JP2019108310A - Sterilization algicidal agent composition and sterilization algicidal method, water treatment agent composition and water treatment method - Google Patents

Abstract

Disclosed is a bactericidal algicidal composition and a bactericidal algicidal method that can be stored for a long period of time and has an excellent slime control effect, as well as an excellent slime control effect, anticorrosive effect, and scale prevention effect that can be stored for a long period of time. Provided are a monolithic water treatment composition and a water treatment method. A bactericidal algicidal composition comprising (A) a brominated sulfamic acid compound and (B) a chlorinated sulfamic acid compound, wherein the composition has a pH of 13 or more. And (1) a water treatment composition containing an azole compound and having a pH of 13 or more, and the water treatment composition further comprises (2) a telomer and / or Or (3) a water treatment composition containing an organophosphate compound and having a pH of 13 or more, and a sterilizing algicidal composition and a drainage system and process for adding these water treatment composition Water-based sterilization method and water treatment method. [Selection figure] None

Description

  The present invention can stably prevent various problems caused by microorganisms in various process drainage systems such as cooling water systems, cold and hot water systems, dust collection water systems, paper pulp process water systems, iron making process water systems, metal processing process water systems, etc. A microbicidal and algicidal composition and a bactericidal and algicidal method to be suppressed, and simultaneously suppressing corrosion and scale adhesion of metal materials of heat exchangers, pipes, and various devices in contact with water in combination with bactericidal and algicidal effects Treatment composition and method for treating water.

  Microorganisms that grow in various process water such as cooling water system, cold and hot water system, dust collection water system, paper pulp process water system, iron making process water system, metal processing process water system grow in the system and are microbes called slime and biofouling. It forms a deposit and causes microbial damage such as heat transfer efficiency reduction of the heat exchanger, blocking of the flow path, and microbial corrosion due to anaerobic bacteria.

  In addition, water contains salts such as carbonates, sulfates and silicates of calcium and magnesium, and it precipitates when it is concentrated in the water system, the pH rises, or the temperature rises. It adheres to the surface and causes scale problems such as heat transfer problems in heat exchangers and clogging of piping. In addition, suspended particles of soil, clay, organic matter, etc. which are mixed in water are deposited at a low speed portion of the system. The formation of scale or deposits on the metal surface causes differences in concentration in the dissolved oxygen in part and causes corrosion. As described above, in the system using water, microbiological disorder, scale disorder and corrosion disorder are universal problems and are dealt with using various slime control agents, scale inhibitors, corrosion inhibitors, dispersants and the like.

  Among slime control agents, hypochlorite such as sodium hypochlorite is mainly used as an inorganic type slime control agent, and it is in an environment with high pH such as a highly concentrated cooling water system or an environment with high ammonia concentration. In addition, hypobromous acid salts such as sodium hypobromous acid are also used. However, since there is a problem that hypochlorite and hypobromite are easily decomposed and long-term storage is difficult, it has been practiced to incorporate a stabilizer to enable long-term storage.

  As a stabilizer, a sulfamic acid compound is frequently used, and hypochlorous acid stabilized by sulfamic acid produces a chlorinated sulfamic acid compound, and hypobromous acid stabilized by sulfamic acid is a brominated sulfamine It produces an acid compound. Chlorinated sulfamic acid has high stability but low oxidizing power. On the other hand, the stability of brominated sulfamic acid is lower than that of chlorinated sulfamic acid, and the oxidizing power is higher than that of chlorinated sulfamic acid. As described above, the effects of various inorganic slime control agents are superior and inferior, and there is still a demand for inorganic slime control agents that can be stored for a long time and can exhibit excellent slime control effects.

  On the other hand, in cooling water systems, cold and hot water systems, etc. using copper-based metals, it is common to use an inorganic slime control agent in combination with an azole compound which is an anticorrosive for copper-based metals such as copper alloys. In addition, organic phosphoric acid compounds and various polymers are used to prevent corrosion and scale of iron-based metals. As described above, when the slime control agent, the anticorrosive agent, and the scale inhibitor are used in combination, if the chemical solution tank and the addition pump are installed for each medicine, there is a problem that the cost increases and the management takes time and effort.

  Also, for example, even if it is intended to supply an inorganic slime control agent and an azole compound to an aqueous system at an appropriate ratio, when the inorganic slime control agent is added in excess compared to the azole compound, the azole compound is There is a risk of decomposition and corrosion of the copper-based metal. In order to prevent such problems, it is desirable that the inorganic slime control agent and the azole compound are always supplied to the water system at a constant ratio, and the inorganic slime control agent and the azole compound should be unified. Is the most desirable.

  For example, in Patent Document 1, a single-agent bactericidal and algicidal composition having a pH of 13 or more and containing a chlorine-based oxidizing agent such as sodium hypochlorite, an azole-based compound, and sulfamic acid or a salt thereof It is presenting a thing. However, in the bactericidal and algicidal composition of Patent Document 1, the chlorine-based oxidizing agent is reacted with sulfamic acid to be stabilized as combined chlorine, so the stability of the composition is increased, but the oxidizing power of the slime control agent There was a problem that was significantly reduced.

  Further, in Patent Document 2, a water treatment agent 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 more. However, the compounding azole is decomposed except using liquid bromine as a bromine-based oxidizing agent, and there is a problem with stability.

  On the other hand, in the patent document 3, the applicant of the present invention is, as a water treatment agent composition for algae growth inhibition, which serves both scale inhibition and corrosion inhibition in a water system, (A) hypobromous acid and / or hypobromous acid A combined bromine compound obtained by the reaction of a salt and sulfamic acid and / or a sulfamate salt, and (B) (1) an unsaturated single monomer having no telogen and hydroxyl group selected from sulfite, water-soluble sulfite and amine thiol (2) an organic phosphinic acid compound obtained by the reaction of (2) hypophosphorous acid and / or a water-soluble hypophosphite with an unsaturated monomer having no hydroxyl group, (3) A water treatment agent in an aqueous system, comprising, as an active ingredient, at least one selected from organic phosphonic acid compounds having neither hydroxyl group nor amino group, and adjusting the pH of the composition to 13 or more Narubutsu has come, but this water treatment agent composition can be long-term storage of 30 days at 40 ° C., a further long-term storage performance is required.

  Thus, attempts to unify the inorganic slime control agent and the azole compound, and unification of the inorganic slime control agent and the anticorrosive agent and the scale inhibitor are still insufficient, and long-term storage is possible, which is excellent. There is a need for a one-component water treatment agent composition that can achieve slime control effect, anticorrosion effect, and scale prevention effect.

Patent No. 3832399 JP, 2015-44765, A Unexamined-Japanese-Patent No. 2017-25046

  The object of the present invention is an inorganic slime control agent which can be stored for a long time and can obtain an excellent slime control effect, and can be stored for a long time and can obtain an excellent slime control effect, an anticorrosion effect and a scale preventing effect. A single agent water treatment composition is provided.

As a result of intensive studies to solve the above-mentioned problems, the inventor of the present invention has been able to store for a long time by coexistence of a brominated sulfamic acid compound and a chlorinated sulfamic acid compound, and unexpectedly superior slime control It has been found that an effect, in particular a bactericidal and algicidal effect can be exhibited. Furthermore, the appropriate content molar ratio of brominated sulfamic acid compound and chlorinated sulfamic acid compound was found out.
In addition, a water treatment agent composition in which the decomposition of the azole compound is small even if the azole compound is further added to the bactericidal algicidal composition in which the brominated sulfamic acid compound and the chlorinated sulfamic acid compound coexist is found, and It has also been found that telomers and organic phosphoric acid compounds can be blended. The present inventors have completed the present invention based on the above findings.

