromide, ammonium bromide, and hydrobromic acid. Among these, sodium bromide, potassium bromide, and ammonium bromide are preferred from the viewpoint of manufacturing cost and the like.

Examples of the chlorine-based oxidizing agent include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chlorous acid or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, chlorinated isocyanuric acid or a salt thereof, etc. . Among these, as salts, for example, hypochlorous acid alkali metal salts such as sodium hypochlorite and potassium hypochlorite, hypochlorous acid alkaline earth metal salts such as calcium hypochlorite and barium hypochlorite, chlorous acid such as sodium chlorite and potassium chlorite Alkali metal salts, alkaline earth metal salts of chlorite such as barium chlorite, other metal salts of chlorite such as nickel chlorite, alkali metal salts of chlorate such as ammonium chlorate, sodium chlorate, potassium chlorate, alkaline earth metal salts of chlorate such as calcium chlorate, barium chlorate, etc. Can be mentioned. These chlorine-based oxidizing agents may be used singly 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 properties and the like.

The sulfamic acid compound is a compound represented by the following general formula (1).

R ₂ NSO ₃ H (1)

(In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

As a sulfamic acid compound that is considered to act as a stabilizer for an inorganic slime control agent constituting the stabilized composition of hypobromic acid, for example, in addition to sulfamic acid (amide sulfuric acid) in which both R groups are hydrogen atoms, N -One of the two R groups, such as methylsulfame acid, N-ethylsulfame acid, N-propylsulfame acid, N-isopropylsulfame acid, and N-butylsulfame acid, is a hydrogen atom, and the other has 1 to 8 carbon atoms. Sulfamic acid compounds which are alkyl groups, N,N-dimethylsulfamic acid, N,N-diethylsulfamic acid, N,N-dipropylsulfamic acid, N,N-dibutylsulfamic acid, N-methyl-N-ethylsulphate A sulfamic acid compound in which both of the two R groups such as pamic acid and N-methyl-N-propylsulfamic acid are alkyl groups having 1 to 8 carbon atoms, and one of the two R groups such as N-phenylsulfamic acid is a hydrogen atom, and the other The sulfamic acid compound, which is an aryl group having 6 to 10 carbon atoms, or a salt thereof, may be mentioned. Examples of sulfamic acid salts include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, strontium salt, and barium salt, manganese salt, copper salt, zinc salt, iron salt, cobalt salt, nickel salt, etc. And other metal salts, ammonium salts, and guanidine salts.

The sulfamic acid compounds and salts thereof may be used singly or in combination of two or more. As the sulfamic acid compound, it is preferable to use sulfamic acid (amide sulfuric acid) from the viewpoint of environmental load and the like.

The azole compound acts as an anticorrosive agent for copper-based metals, such as copper and a copper alloy. As an azole compound, for example, 1,2,3-benzotriazole, tolyltriazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, imidazole, 2-mer And captobenzoimidazole, 2-mercaptobenzothiazole, and the like, and may be used singly or in combination of two or more. Among these, benzotriazole and tolyltriazole are preferable from the viewpoint of manufacturing cost and the like.

The water treatment composition according to the present embodiment may further contain an alkali. Examples of the alkali include alkali hydroxides such as sodium hydroxide and potassium hydroxide. Sodium hydroxide and potassium hydroxide may be used in combination from the viewpoint of product stability at low temperatures. In addition, alkali is not solid, and may be used as an aqueous solution.

When the hypobromic acid stabilized composition and the azole compound are liquefied in one liquefaction, pH control is very important, and it is preferable that the pH is 13.0 or higher before and after mixing the hypobromic acid stabilized composition and the azole compound. The pH of the composition is preferably 13.0 or more, more preferably 13.2 or more, even more preferably 13.5 or more, and particularly preferably 13.7 or more. If the pH of the composition is less than 12.0, the stability of the hypobromic acid stabilizing composition changes and decomposes the azole compound, so that one liquefaction becomes difficult. In this regard, it is a very different idea from the first formulation of N-monochlorosulfamic acid and an azole compound formed of sodium hypochlorite and sulfamic acid.