  That is, the invention according to claim 1 is a microbicidal and algicidal composition containing (A) a brominated sulfamic acid compound and (B) a chlorinated sulfamic acid compound, and the pH of the composition is 13 or more. It is a microbicidal and algicidal composition characterized by the above-mentioned.

  The invention according to claim 2 is characterized in that the content molar ratio of the (A) brominated sulfamic acid compound and the (B) chlorinated sulfamic acid compound is (A) :( B) = 5: 5 to 1: 9. It is a microbicidal and algicidal composition of Claim 1 characterized by the above-mentioned.

  The invention according to claim 3 is a water treatment agent composition comprising the microbicidal and algicidal composition according to claim 1 or 2 and further comprising (1) an azole compound, wherein the pH of the composition is It is a water treatment agent composition characterized by being 13 or more.

  The invention according to claim 4 is the water treatment agent composition according to claim 3, which further comprises (2) a telomer and / or (3) an organic phosphoric acid compound.

  The invention according to claim 5 is a waste water system characterized by adding the microbicidal and algicidal composition according to claim 1 or 2 in water, and a method for bactericidal and algicidal process of process water system.

  The invention according to claim 6 is a water treatment method for a drainage system and a process water system characterized in that the water treatment agent composition according to claim 3 or 4 is added to water.

  By applying the microbicidal and algicidal composition and the water treating agent composition of the present invention, which can be stored for a long time, to various water systems, stable and effective slime and scale deposits and metal corrosion can be maintained throughout the year As a result, it is possible to suppress and reduce the amount of heat transfer pipe deposits in various water systems to prevent a decrease in heat transfer efficiency, which contributes to a great deal of energy saving. In addition, the number of times of plant operation downtime due to the failure can be reduced, and the period of downtime can be shortened. As a result, long-term operation is possible, productivity is improved, and the cost for operation suspension and maintenance is also possible. It can be reduced.

It is the schematic of the test apparatus used for the corrosion test of an Example, a scale prevention test, and a sterilization test.

  Embodiments of the present invention will be described below. The present embodiment is an example for implementing the present invention, and the present invention is not limited to the present embodiment.

  The brominated sulfamic acid compound used in the microbicidal and algicidal composition of the present invention is a decomposable and unstable hypobromous acid salt stabilized with sulfamic acid or sulfamic acid derivative and salts thereof, and similarly Chlorinated sulfamic acid compounds are those obtained by stabilizing hypochlorite with sulfamic acid or sulfamic acid derivatives and salts thereof.

  Brominated sulfamic acid compounds and chlorinated sulfamic acid compounds can be produced by known methods. Brominated sulfamic acid can be produced by reacting bromide and hypochlorite to form hypobromite, which is then reacted with sulfamate. For example, in Japanese Patent Publication No. 11-506139, mixing about 5 to 70% aqueous solution of an alkali or alkaline earth metal hypochlorite with a bromide ion source; a bromide ion source and hypochlorous acid Reacting the salt to form an aqueous solution of 0.5 to 70% by weight of an alkali or alkaline earth metal hypobromite; A process is disclosed comprising the steps of adding in an amount such that the molar ratio is between 0.5 and 7. Chlorinated sulfamic acid can also be produced by reacting hypochlorite with sulfamic acid. For example, in JP 2009-84163 A, when sulfamate is added to hypochlorite, N-monochlorosulfamate or N, N-dichlorosulfamate is formed, and the active chlorine component is stabilized. Being disclosed.

  Moreover, the hypobromous acid salt and hypochlorite which are used at this time can be manufactured by the following well-known methods. Hypobromous acid salts include, for example, a method of dissolving bromine in water, a method of electrolyzing an aqueous solution of hydrogen bromide or bromide, an oxidant such as bromide and chlorine, hypochlorite, persulfate, ozone, etc. It can be obtained by a method such as reaction. The hypobromous salt forms include alkali metal salts such as sodium, potassium and lithium, alkaline earth metal salts such as calcium and magnesium, zinc salts and the like, and the microbicidal and algicidal composition of the present invention and water treatment In the agent composition, since the pH of these compositions is 13 or more, alkali metal salts of sodium and potassium having high solubility even with strong alkali are preferable. In addition, hypochlorite can be obtained, for example, by a method in which chlorine is passed through an aqueous alkaline solution such as sodium hydroxide. The forms of hypochlorous salts include alkali metal salts such as sodium, potassium and lithium, alkaline earth metal salts such as calcium and magnesium, zinc salts and the like, and the microbicidal and algicidal composition of the present invention and the water treatment agent In the composition, since the pH of these compositions is 13 or more, alkali metal salts of sodium and potassium, which are strongly alkaline but have high solubility, are preferable.

  On the other hand, as another method for producing the brominated sulfamic acid compound of the present invention, the reaction between the formation of hypobromite and the sulfamic acid salt is performed by adding an oxidizing agent after mixing the bromide and sulfamic acid. There is a method of simultaneously carrying out to produce brominated sulfamic acid, for example, in Japanese Patent No. 4749544, providing a solution containing an alkali or alkaline earth metal bromide and a halogen stabilizer such as sulfamic acid, pH An oxidizing agent selected from ozone, peracetic acid, hydrogen peroxide and an oxidizing bromine compound is added to form a bound bromine compound by the reaction of hypobromous acid salt with sulfamate, by adjusting in steps 4-8. Methods are disclosed.

  The method further includes the step of adding bromine to a mixed solution containing water, an alkali hydroxide and sulfamic acid under an inert gas atmosphere to react, and the addition ratio of bromine is 25 with respect to the total amount of the water treatment agent composition. Japanese Patent Laid-Open No. 2014-101251 discloses a method for producing a bound bromine compound by the reaction of a hypobromous acid salt and a sulfamate salt which is not more than% by weight.

  The method for producing the brominated sulfamic acid compound used in the present invention is not limited to the method shown here, but in consideration of safety during production, influence on the environment, availability of raw materials, etc., bromide and It is preferable to use a method in which sulfamic acid or a sulfamic acid derivative, or a salt thereof is added after hypochlorous acid salt is reacted to form a hypobromous acid aqueous solution. The hypochlorite here is preferably an alkali metal salt of hypochlorous acid and the bromide is preferably an alkali metal of bromide or hydrobromic acid. The alkali metal is selected from the group consisting of sodium, potassium and lithium.

The method for producing the chlorinated sulfamic acid compound used in the present invention is not limited to the method shown here, but in view of safety during production, environmental impact, availability of raw materials, etc. Preferred is a method of adding sulfamic acid or sulfamic acid derivatives and salts thereof to chlorate. Here, hypochlorite is preferably an alkali metal salt of hypochlorous acid, and the alkali metal is selected from the group consisting of sodium, potassium and lithium.
The salt of brominated sulfamic acid and the salt of chlorinated sulfamic acid used in the present invention is sodium having high solubility even in strong alkali because the pH of the microbicidal and algicidal composition of the present invention and the water treatment agent composition is 13 or more. And alkali metal salts of potassium are preferred.

（式中、Ｒ_１、Ｒ_２は、それぞれ独立に水素原子、炭素数１〜８のアルキル基又は炭素数６〜１０のアリール基を表し、Ｘ_１は水素原子、１価の金属原子、アンモニウム基又は有機アンモニウム基を表す。）

（式中、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６は、それぞれ独立に水素原子、炭素数１〜８のアルキル基又は炭素数６〜１０のアリール基を表し、Ｘ_２は２価の金属原子を表す。） The sulfamic acid and sulfamic acid derivative which is a stabilizer used when manufacturing the brominated sulfamic acid compound and the chlorinated sulfamic acid compound used for this invention, and their salts have the following general formula (1) or general formula It is a compound shown by (2).

(Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and X ₁ represents a hydrogen atom, a monovalent metal atom, ammonium Represents a group or an organic ammonium group.)

(Wherein, R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and X ₂ is a divalent metal Represents an atom)

In the general formula (1), when both R ₁ and R ₂ are hydrogen atoms and X ₁ is a hydrogen atom, it is sulfamic acid (amidosulfuric acid). As an example where _{one of} R ₁ and R ₂ is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms, and X ₁ is a hydrogen atom, N-methylsulfamic acid, N-ethylsulfamic acid, N-propyl Sulfamic acid, N-isopropylsulfamic acid, N-butylsulfamic acid and the like can be mentioned. As an example in which both R ₁ and R ₂ are an alkyl group having 1 to 8 carbon atoms and X ₁ is a hydrogen atom, N, N-dimethylsulfamic acid, N, N-diethylsulfamic acid, N, N- Dipropylsulfamic acid, N, N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid, N-methyl-N-propylsulfamic acid and the like can be mentioned. In addition to hydrogen atoms, monovalent metal atoms can also be selected as X ₁ , and examples thereof include alkali metal salts such as sodium salts and potassium salts. In addition, X ₁ can also be selected from an ammonium group or an organic ammonium group, and examples of the organic ammonium group include a guazinino group.

Further, in the compound represented by the general formula (2), X ₂ is a divalent metal atom. In the general formula (2), R ₃ , R ₄ , R ₅ and R ₆ can be selected in the same manner as R ₁ and R _{2 in} the general formula (1), and X ₂ is an alkaline earth such as calcium, strontium or barium And metals such as manganese, copper, zinc, iron, cobalt and nickel.

  Two or more of sulfamic acid or sulfamic acid derivatives and salts thereof may be used alone as a stabilizer used in producing the brominated sulfamic acid compound and the chlorinated sulfamic acid compound used in the present invention. Although it may be used in combination, it is preferable to use sulfamic acid from the point of environmental load etc.

The preferred blending ratio of hypobromite and hypochlorite and sulfamic acid in the present invention converts hypobromite and hypochlorite into brominated sulfamate and chlorinated sulfamate. Although it is a sufficient amount, specifically, it is in the range of 0.8 to 3.0 moles of sulfamic acid with respect to 1 mole of the effective halogen amount (in terms of Cl ₂ ). If this molar ratio is less than 0.8, a sufficient amount of brominated sulfamic acid and chlorinated sulfamic acid may not be formed, and therefore, the microbe suppressing effect may be inferior, and if the molar ratio exceeds 3.0, bromination Sulfamic acid and sulfamic acid which does not contribute to the formation of chlorinated sulfamic acid will remain, which is a cost and a waste of resources.

  (A) Brominated sulfamic acid compound (hereinafter, sometimes referred to as component (A)) and (B) chlorinated sulfamic acid compound (hereinafter, component (B)) contained in the microbicidal and algicidal composition of the present invention ) May be produced as a mixed solution by a series of reactions, or may be separately manufactured and then mixed. When manufacturing as a mixed solution, the concentration and the molar ratio of the components (A) and (B) can be adjusted to obtain the bactericidal and algicidal composition of the present invention as it is, and when manufactured separately, The germicidal and algicidal composition of the present invention can be prepared by adjusting the mixing ratio of the component (A) and the component (B) and combining the concentration and the contained molar ratio. In this case, the order of mixing the component (A) and the component (B) and the method of mixing are not particularly limited.

  The microbicidal and algicidal composition of the present invention contains the (A) component and the (B) component, and the preferable content molar ratio thereof is (A) :( B) = 5: 5 to 1: 9. For example, when preparing the bactericidal and algicidal composition of (A) :( B) = 5: 5 containing a component (A) and a component (B) by a series of reactions as a liquid mixture and containing molar ratio (A): (B), first Bromide and hypochlorite are reacted at a ratio of 2 moles of hypochlorite to 1 mole of bromide, and the reaction product hypobromide and moles of unreacted hypochlorite are reacted. A mixed solution with a ratio of 5: 5 is obtained. A stabilization reaction is carried out by adding sulfamic acid corresponding to the total mole of hypobromite and hypochlorite in the mixed solution to this mixed solution to perform a stabilization reaction, and a brominated sulfamic acid compound (component (A)) and A bactericidal and algicidal composition of the present invention in which the chlorinated sulfamic acid compound (component (B)) is a mixed solution of (A) :( B) = 5: 5 is prepared. When the molar ratio of components exceeds (A) :( B) = 5: 5 and the component (A) is in excess of the component (B), the effective halogen tends to be reduced, and the product stability and slime control performance are improved. It may decrease.

  The microbicidal and algicidal composition of the present invention is a mixed solution of the (A) component and the (B) component, and the solvent is usually water. The water used here may be any of pure water, ion exchange water and softened water. In the microbicidal and algicidal composition of the present invention, the final pH of the composition is 13 or more for product stability. In order to adjust the pH of the composition to 13 or more, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide is added.

  The water treatment agent composition of the present invention has a final pH of 13 after the sterilizing and algicidal composition of the present invention further contains an azole compound which acts as an anticorrosive for copper-based metals such as copper and copper alloys. Prepared by the above. In order to adjust the pH of the composition to 13 or more, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide is added.

  Examples of the (1) azole compound used in the water treatment agent composition of the present invention include 1,2,3-benzotriazole, tolyltriazole, 1,2,4-triazole, 3-amino-1,2,4- Triazole, imidazole, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, etc. may be mentioned, and 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 preferable in terms of production cost and the like.

  The water treatment agent composition of the present invention contains the microbicidal and algicidal composition of the present invention and an azole compound, and can further contain (2) telomer and / or (3) organic phosphoric acid compound.

  The telomer used in the water treatment agent composition of the present invention is a polymer having a low degree of polymerization obtained by the presence of a certain substance called telogen in vinyl polymerization, and the telogen and a single unsaturated amount thereof. The polymerization reaction with the body (= vinyl monomer) is called telomerization or telomerization.

  Examples of telogen include sulfite, water soluble sulfite, amine thiol, mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, isopropyl alcohol, toluene, xylene and the like, and the telomers used in the water treatment agent composition of the present invention As telogen to be present in the polymerization reaction, sulfite, water-soluble sulfite and amine thiol are preferable.

  The water-soluble sulfite may be anything that dissolves in water to generate sulfite ion or hydrogen sulfite ion, and examples thereof include sodium sulfite, sodium bisulfite, disodium disulfite (sodium pyrosulfite sodium), sulfite and the like. It can be mentioned. What is industrially marketed as sodium bisulfite can also be used, but this is mainly composed of disodium disulfite.