As surfactants contained in the water treatment composition according to the present embodiment, amphoteric surfactants, anionic surfactants, and nonionic surfactants can be exemplified, and from the viewpoint of storage stability of drugs when irradiated with sunlight, amphoteric surfactants Or it is preferable that it is a nonionic surfactant.

Examples of the amphoteric surfactant contained in the water treatment composition according to the present embodiment include an alkylamino fatty acid type surfactant, an alkyl betaine type surfactant, and an alkylamine oxide type surfactant. Examples of the alkylamino fatty acid type surfactant include alkylamino monopropionate and alkylaminodipropionate. As the alkyl betaine type surfactant, in addition to alkyldimethylamidoacetic acid betaine, etc., sulfobetaine type surfactants such as alkylamidopropylhydroxysultaine, alkylamidopropyl betaine, palm oil fatty acid amidopropyl betaine, etc. Fatty acid amidopropyl betaine type surfactant, imidazolium betaine type surfactant such as 2-alkyl-N'-carboxymethyl-N'-hydroxyethyl imidazonium betaine, 2-alkyl-N'-carboxymethyl- Ethylenediamine betaine type surfactants such as N'-hydroxyethylethylenediamine salt or 2-palm oil fatty acid-N'-carboxyethyl-N'-hydroxyethylethylenediamine salt, phosphatidylcholine, alkylhydroxyphosphobetaine, etc. Phosphobetaine type surfactant, etc. are mentioned. Examples of the alkylamine oxide type surfactant include alkyldimethylamine N-oxide and higher fatty acid amidopropyldimethylamine oxide. From the standpoint of storage stability, etc., it is preferable that it is at least one selected from alkylamino fatty acid type surfactant, alkyl betaine type surfactant, and alkylamine oxide type surfactant, and from the viewpoint of formulation stability, alkyl betaine type surfactant and alkyl It is more preferable that it is at least 1 type selected from amine oxide type surfactant.

The alkylamino fatty acid type surfactant contained in the water treatment composition according to the present embodiment is preferably one represented by the following general formula (2):

(In formula (2), R ¹ is a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, preferably 1 to 19. n is a number of 1 to 10, and n is preferably 1 to 3. R ² , R ³ is each independently an alkylene group having 0 to 5 carbon atoms or a hydroxyalkylene group, and from the viewpoint of storage stability, an alkylene group having 1 to 3 carbon atoms is preferred. A ¹ and A ² are each independently -H, -COOH, -CONH ₂ , -OCOH, -NHCOH, -NHCOR ⁴ , -OH,-[(CH ₂ ) _m -N((CH ₂ ) _p COOH)]-(CH ₂ ) _q is a group selected from COOH, and terminal H When the group is decomposed, it exists as a salt such as sodium or potassium, etc. R ⁴ is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 19. m, p, and q are each independently a number of 1 to 20. In addition, "R ² , R ³ is an alkylene group or hydroxyalkylene group having 0 carbon atoms" in the formula (2), wherein R ² and R ³ do not exist, and A ¹ and A ² are directly bonded to N. Indicate what you are doing.)

As the alkylamino fatty acid type surfactant, from the viewpoint of formulation stability, etc., a compound in which R is an alkyl group having 8 to 18 carbon atoms and n is 1 to 3 is preferable.

The alkyl betaine-type surfactant contained in the water treatment composition according to the present embodiment is preferably one represented by the following general formula (3):

(In formula (3), R ¹ is an alkyl group having 8 to 16 carbon atoms, preferably 10 to 16, more preferably 10 to 14. R ² and R ⁵ are each independently 1 to 5 carbon atoms, preferably It is an alkylene group or a hydroxyalkylene group of 1 to 3. R ³ and R ⁴ are each independently an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of storage stability. Is a group selected from -COO-, -CONH-, -OCO-, -NHCO-, -O-, and n is preferably a number of 0 or 1. X is -COO- or -SO ₃ -.)