  Aminethiol is a compound having one or more amino groups and one or more thiol groups in the molecule, and examples thereof include cysteine, aminoethanethiol, glutathione, N-acylcysteine, N-butylaminoethanethiol, N , N-diethylaminoethanethiol or salts thereof and the like.

  A telomer using sulfite or water-soluble sulfite as telogen can be produced by a known method, for example, a method in which an aqueous sodium persulfate solution is dropped into an aqueous solution containing sodium bisulfite and acrylic acid under nitrogen gas flow to promote polymerization ( JP-B-47-11487), a method in which an aqueous solution of maleic anhydride is adjusted to pH 2.5 to 6.5 and then bisulfite is added, and air is blown to promote polymerization (JP-A-63-236600) JP-A 11-315115), or the like, in which acrylic acid, an aqueous persulfate solution and an aqueous bisulfite solution are separately dropped separately in boiling water, for example, to promote polymerization (see JP-A-11-315115).

  Moreover, the telomer obtained by reacting with an unsaturated monomer having no hydroxyl group using an amine thiol as a telogen is, for example, a method described in Japanese Patent No. 4095691 and Japanese Patent Laid-Open No. 2008-224663. It can be prepared, specifically, one or more monoethylenically unsaturated monomers and an initiator as well as an amine thiol as a chain transfer agent in a reaction vessel filled with water and heated under aeration of an inert gas such as nitrogen. Can be manufactured by supplying each separately.

  Temporal stability of water treatment agent composition obtained by mixing telomer prepared with telogen selected from the group consisting of sulfite, water soluble sulfite and amine thiol with brominated sulfamic acid compound and chlorinated sulfamic acid compound The present invention is significantly superior to a water treatment agent composition obtained by mixing an addition polymer produced without using these telogens with a brominated sulfamic acid compound and a chlorinated sulfamic acid compound. The person found it.

  In addition, examples of unsaturated monomers that form telomers include ethylene, styrene, methyl methacrylate and the like, and as unsaturated monomers that form telomers used in the water treatment agent composition of the present invention, hydroxyls are mentioned. Unsaturated monomers having no group are preferred. Among the unsaturated monomers having no hydroxyl group, most preferably a monoethylenically unsaturated carboxylic acid alone or a monoethylenically unsaturated monomer having no other hydroxyl group copolymerizable with the monoethylenically unsaturated carboxylic acid. It is a combination with a saturated monomer. Here, the monoethylenically unsaturated carboxylic acid is preferably acrylic acid, maleic acid, maleic anhydride, methacrylic acid, crotonic acid, fumaric acid, itaconic acid or the like. Further, as an example of monoethylenically unsaturated monomer having no hydroxyl group copolymerizable with monoethylenically unsaturated carboxylic acid, 2- (meth) acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid , Sulfoalkyl (meth) acrylate esters, sulfoalkyl (meth) allyl ethers, monoethylenically unsaturated sulfonic acids such as (meth) allyl sulfonic acid and vinyl sulfonic acid, and water-soluble salts thereof, vinyl phosphonic acid and allyl phosphonic acid Monoethylenically unsaturated phosphonic acids such as acids and their water-soluble salts, (meth) acrylamide, N-alkyl substituted (meth) acrylamide, alkyl (meth) acrylate esters, alkyl (meth) allyl ethers and the like . As water-soluble salts of monoethylenically unsaturated carboxylic acids and monoethylenically unsaturated sulfonic acids, sodium salts and potassium salts are common. The ratio of monoethylenically unsaturated carboxylic acid in the unsaturated monomer is preferably 40 to 100% by weight, and if this ratio is less than 40% by weight, the formed telomer has a sufficient scale suppressing effect. May not be shown.

  A monoethylenically unsaturated carboxylic acid and a monoethylenically unsaturated single monomer having no other hydroxyl group copolymerizable with the monoethylenically unsaturated carboxylic acid, which forms a telomer, for use in the water treatment agent composition of the present invention More preferably, a combination of acrylic acid and / or methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, and a combination of acrylic acid and / or methacrylic acid and 2-acrylamido-2-methylpropane sulfone as a combination with a monomer A combination of acid and N-substituted (meth) acrylamide. Here, preferred examples of the N-substituted (meth) acrylamide include N, N'-dimethyl acrylamide, N-isopropyl acrylamide, acryloyl morpholine, N-tert-butyl acrylamide and the like. Moreover, the preferable copolymerization ratio in the combination mentioned as said more preferable example is 45-85 weight% of the total amount of acrylic acid and methacrylic acid, and 15-55 weight% of 2-acrylamido 2-methylpropane sulfonic acid And 0 to 30% by weight of N-substituted acrylamide.

  A preferred combination of telogen and unsaturated monomer as the telomer for use in the water treatment agent composition of the present invention is selected from the group consisting of sulfurous acid, water-soluble sulfite and amine thiol, and telogen and non-hydroxyl group free Saturated monomers, this combination of telomers is prepared by heating an aqueous solution containing telogen and unsaturated monomers in the presence of an inert gas under suitable initiators, oxygen, ultraviolet light, etc. be able to. The reaction mechanism is that, at the initiation stage of the reaction, telogen radicals are generated by the action of an initiator, ultraviolet light and the like, and then polymer radicals in which unsaturated monomers are bonded to telogen radicals are generated. Then, a radical addition reaction of a new unsaturated monomer to the polymer radical (growth reaction of telomer) or a chain transfer reaction (radical termination reaction of telomer) in which a radical is transferred from the polymer radical to telogen is generated. The telogen radical repeats the above reaction again. The telomer produced here is a compound in which one or more unsaturated monomers are added to a telogen residue at the telomer end. Since the higher the concentration ratio of telogen to unsaturated monomer, the smaller the number of unsaturated monomers added to telogen, telogen acts as a molecular weight regulator.

  The reaction of telomer using sodium sulfite as telogen and acrylic acid as unsaturated monomer having no hydroxyl group is shown by the following reaction formula (3), n acrylics having a sulfonic acid group at the end The acid becomes a polymerized telomer. In this reaction, the degree of polymerization of telomer can be changed by changing the reaction ratio of sodium sulfite to acrylic acid, for example, increasing the ratio of sodium sulfite lowers the molecular weight of telomer.

  In telogen selected from the group consisting of an unsaturated monomer having no hydroxyl group, which is a preferable combination, sulfite, water-soluble sulfite and amine thiol, which is a preferable combination as a telomer used in the water treatment agent composition of the present invention The reaction molar ratio is usually such that the ratio of telogen selected from the group consisting of sulfite, water-soluble sulfite and amine thiol to unsaturated monomer having no hydroxyl group is usually in the range of 0.01 to 0.1. However, the preferred reaction molar ratio is the amount necessary to obtain the optimum molecular weight of telomer for corrosion inhibition and scale inhibition, and the optimum molar ratio is the kind of unsaturated monomer having no hydroxyl group. It changes with For example, monomers having high radical reactivity such as acrylic acid, methacrylic acid, 2- (meth) acrylamido-2-methylpropane sulfonic acid, N-alkyl substituted (meth) acrylamide, alkyl (meth) acrylate esters, etc. require telogen Although the amount is relatively high, the amount of telogen required is relatively low for low radically reactive monomers such as maleic acid, fumaric acid, sulfoalkyl (meth) allyl ethers, (meth) allyl sulfonic acid and the like.

  As initiators used for producing telomers, compounds known as radical initiators can be used, for example, hydrogen peroxide, inorganic peroxides such as persulfates, di-tert-butyl peroxide, benzoyl peroxide, Organic peroxides such as tert-butyl peroxybenzoate, tert-butyl hydroperoxide, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [2- (2-imidazolin-2-yl) propane] and its dihydrochloride and disulfate, 2,2'-azobis [N- ( And water-soluble azo compounds such as 2-carboxyethyl) -2-methylpropionamidine] n.

  In addition, under appropriate polymerization initiators, oxygen, ultraviolet rays and the like, mercapto compounds such as mercaptoacetic acid, mercaptopropionic acid and mercaptoethanol, secondary alcohols such as isopropyl alcohol, and aromatic compounds such as toluene and xylene Etc. can also be used as telogen.

  The molecular weight of the telomer used in the water treatment agent composition of the present invention is preferably in the range of 500 to 40,000. When the molecular weight exceeds 40000, the improvement effect on the temporal stability of the (A) brominated sulfamic acid compound and (B) the chlorinated sulfamic acid compound to be added simultaneously decreases, and when the molecular weight is less than 500, the scale inhibiting effect becomes small. Both may be undesirable. The molecular weight can be measured, for example, by using polyethylene glycol of known molecular weight as a standard substance by gel permeation chromatography, and the molecular weight can be calculated using commercially available computer software for molecular weight calculation.

  The telomer obtained by the reaction using sulfuric acid and water-soluble sulfite as telogen and using acrylic acid and 2-acrylamido-2-methylpropane sulfonic acid as unsaturated monomers having no hydroxyl group is Acumer 2000 from Dow Chemical Co. Or commercially available from SNF under the tradenames Flosperse 3018 CS, 3018 CSA 50, 3024 CSA 50, 3037 CSA 50, 9018 CSA 50, 9037 CSA 50, and the like. A telomer obtained by a reaction using sulfuric acid or a water-soluble sulfite as telogen, and using acrylic acid, 2-acrylamido-2-methylpropane sulfonic acid and N-tert-butyl acrylamide as unsaturated monomers having no hydroxyl group Is commercially available from Dow Chemical under the tradename Acumer 3100, or from SNF under the tradename Flosperse 3225D.

  Moreover, the telomer obtained by the reaction using acrylic thiol and 2-acrylamido-2-methylpropane sulfonic acid as an unsaturated monomer which does not have an amine thiol as a telogen and does not have a hydroxyl group is a product of Optidose 2000 from Dow Chemical Co. It is obtained by the reaction using amine thiol as telogen and using acrylic acid, 2-acrylamido-2-methylpropane sulfonic acid and N-tert-butyl acrylamide as unsaturated monomers having no hydroxyl group. Telomers are commercially available from Dow Chemical under the trade name Optidose 3100.

  The (3) organic phosphoric acid compound used in the water treatment agent composition of the present invention is preferably an organic phosphinic acid compound and an organic phosphonic acid compound, both of which can be produced by known methods. The organic phosphinic acid compound can be obtained, for example, by adding an aqueous solution of an unsaturated monomer dropwise to an aqueous solution of hypophosphite in the presence of a polymerization initiator and polymerizing (JP-A-55-11092). JP-A-63-114986 and JP-B-6-47713). The organic phosphonic acid compound is polymerized, for example, by dropping an aqueous solution of monoethylenically unsaturated carboxylic acid into an aqueous solution of a phosphite in the presence of a polymerization initiator (see JP-A-4-334392), Alternatively, it can be produced by a method of polymerizing dialkyl hydrogen phosphite and a monoethylenically unsaturated carboxylic acid and then hydrolyzing with an acid (see JP-A-2-134389).

  Among the organic phosphoric acid compounds, the present inventor is an organic phosphinic acid compound obtained by the reaction of hypophosphorous acid and / or a water-soluble hypophosphite with an unsaturated monomer having no hydroxyl group, and Organic phosphonic acid compounds having no hydroxyl group and no amino group are brominated sulfamic acid compounds and chlorination in comparison with organic phosphinic acids having other hydroxyl groups and organic phosphonic acid compounds having hydroxyl or amino groups It has been found that the temporal stability of the water treatment agent composition obtained by mixing with the sulfamic acid compound is extremely excellent.

  The unsaturated monomer used in the preparation of the organic phosphoric acid compound used in the water treatment agent composition of the present invention is preferably an unsaturated monomer having no hydroxyl group, more preferably monoethylenically unsaturated It is a combination of a carboxylic acid alone or a monoethylenically unsaturated monomer copolymerizable with a monoethylenically unsaturated carboxylic acid. Here, as the monoethylenically unsaturated carboxylic acid and the copolymerizable monoethylenically unsaturated monomer, the same unsaturated monomer having no hydroxyl group used in the above-mentioned (2) telomer is used be able to.

  Preferred chemical structures of the organic phosphoric acid compounds used in the water treatment agent composition of the present invention are organic phosphinic acid compounds and organic phosphonic acid compounds. The organic phosphinic acid is preferably an organic phosphinic acid compound obtained by the reaction of hypophosphorous acid and / or a water-soluble hypophosphite with an unsaturated monomer having no hydroxyl group, for example, hypophosphorous acid. The compound obtained by the reaction of phosphoric acid and / or water-soluble hypophosphite with acrylic acid is bis-poly (2-carboxyethyl) phosphinic acid represented by the following general formula (4) or an alkali metal salt thereof, bis- A compound which is poly (1-carboxyethyl) phosphinic acid or an alkali metal salt thereof and is obtained by the reaction of hypophosphorous acid and / or water-soluble hypophosphite with maleic acid is represented by the following general formula (5) Bis-poly (1,2-dicarboxyethyl) phosphinic acid or its alkali metal salt.

（ここで、Ｍ_１、Ｍ_２、Ｍ_３はそれぞれ独立に水素原子又はアルカリ金属原子を表し、ｍ_１、ｎ_１はそれぞれ独立に１〜３０の整数である。）

(Here, M ₁ , M ₂ and M ₃ each independently represent a hydrogen atom or an alkali metal atom, and m ₁ and n ₁ each independently represent an integer of 1 to 30.)

（ここで、Ｍ_４、Ｍ_５、Ｍ_６、Ｍ_７、Ｍ_８はそれぞれ独立に水素原子又はアルカリ金属原子を表し、ｍ_２、ｎ_２はそれぞれ独立に１〜３０の整数である。）

(Here, M ₄ , M ₅ , M ₆ , M ₇ and M ₈ each independently represent a hydrogen atom or an alkali metal atom, and m ₂ and n ₂ each independently represent an integer of 1 to 30.)