As the alkyl betaine type surfactant, from the viewpoint of formulation stability, etc., R ¹ is an alkyl group having 10 to 14 carbon atoms, R ³ and R ⁴ are methyl groups, and alkyldimethylaminoacetic acid betaine wherein n=0 is preferable, and R ¹ It is this C12 alkyl group, R ³ and R ⁴ are methyl groups, and lauryldimethylaminoacetic acid betaine of n=0 is more preferable.

The alkylamine oxide type surfactant contained in the water treatment composition according to the present embodiment is preferably one represented by the following general formula (4):

(In formula (4), R ¹ is an alkyl group having 8 to 16 carbon atoms, preferably 10 to 16, more preferably 10 to 14. R ² is an alkylene group having 1 to 5, preferably 2 or 3 carbon atoms. R ³ and R ⁴ are each independently a C 1 to C 3 alkyl group or a hydroxy alkyl group, and from the viewpoint of storage stability, a C 1 to C 3 alkyl group is preferred. A is -COO-, -CONH-, -OCO It is a group selected from -, -NHCO-, -O-, n is a number of 0 or 1, and n=0 is preferable from the viewpoint of storage stability.)

As the alkylamine oxide type surfactant, from the viewpoint of formulation stability and the like, R ¹ is an alkyl group having 10 to 12 carbon atoms, R ³ and R ⁴ are methyl groups, and a palm oil alkylamine oxide having n=0 is preferable.

As anionic surfactants contained in the water treatment composition according to the present embodiment, fatty acid-type surfactants such as lauric acid and palmitic acid, alkyl ether carboxylic acids, alkyl sulfates, alkyl sulfuric acid ester salts, acylactates, N- Acylamino acid salt, alkanesulfonic acid salt, α-olefin sulfonate, α-sulfo fatty acid methyl ester salt, alkyl diphenyl ether disulfonate, straight chain alkyl naphthalene sulfonate, alkyl ether sulfuric acid ester salt, polyoxyethylene alkyl sulfuric acid ester Salts, polyoxyethylene alkylaryl sulfate ester salts, polyoxyethylene alkylphenyl ether sulfonic acid salts, alkyl phosphoric acid ester salts, and alkyl sulfosuccinic acid salts. From the standpoint of formulation stability, etc., compared to alkyl sulfates, alkylbenzene sulfonates, etc., anionic surfactants having an alkyl ether structure are preferred, and in particular, anionic interfaces containing polyoxyethylene chains such as polyoxyethylene alkyl ether sulfates It is preferably an active agent.

As nonionic surfactants, polyoxyethylene alkylphenyl ether type surfactants such as polyoxyethylene alkyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, polyoxyethylene poly Polyhydric alcohol fatty acid ester type surfactants such as oxypropylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, alkyl glucoside, polyoxyethylene fatty acid ester, polyoxyethylene castor oil, sucrose fatty acid ester and sorbitan fatty acid ester, and polyhydric Alcohol alkyl ether type surfactants, fatty acid alkanolamides, ethylene oxide/propylene oxide adducts of lower/higher alcohols, sucrose fatty acid esters, alkanolamides, and the like. From the viewpoint of formulation stability and the like, a nonionic surfactant having an alkyl ether structure is preferable, and in particular, a nonionic surfactant containing a polyoxyethylene chain such as polyoxyethylene alkylphenyl ether is preferable.