  In addition to the above-mentioned reaction products of hypophosphorous acid and / or water-soluble hypophosphite and acrylic acid, and reactions of hypophosphorous acid and / or water-soluble hypophosphite and maleic acid, As an organic phosphinic acid compound obtained by the reaction of hypophosphorous acid and / or water-soluble hypophosphite with an unsaturated monomer having no hydroxyl group, poly (2-carboxyethyl) (1,2) can be used. -Dicarboxyethyl) phosphinic acid or alkali metal salt thereof, bis-poly (2-carboxyethyl) (1,2-dicarboxyethyl) phosphinic acid or alkali metal salt thereof, poly (1-carboxyethyl) (1,2 -Dicarboxyethyl) phosphinic acid or its alkali metal salt, bis-poly (1-carboxyethyl) (1,2-dicarboxyethyl) phosphinic acid or its alkali metal Of hypophosphorous acid and / or water-soluble hypophosphite and acrylic acid and maleic acid, or hypophosphorous acid and / or water-soluble hypophosphite and acrylic acid and 2-acrylamido-2 -A reaction product of methyl propane sulfonic acid and the like can be mentioned. In addition, an organic phosphinic acid compound obtained by the reaction of hypophosphorous acid and / or water-soluble hypophosphite with acrylic acid is hypophosphorous acid and / or water-soluble under the trade name of Belclene 500 or Belsperse 164 from BWA. The reaction products of the hypophosphite with acrylic acid and 2-acrylamido-2-methylpropane sulfonic acid are commercially available from BWA under the trade name Belclene 400, respectively.

  The molecular weight of the organic phosphinic acid compound used in the water treatment agent composition of the present invention is preferably in the range of 200 to 20,000. When the molecular weight exceeds 20000, the effective halogen content and the azole residual ratio decrease, and when the molecular weight is less than 200, the scale preventing effect is reduced, and both may be undesirable.

  The organic phosphonic acid compound as the organic phosphoric acid compound used in the water treatment agent composition of the present invention is preferably an organic phosphonic acid compound having no hydroxyl group and no amino group, and as a specific example, JP-B-53-12913. And 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphono-3-methylbutane-1,2,4-tricarboxylic acid, 2-phosphonopentane described in JP-B-54-38086. 1,2,4-tricarboxylic acid, 2-phosphonobutane-1,2,3,4-tetracarboxylic acid, or 1-phosphonopropane-1,2,3 described in JP-B-54-9593 Tricarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, 1,1-diphosphonopropane-2,3-dicarboxylic acid, 2-phosphonobuta 2,3,4-tricarboxylic acid, 2,2-phosphonomethylglycine propanoic-3,4-dicarboxylic acid. Here, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphono-3-methylbutane-1,2,4-tricarboxylic acid, 2-phosphonopentane-1,2,4-tricarboxylic acid, 2- Phosphonobutane-1,2,3,4-tetracarboxylic acid reacts phosphonosuccinic acid tetraalkyl ester with acrylic acid methyl ester, crotonic acid ethyl ester, methacrylic acid methyl ester and maleic acid dimethyl ester in the presence of a basic catalyst Can be prepared by hydrolysis of the ester obtained. 2-phosphonobutane-1,2,4-tricarboxylic acid is commercially available from BAYER under the trade name Bayhibit-AM, or from BWA under the trade name Belclene 650.

  Also, 1-phosphonopropane-1,2,3-tricarboxylic acid can be produced by reacting ester obtained by reacting maleic acid ester with phosphonoacetic acid ester in the presence of alcoholate, and hydrolyzing ester obtained, 1-phosphonobutane- 2,3,4-Tricarboxylic acid can be prepared by reacting dimethylphosphorous acid with 1-butene-2,3,4-tricarboxylic acid ester in the presence of sodium alcoholate and hydrolyzing the ester obtained 1,1-Diphosphonopropane-2,3-dicarboxylic acid is prepared by reacting methylenediphosphonic acid alkyl ester and maleic acid alkyl ester in the presence of sodium alcoholate and hydrolyzing the ester obtained 2-phosphonobutane-2,3,4-tricarboxylic acid is an alcoholate It can be prepared by hydrolyzing the ester obtained by reacting α-diethylphosphonopropionic acid methyl ester with maleic acid diethyl ester in the presence of 2,2-diphosphonopropane-3,4-dicarboxylic acid It can be prepared by respectively reacting the ester obtained by reacting maleic acid ester with ethane-1,1-diphosphonic acid ester in the presence of sodium alcoholate.

（ここで、Ｒ_７、Ｒ_８はそれぞれ独立に水素又はＣＯＯＭ_１１であるが、Ｒ_７、Ｒ_８が同時に水素となることはなく、Ｒ_９、Ｒ_１０はそれぞれ独立に水素、ＣＯＯＭ_１１又はメチル基であり、Ｍ_９、Ｍ_１０、Ｍ_１１はそれぞれ独立に水素又はアルカリ金属原子であり、ｍ_３は１〜４の整数である。） Another example of the organic phosphonic acid compound having no hydroxyl group and amino group which is preferable as the organic phosphoric acid compound used in the water treatment agent composition of the present invention is an organic phosphonic acid compound represented by the following general formula (6) .

(Here, R ₇ and R ₈ are each independently hydrogen or COOM ₁₁ but R ₇ and R ₈ are not simultaneously hydrogen, and R ₉ and R ₁₀ are each independently hydrogen, COOM ₁₁ or methyl And M ₉ , M ₁₀ and M ₁₁ each independently represent a hydrogen or an alkali metal atom, and m ₃ is an integer of 1 to 4.)

  The organic phosphonic acid compound of the above general formula (6) is, for example, a phosphorous acid, a phosphite or a phosphite and an unsaturated monomer having no hydroxyl group, while being aerated with an inert gas and a radical It can be produced by heating and reacting in the presence of an initiator. Here, as the phosphite ester, for example, dialkyl hydrogen phosphites such as dimethyl hydrogen phosphite and diethyl hydrogen phosphite are used. The unsaturated monomer having no hydroxyl group used here is preferably a monoethylenically unsaturated carboxylic acid alone or a monoethylenically unsaturated monomer copolymerizable with the monoethylenically unsaturated carboxylic acid. It is a combination. Here, as the monoethylenically unsaturated carboxylic acid and the copolymerizable monoethylenically unsaturated monomer, the same unsaturated monomers used in the above-mentioned (2) telomer can be used.

  Specific examples of the organic phosphonic acid compound represented by the above general formula (6) include poly (2-carboxyethyl) phosphonic acid obtained by the reaction of phosphorous acid and / or phosphite and acrylic acid or alkali thereof Metal salt, poly (1-carboxyethyl) phosphonic acid or alkali metal salt thereof, phosphorous acid and / or poly (1,2-dicarboxyethyl) phosphonic acid obtained by reaction of phosphite and maleic acid or maleic acid Poly (2-carboxyethyl) (1,2-dicarboxyethyl) phosphonic acid or its alkali which is obtained by the reaction of phosphorous acid and / or phosphorous acid with acrylic acid and maleic acid, which is an alkali metal salt. Metal salt, poly (1-carboxyethyl) (1,2-dicarboxyethyl) phosphonic acid or alkali metal salt thereof And the like. The most preferable example of the organic phosphonic acid compound represented by the above general formula (6) is an organic phosphonic acid compound obtained by the reaction of a phosphite and maleic acid, which is, for example, BriCorr288 from SOLVAY. It is marketed under the trade name.