The N-vinylpyrrolidone monomer-containing polymer contained in the water treatment composition according to the present embodiment may be a polymer containing N-vinyl-2-pyrrolidone as a monomer constituting the polymer, and is not particularly limited. As the N-vinylpyrrolidone monomer-containing polymer, in addition to polyvinylpyrrolidone, a copolymerized polymer containing an N-vinylpyrrolidone monomer may be mentioned. As a polymerizable monomer copolymerizable with N-vinylpyrrolidone, (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acrylate hydroxyethyl )Acrylic acid esters, (meth)acrylamide, N-monomethyl (meth)acrylamide, N-monoethyl (meth)acrylamide, induction of (meth)acrylamide such as N,N-dimethyl (meth)acrylamide Retention, basic unsaturated monomers such as dimethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, vinylpyridine, vinylimidazole, and salts or quaternary products thereof, vinyloxazoline, isopropenyloxa Iminoethers such as zoline, carboxyl group-containing unsaturated monomers such as (meth)acrylic acid, itaconic acid, maleic acid, and pmalic acid, and salts thereof, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) )Acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, methyl 2 -(Hydroxymethyl)acrylate, ethyl 2-(hydroxymethyl)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, tris(hydroxyethyl)isocyanuric acid Mono(meth)acrylate, tris(hydroxyethyl)isocyanuric acid di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri( Unsaturated monomers having a hydroxyl group such as meth)acrylate, unsaturated anhydrides such as maleic anhydride and itaconic anhydride, vinyl esters such as vinyl acetate and vinyl propionate, vinylethylene carbonate and derivatives thereof, styrene and derivatives thereof, ( Ethyl meth)acrylate-2-sulfonic acid and derivatives thereof, vinyl sulfonic acid and derivatives thereof, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, ethylene, propylene, octene, butadiene, etc. Olefins and unsaturated monomers having a glycidyl group such as glycidyl (meth)acrylate. have. Among these N-vinylpyrrolidone monomer-containing polymers, polyvinylpyrrolidone is particularly preferred from the viewpoints of formulation stability and cost.

In the water treatment composition according to the present embodiment, it is preferable to blend a scale dispersant in addition to the above-described components, if necessary. The scale dispersant is for suppressing the generation of scale by chelating calcium ions, magnesium ions, etc. involved in the generation of scale to improve the solubility of the ions in water. Thereby, deposition of sludge in the cooling tower or the like is suppressed, and corrosion due to deposited sludge or the like can be suppressed.

As this scale dispersant, for example, polyacrylic acid or its salt, polymaleic acid or its salt, acrylamide polymer and acrylic acid polymer, monomer units of (meth)acrylic acid and/or salt thereof, (meth)acrylamide-alkyl -And/or polyacrylic acid, copolymer of acrylic acid and acrylamide, phosphinic acid or bis(poly-2), such as a water-soluble copolymer consisting of monomer units of aryl-sulfonic acid and/or salts thereof and monomer units of substituted (meth)acrylamide -Phosphinic acid compounds such as carboxyethyl)phosphinic acid, phosphinocarboxylic acid, aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, 2-phosphonobutane-1,2,4-1.2-tricarboxylic acid, 1 -Selected from the group consisting of phosphonic acid salts such as hydroxyethylidene-1,1-diphosphonic acid, hydroxyphosphonoacetic acid, polymerized phosphate, ethylenediamine tetraacetic acid, nitrotriacetic acid, and salts thereof At least one type is mentioned.

The content of bromate ions in the water treatment composition according to the present embodiment is preferably 10 mg/kg or less, and more preferably 5 mg/kg or less. When the content of bromate ions exceeds 10 mg/kg, there is a possibility that the decomposition of the azole compound may be accelerated.

The proportion of free halogen in the water treatment composition according to the present embodiment is preferably 10% or more, more preferably 70% or more, and still more preferably 90% or more. When the proportion of free halogen is less than 10%, the sterilization effect may be lowered.

In the water treatment composition according to the present embodiment, at least one of a surfactant (at least one selected from an amphoteric surfactant, an anionic surfactant, and a nonionic surfactant) and an N-vinylpyrrolidone monomer-containing polymer is used in the composition. It is preferable to include 0.01% by weight or more and 30% by weight or less based on the total weight, more preferably more than 0.01% by weight and 30% by weight or less, even more preferably 0.05% by weight or more and 10% by weight or less, and 0.05% by weight It is particularly preferable to contain more than 5% by weight. If the content of at least one of the surfactant and the N-vinylpyrrolidone monomer-containing polymer is less than 0.01% by weight relative to the total weight of the composition, the azole compound may be decomposed to form a precipitate, and if it exceeds 30% by weight, preparation The cost may be high.