  A preferred combination example of three components of (1) azole compound (2) telomer (3) organic phosphoric acid compound in the water treatment agent composition of the present invention is (1) azole compound: 1,2,3-benzotriazole, ((1) 2) Telomer: telomer obtained by the reaction of telogen selected from the group consisting of sulfite, water soluble sulfite and amine thiol with acrylic acid and 2-acrylamido-2-methylpropane sulfonic acid and (3) organophosphate compound : A combination of organic phosphonic acid compounds obtained by the reaction of phosphite and maleic acid, or (1) an azole compound: 1,2,3-benzotriazole, (2) telomer: sulfurous acid, water soluble sulfite and amine Telogen and acrylic acid selected from the group consisting of thiols and 2-acrylamido-2-methylpropanesul Telomer obtained by reaction of a phosphate and (3) an organic phosphoric acid compound: which is a combination of an organic phosphinic acid compound obtained by the reaction of hypophosphorous acid with acrylic acid.

  The total active ingredient content of the three components of (1) azole compound (2) telomer (3) organic phosphoric acid compound in the water treatment agent composition of the present invention is an effective total of (A) component and (B) component The amount is preferably in the range of 1/2 to 10 times (weight conversion), more preferably 1/10 to 5 times (weight conversion) with respect to the component blending amount. If it is less than 1/20 times the amount (weight conversion) with respect to the total amount of the active ingredient blending amount of the components (A) and (B), it may be insufficient for stabilization of the bound bromine compound, and 10 times amount ( If it is more than weight conversion, it may be economically disadvantageous because it does not contribute to further stabilization.

  The water treatment agent composition of the present invention usually uses water as a solvent. The water used here may be any of pure water, ion exchange water and softened water. In addition, the final pH of the water treatment agent composition is 13 or more for product stability. If the pH of the composition is less than 13, the temporal stabilization effect of the water treatment agent composition of the present invention may not be sufficiently exhibited. In order to set the pH of the water treatment agent composition of the present invention to 13 or more, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide is added.

  In the water treatment agent composition of the present invention, in addition to the component (A), the component (B) and the components (1) to (3), other types of chemicals are blended in the range where the effect of the present invention is not impaired. can do. For example, inorganic corrosion inhibitors such as orthophosphates, polymerized phosphates, molybdates, tungstates, zincates and aluminates, various nonionic surfactants, and anionic surfactants And detergents such as cationic surfactants and amphoteric surfactants.

The microbicidal and algicidal composition and the water treatment agent composition of the present invention are various systems such as cooling water system, cold and warm water system, dust collection water system, paper pulp process water system, iron making process water system, metal processing process water system etc. Applicable to etc. When the bactericidal and algicidal composition and the water treatment agent composition of the present invention are applied to such aqueous water, the pH of the water to be treated is not particularly limited, but is usually in the range of pH 5 to 10. The addition amount, addition method, and the like of the microbicidal and algicidal composition of the present invention and the water treatment agent composition differ depending on the condition of the water system to be treated; In the agent composition, 0.1 to 100 mg / L of the component (A) and the component (B) as effective halogen (in terms of Cl ₂ ) is continuously or intermittently added, and in the water treatment agent composition, the component (A) and 0.1 to 100 mg / L of the component (B) as effective halogen (in terms of Cl ₂ ) and 0.1 to 100 mg / L of the components (1) to (3) as a total concentration (in terms of activity) continuously or intermittently Add. For continuous addition, a chemical pump is usually used. Moreover, the biofilm and the inorganic deposit which exist in a to-be-processed water system can also be exfoliated and dispersed by collectively adding the bactericidal and algicidal composition and the water treatment agent composition of the present invention at high concentration. In addition, the addition of the microbicidal and algicidal composition and the water treatment agent composition of the present invention suppresses the growth of fungi and algae in the water system to be treated, thereby suppressing the formation of biofilm and the adhesion of inorganic deposits. be able to.

  The effective halogen content in the microbicidal and algicidal composition of the present invention and the water treatment agent composition and the residual halogen concentration in the water to be treated are determined according to the diethyl-p-phenylenediammonium (DPD) -ammonium iron (II) sulfate titration method, DPD. It can measure by well-known methods (refer JISK 0101-1991), such as a colorimetric method and an iodine titration method.

  As a means for measuring the concentration of the (1) azole compound in the water treatment agent composition of the present invention, known methods can be used, and for example, it can be measured by liquid chromatography.

  The microbicidal and algicidal composition and the water treating agent composition of the present invention kill various aerobic bacteria, anaerobic bacteria, facultative anaerobic bacteria, fungi, microorganisms such as mold and yeast, shellfish, protozoa, algae and the like Not only that, it is also possible to exfoliate and remove microorganisms and aquatic organisms already adhering to the system. It is also effective against Legionella pneumophila.

  The type of scale to be subjected to scale adhesion suppression of the water treatment agent composition of the present invention is not particularly limited, but carbonate scales such as calcium carbonate and magnesium carbonate; sulfate scales such as calcium sulfate, barium sulfate and strontium sulfate; Phosphate scales such as calcium phosphate, zinc phosphate, iron phosphate and aluminum phosphate; silicate scales such as magnesium silicate, calcium silicate, aluminum silicate, iron silicate and zinc silicate; amorphous silica scale Magnesium hydroxide; aluminum hydroxide; iron oxide, iron hydroxide and the like.

  The present invention will be specifically described below, but the present invention is not limited to these examples.

1. Azole compound used in the test [Azole compound No. 1H]
BT-120 (trade name, manufactured by Johoku Chemical Co., Ltd.): 1,2,3-benzotriazole [azole compound No. 1 2H]
VERZONE TTA (trade name, manufactured by Daiwa Kasei Co., Ltd.): Tolyltriazole azole compound No. 1 1H to no. The outline of 2H is shown in Table 1.

2. Telomers used in the test Telomer No. shown below. 1A to telomer No. 1 13A corresponds to a telomer obtained by the reaction of a telogen selected from the group consisting of sulfite, water-soluble sulfite and amine thiol with an unsaturated monomer having no hydroxyl group, 1B to telomer No. 1 3B is another telomer.

[Terror No. 1A]
34.5 g of water was added to a 500 mL four-neck separable flask equipped with a stirrer, a thermometer, a nitrogen gas vent, and a glass reflux tube, and nitrogen gas aeration and stirring were started, and heated to 90 ° C. Next, while maintaining the liquid temperature at 90 ° C., the monomer solution, the initiator solution and the telogen solution were separately dropped continuously for 3 hours using three tube pumps. Here, a monomer solution was prepared by stirring and mixing 30 g of 80% acrylic acid, 16 g of 2-acrylamido-2-methylpropane sulfonic acid (abbreviation: AMPS) and 6.5 g of 48% sodium hydroxide. The initiator solution was prepared by dissolving 1 g of sodium persulfate in 3 g of water. The telogen solution was prepared by dissolving 1 g of sodium pyrosulfite in 8 g of water. That is, the compounding weight ratio of acrylic acid and AMPS is 60:40, and the reaction molar ratio (t / m) of telogen (t) consisting of sodium pyrosulfite to monomer (m) consisting of acrylic acid and AMPS is 0.013. . After completion of the dropwise addition of each solution, the mixture was heated at 90 ° C. for an additional hour, water was added to make the total amount 100 g, and the telomer no. I got 1A. The total content of acrylic acid and AMPS in the telomer was 40%, the conversion of each monomer was 99% or more, and the average molecular weight of the telomer was about 40,000.