<Method of manufacturing water treatment composition>

The water treatment composition according to the present embodiment is, for example, after mixing an alkali in water as necessary, and then a surfactant (at least one selected from amphoteric surfactants, anionic surfactants and nonionic surfactants) and N -Mixing at least one of the vinylpyrrolidone monomer-containing polymers, then mixing the azole compound, further mixing a bromine-based oxidizing agent and a sulfamic acid compound, or a reaction product of a bromine compound and a chlorine-based oxidizing agent, and sulfamic acid It is obtained by mixing the compounds.

At least one of a bromine, a sulfamic acid compound, an azole compound, a surfactant (at least one selected from an amphoteric surfactant, an anionic surfactant, and a nonionic surfactant) and an N-vinylpyrrolidone monomer-containing polymer As a method for producing a water treatment composition containing water, if necessary, an alkali, a surfactant (at least one selected from amphoteric surfactants, anionic surfactants and nonionic surfactants), and N-vinylpyrrolidone monomer contained A step of reacting by adding bromine to a mixed solution containing at least one of the polymers, an azole compound and a sulfamic acid compound in an inert gas atmosphere, or water, if necessary, an alkali, a surfactant (an amphoteric surfactant, an anionic interface At least one selected from activators and nonionic surfactants) and at least one of the N-vinylpyrrolidone monomer-containing polymer, an azole compound, and a sulfamic acid compound, adding bromine in an inert gas atmosphere It is preferable to include. Bromine is added and reacted in an inert gas atmosphere, or bromine is added in an inert gas atmosphere to lower the bromate ion concentration in the composition.

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

The oxygen concentration in the reactor at the time of 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. When 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.

The addition rate of bromine is preferably 25% by weight or less, and more preferably 1% by weight or more and 20% by weight or less with respect to the total amount of the composition. When the addition rate of bromine exceeds 25% by weight with respect to the total amount of the 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 inferior.

The reaction temperature at the time of addition of bromine is preferably controlled to a range of 0°C or more and 25°C or less, but more preferably control to a range of 0°C or more and 15°C or less from the viewpoint of manufacturing cost and the like. When the reaction temperature at the time of addition of bromine exceeds 25°C, the amount of bromic acid produced in the reaction system may increase, and when it is less than 0°C, it may be frozen.

By the method for producing the water treatment composition according to the present embodiment, mainly the sulfamic acid-hypobromate composition does not substantially contain bromate ions, and can be safely handled. By the method for producing a water treatment composition according to the present embodiment, a water treatment composition of a one-agent system that does not substantially contain bromate ions, has excellent sterilization performance, and is excellent in storage stability can be obtained.

<Water treatment method using water treatment composition>

The water treatment composition according to the present embodiment can be used in water treatment methods such as water treatment of industrial water systems such as cooling water, and pipe washing in which bioadhesive contamination has advanced.

It is preferable that the effective bromine concentration in the aqueous system to which the water treatment agent composition according to the present embodiment is added is 0.01 to 100 mg/L (as Cl ₂ ). If it is less than 0.01㎎ / ℓ (as Cl _2), and may not be able to obtain enough slime inhibiting effect, it is more than (as Cl ₂₎ 100㎎ / ℓ, there is a possibility of causing corrosion and so on, such as a pipe.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

About Examples and Comparative Examples, formulation was carried out by adding in the blending composition (% by weight) shown in Tables 1 to 5. In the order of addition, after mixing water and alkali, a surfactant or a polymer containing an N-vinylpyrrolidone monomer was mixed, the azole compound was then mixed, and a hypobromic acid stabilized composition was further added. Formulation was carried out by cooling to room temperature or lower in a container made of PTFE (polytetrafluoroethylene), and adding each drug while stirring with a stirrer.

In addition, in Tables 1 to 5, hypobromic acid stabilizing compositions A, a, B, C, and D are as follows.

[Preparation of hypobromic acid stabilizing composition A]

In a nitrogen atmosphere, liquid bromine: 16.9% by weight (wt%), sulfamic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.94% by weight, water: by mixing the residue, hypobromic acid stabilized composition A Prepared. The pH of the hypobromic acid stabilizing composition A was 14, and the bromine content (concentration) was 16.9% by weight (as Br ₂ ). In addition, the bromine concentration in terms of total chlorine was 7.5% by weight (as Cl ₂ ). The detailed preparation method of hypobromic acid stabilizing composition A is as follows.

To keep the oxygen concentration in the reaction vessel at 1%, 1436 g of water and 361 g of sodium hydroxide were added and mixed to a 2 liter four-necked flask sealed by continuous injection while controlling the flow rate of nitrogen gas by the mass flow controller. After mixing by adding sulfamic acid, 473 g of liquid bromine was added while maintaining cooling so that the temperature of the reaction solution became 0 to 15°C, and 230 g of a 48% potassium hydroxide solution was added, in a weight ratio to the total amount of the composition. Sulfamic acid 10.7%, bromine 16.9%, the equivalent ratio of sulfamic acid to the equivalent of bromine was 1.04, to obtain the desired hypobromic acid stabilized composition A. The pH of the obtained solution was 14 as measured by the glass electrode method. The bromine content of the obtained solution is 16.9% as measured by a method of converting bromine to iodine with potassium iodide and then performing redox titration using sodium thiosulfate, and is 100.0% of the theoretical bromine content (16.9%). Was. In addition, the oxygen concentration in the reaction vessel during the bromine reaction was measured using "Oxygen Monitor JKO-02 LJDII" manufactured by Zico Corporation. In addition, the bromic acid concentration was less than 5 mg/kg.

In addition, the measurement of pH was performed under the following conditions.

Electrode type: Glass electrode type

pH meter: manufactured by Toa DKK, type IOL-30

Electrode calibration: 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) were calibrated at two points.

Measurement temperature: 25℃

Measured value: The electrode is immersed in the measuring solution, the value after stabilization is used as the measured value, and the average value of three measurements

The effective halogen concentration is a value measured by the effective total chlorine measurement method (DPD (diethyl-p-phenylenediamine) method) by diluting a sample by 20,000 times and using a HACH multi-item water quality analyzer DR/4000 ( Mg/l, as Cl ₂ ). In addition, effective halogen referred to herein is a value measured by the effective total chlorine measurement method (DPD method). Further, from the effective chlorine concentration, the effective bromine concentration (mg/L, as Cl ₂ ), which is the effective halogen concentration in terms of chlorine, can be calculated, and the measured value by the effective total chlorine measurement (DPD method) is 2.25 (159.8 (g /㏖)/70.9(g/㏖)) can be multiplied (the molecular weight of chlorine (Cl ₂ ) is 70.9 (g/㏖), and the molecular weight of bromine (Br ₂ ) is 159.8 (g/㏖). do)

The turbidity was measured by the photometric method using the HACH multi-item water quality analyzer DR/2800.

[Hypobromic acid stabilizing composition a]

The target hypobromic acid stabilized composition a was obtained by the same composition ratio and production method as the hypobromic acid stabilized composition A except for reacting in the atmosphere without flowing nitrogen gas. The hypobromic acid stabilizing composition a had a pH of 14 and a bromine content of 16.9% by weight.

[Hypobromic acid stabilizing composition B]

Based on the description of Japanese Patent Application Laid-Open No. 11-506139, it is a composition produced in the following procedure. The pH of the hypobromic acid stabilizing composition B was 14 and the bromine content was 9.2% by weight.

(1) To 60.0 grams of a 40% by weight pure sodium bromide solution, 50.0 grams of a 12% sodium hypochlorite solution was added, followed by stirring.

(2) A stabilizing solution was prepared from 20.6 grams of pure water, 9.6 grams of sulfamic acid, and 6.6 grams of sodium hydroxide.

(3) To the solution of (1), the stabilizing solution of (2) was added while stirring to obtain the desired stabilized hypobromic acid composition B.

[Hypobromic acid stabilizing composition C]

It is a composition containing bromine chloride, sulfamic acid, and sodium hydroxide. The pH of the hypobromic acid stabilized composition C was 14, and the bromine content was 15.5%.

In Examples and Comparative Examples, the free halogen concentration and the total halogen concentration were obtained by diluting a sample by 20,000 times, and using the HACH multi-item water quality analyzer DR/4000, the effective chlorine measurement method (DPD (diethyl-p-phenylene It measured by the diamine) method). In addition, the free bromine concentration and the total bromine concentration were calculated as the free chlorine concentration and the total chlorine concentration, and then the values calculated from the molecular weights of chlorine and bromine were used.

[Hypobromic acid stabilizing composition D]

Based on the description of International Patent Application Publication No. 03/093171, a hypobromic acid stabilized composition D was prepared. The hypobromic acid stabilizing composition D is a composition containing liquid bromine, sulfamate, and sodium hydroxide. The pH of the hypobromic acid stabilizing composition D was 14, and the bromine content (concentration) was 16.1% by weight (as Br ₂ ). Moreover, the total concentration in terms of chlorine of bromine was 7.1% by weight (as Cl ₂ ). The equivalent ratio of sulfamic acid to the equivalent of bromine was 1.45.

[Sodium hypobromate composition]

Pure water: 24.6% by weight (wt%), sodium hydroxide: 2.0% by weight, sodium hypochlorite: 62.5% by weight (wt%), sodium bromide: 10.9% by weight were mixed in this order to prepare a sodium hypobromate composition . The bromine content (concentration) was 17% by weight (as Br ₂ ). Moreover, the total concentration of bromine in terms of chlorine was 7.5% by weight (as Cl ₂ ).

<Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-3>

As the hypohalogen salt, a hypobromic acid stabilizing composition A was blended, and benzotriazole was blended as an azole compound such as an anticorrosive agent for copper-based metals such as copper or a copper alloy. As surfactants, lauryldimethylaminoacetic acid betaine (Example 1-1), palm oil alkylamine oxide (Example 1-2) as amphoteric surfactants, polyoxyethylene alkyl ether sulfate as anionic surfactant (Example 1-1) Example 1-3), poly(oxyethylene) alkylphenyl ether as a nonionic surfactant (Example 1-4), polyvinylpyrrolidone as a polymer containing N-vinylpyrrolidone monomer (weight average molecular weight: 8,000) (Example 1-5), dimethyloctylamine (Comparative Example 1-2) and alkyltrimethylammonium chloride (Comparative Example 1-3) as cationic surfactants were blended. In Comparative Example 1-1, no surfactant or N-vinylpyrrolidone monomer-containing polymer was blended. After formulation, it was stored outdoors and the presence or absence of a precipitate after irradiation in the sun for one week was visually confirmed.

From Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3, a hypobromic acid stabilizing composition A was blended, and lauryldimethylaminoacetic acid betaine, which are amphoteric surfactants, palm oil alkylamine oxide, It is possible to formulate a water treatment composition when polyoxyethylene alkyl ether sulfate as an anionic surfactant, poly(oxyethylene) alkylphenyl ether as a nonionic surfactant, and a polymer containing N-vinylpyrrolidone monomer are blended. , Even after irradiation with sunlight, precipitation hardly occurred, and it was a liquid water treatment composition having excellent quality.

On the other hand, when a surfactant or an N-vinylpyrrolidone monomer-containing polymer was not blended, white precipitates were formed by sunlight irradiation, and it was found that the formulation stability was low (Comparative Example 1-1). In addition, from Comparative Examples 1-2 and 1-3, without mixing amphoteric surfactant, anionic surfactant or nonionic surfactant, dimethyloctylamine of tertiary amine or alkyl of quaternary amine as cationic surfactant When trimethylammonium chloride was blended, a white precipitate was formed, and formulation could not be performed.

<Examples 2-1 to 2-5, Comparative Example 2-1>

As the hypohalogen, hypobromic acid stabilizing composition A (Example 2-1), hypobromic acid stabilizing composition a (Example 2-2), hypobromic acid stabilizing composition B (Example 2-3), hypobromic acid Using the stabilized composition C (Example 2-4), the hypobromic acid stabilized composition D (Example 2-5), or the sodium hypobromate composition (Comparative Example 2-1), formulated as shown in Table 2 , After formulation, it was stored outdoors and the presence or absence of a precipitate after irradiation in the sun for one week was visually confirmed.

From Examples 2-1 to 2-5 and Comparative Example 2-1, when the hypobromic acid stabilizing composition was blended, precipitates hardly occurred even after irradiation with sunlight, resulting in a liquid water treatment composition having excellent quality. When the sodium hypobromate composition was blended, white precipitates were generated by sunlight irradiation, and it was found that the formulation stability was low.

<Examples 3-1 to 3-7>

As the hypohalogen salt, a hypobromic acid stabilizing composition A was formulated, and as shown in Table 3, the amount of lauryldimethylaminoacetic acid betaine or palm oil alkylamine oxide, which is an amphoteric surfactant, was changed to be formulated, after formulation, and stored outdoors. Then, the presence or absence of a precipitate after irradiation for one week in the sun was visually confirmed.

From Examples 3-6 and 3-7, when 0.01% by weight of lauryldimethylaminoacetic acid betaine or palm oil alkylamine oxide as an amphoteric surfactant was blended with respect to the total amount of the composition, after formulation, it was stored outdoors and stored in sunlight. After 1 week of irradiation, very little precipitates occurred.

<Examples 4-1 and 4-2>

As the hypohalogen salt, a hypobromic acid stabilizing composition A was blended, and in Examples 4-1 and 4-2 as shown in Table 4, tolyltriazole was blended and formulated as an azole compound, and after formulation, it was stored outdoors and stored in the sun. The presence or absence of a precipitate after irradiation for a week was visually confirmed.

From Examples 4-1 and 4-2, even after irradiation with sunlight, precipitates hardly occurred, and the liquid water treatment composition was excellent in quality.

<Examples 5-1 to 5-10>

As the hypohalogen salt, the hypobromic acid stabilizing composition A was blended, formulated in the amount shown in Table 5, and stored outdoors after formulation, and the presence or absence of a precipitate after irradiation in the sun for one week was confirmed.

Even after irradiation from Examples 5-1 to 5-10, almost no precipitates were formed, and the liquid water treatment composition was excellent in quality. In addition, although not described in Table 5, when the pH of the water treatment agent composition was less than 13.0, the effective halogen concentration tended to decrease.

As described above, in Examples, the generation of precipitates was reduced even under conditions such as outdoor storage irradiated with light such as sunlight, and a stable water treatment composition was obtained.

Claims (7)

A bromine-based oxidizing agent,
A sulfamic acid compound,
An azole compound,
A water treatment composition comprising at least one of a surfactant and an N-vinylpyrrolidone monomer-containing polymer,
The surfactant is at least one selected from amphoteric surfactants, anionic surfactants and nonionic surfactants,
The water treatment composition, characterized in that the pH of the water treatment composition is 13.0 or higher. The method of claim 1,
The water treatment agent composition, wherein the surfactant is at least one amphoteric surfactant selected from an alkylamino fatty acid type surfactant, an alkyl betaine type surfactant, and an alkylamine oxide type surfactant. The method of claim 1,
The water treatment agent composition, wherein the surfactant is an anionic surfactant or a nonionic surfactant having an alkyl ether structure. The method according to any one of claims 1 to 3,
Water treatment composition, characterized in that the bromine-based oxidizing agent is bromine. The method according to any one of claims 1 to 3,
The water treatment composition, wherein the amount of at least one of the surfactant and the N-vinylpyrrolidone monomer-containing polymer in the water treatment composition is 0.01% by weight or more and 30% by weight or less with respect to the total weight of the water treatment composition. delete A water treatment method comprising treating water using the water treatment composition according to any one of claims 1 to 3.