[Terror No. 2A]
For Telomer No. 1 except that the blending amount of sodium pyrosulfite was changed and the reaction molar ratio (t / m) was 0.026. In the same manner as in 1A, telomer no. I got 2A. The total content of acrylic acid and AMPS in the telomer was 40%, the conversion of each monomer was 99% or more, and the average molecular weight of the telomer was about 20000.

[Terror No. 3A]
As to telomer No. 1 except that the blending amount of sodium pyrosulfite was changed and the reaction molar ratio (t / m) was set to 0.051. In the same manner as in 1A, telomer no. I got 3A. The total content of acrylic acid and AMPS in the telomer was 40%, the conversion of each monomer was 99% or more, and the average molecular weight of the telomer was about 10,000.

[Terror No. 4A]
The blending amount of sodium pyrosulfite is changed to set the reaction molar ratio (t / m) to 0.036, and at the same time, the blending amount of 80% acrylic acid in the monomer solution is changed to 40 g, 2-acrylamido-2-methylpropane sulfonic acid (= Telomer No. 1 except that the amount of AMPS was changed to 8 g. In the same manner as in 1A, telomer no. I got 4A. The blending weight ratio of acrylic acid to AMPS was 80:20, and the total content of acrylic acid and AMPS in the telomer was 40%, and the conversion of each monomer was 99% or more.

[Terror No. 5A]
As to telomer No. 1 except that the blending amount of sodium pyrosulfite was changed and the reaction molar ratio (t / m) was set to 0.051. In the same manner as in 4A, telomer No. I got 5A. The total content of acrylic acid and AMPS in the telomer was 40%, and the conversion of each monomer was 99% or more.

[Terror No. 6A]
A monomer solution prepared by stirring and dissolving 30 g of 80% acrylic acid and 16 g of sodium styrene sulfonate (abbreviation: SS) in 20 g of water is used, and 4 g of sodium pyrosulfite is dissolved in 8 g of water as a telogen solution Telomer no. In the same manner as in 1A, telomer no. I got 6A. That is, the compounding weight ratio of acrylic acid and SS is 60:40, the reaction molar ratio (t / m) of telogen (t) consisting of sodium pyrosulfite to the monomer (m) consisting of acrylic acid and SS is 0.051, The total content of acrylic acid and SS in telomer is 40%.

[Terror No. 7A]
A monomer solution prepared by stirring and mixing 24 g of methacrylic acid, 16 g of 2-acrylamido-2-methylpropane sulfonic acid (= AMPS) and 6.5 g of 48% sodium hydroxide was used as a telogen solution. For Telomer No. 1 except using 3.3 g of sodium sulfite dissolved in 8 g of water. In the same manner as in 1A, telomer no. I got 7A. That is, the compounding weight ratio of methacrylic acid to AMPS is 60:40, and the reaction molar ratio (t / m) of telogen (t) consisting of sodium pyrosulfite to the monomer (m) consisting of methacrylic acid and AMPS is 0.049, The total content of methacrylic acid and AMPS in the telomer is 40%.

[Terror No. 8A]
As telogen No. 1 except that 2.6 g of cysteine was added instead of sodium pyrosulfite as telogen. In the same manner as in 1A, telomer no. I got 8A. That is, the reaction molar ratio (t / m) of telogen (t) consisting of cysteine to monomer (m) consisting of acrylic acid and AMPS is 0.052.

[Terror No. 9A]
Prepared as a monomer solution by stirring and dissolving 30 g of 80% acrylic acid, 8 g of 2-acrylamido-2-methylpropane sulfonic acid (= AMPS) and 8 g of N-tert-butyl acrylamide (abbreviation: tBuAAm) in 20 g of water Telomer No. 1 was used except that 4 g of sodium pyrosulfite sodium was used as a telogen solution. In the same manner as in 1A, telomer no. I got 9A. That is, the blending weight ratio of acrylic acid to AMPS to tBuAAm is 60:20:20, and the reaction molar ratio (t / m) of telogen (t) consisting of sodium pyrosulfite to monomer (m) consisting of acrylic acid and AMPS and tBuAAm (t / m) Is 0.048, and the total content of acrylic acid, AMPS and tBuAAm in the telomer is 40%.

[Terror No. 10A]
As a monomer solution, 50 g of 80% acrylic acid was used, and telomer No. 1 was used except that 6.3 g of sodium pyrosulfite sodium was used as a telogen solution. In the same manner as in 1A, telomer no. I got 10A. That is, the reaction molar ratio (t / m) of telogen (t) consisting of sodium pyrosulfite to monomer (m) consisting solely of acrylic acid and acrylic acid alone is 0.060, the content of acrylic acid in the telomer Is 40%.

[Terror No. 11A]
Optidose 2000 (trade name, manufactured by Dow Chemical Co.)
A telomer with a molecular weight of 4500 wherein the telogen is an amine thiol and the unsaturated monomers are acrylic acid and AMPS.

[Terror No. 12A]
Optidose 3100 (trade name, manufactured by Dow Chemical Co.)
A telomer with a molecular weight of 4500 wherein the telogen is an amine thiol and the unsaturated monomers are acrylic acid, AMPS and tBuAAm.

[Terror No. 13A]
Flosperse 3024 CSA 50 (trade name, manufactured by SNF)
Telomer with a molecular weight of 5500, in which the telogen is sulfite and the unsaturated monomers are acrylic acid and AMPS. The blending weight ratio of acrylic acid to AMPS is 75:25.

[Terror No. 1B]
Telomer No. 34.5 g of isopropyl alcohol was added to the same four-necked flask as in the production of 1A, nitrogen gas bubbling and stirring were started, and heating was maintained at 70 ° C. The monomer solution similar to 1A and the initiator solution are separately added dropwise separately over 3 hours, and after completion of the addition of each solution, the mixture is heated at 70 ° C. for an additional 1 hour, isopropyl alcohol is distilled off, and water is added. In addition, the total amount is 100 g and telomer No. I got 1B. Here, the telogen in the telomer is isopropyl alcohol, the compounding weight ratio of acrylic acid and AMPS as monomers is 60:40, and the reaction of telogen (t) consisting of isopropyl alcohol to the monomer (m) consisting of acrylic acid and AMPS The molar ratio (t / m) is 1.4. The total content of acrylic acid and AMPS in the telomer was 40%, and the conversion of each monomer was 99% or more.

[Terror No. 2B]
For Telomer No. 1 except that 1.5 g of β-mercaptopropionic acid was added instead of sodium pyrosulfite as telogen. In the same manner as in 1A, telomer no. I got 2B. Here, the telogen in the telomer is β-mercaptopropionic acid, and the reaction molar ratio (t / m) of the telogen (t) consisting of β-mercaptopropionic acid to the monomer (m) consisting of acrylic acid and AMPS is 0. It is 034.

[Terror No. 3B]
Telomer No. 10 parts by weight of maleic anhydride and 50 parts by weight of o-xylene were placed in the same four-necked flask as in the production of 1A, and the temperature was raised to 140 ° C., and the mixture was stirred and dissolved. An initiator solution in which 0.3 parts by weight of di-tert-butyl peroxide was dissolved in 10 parts by weight of xylene was added dropwise over 15 minutes while maintaining 140 ° C. under nitrogen gas flow. After completion of the dropwise addition, the temperature was maintained at 140 ° C. for 90 minutes under nitrogen gas flow, and it was confirmed that the polymer was precipitated at the bottom of the flask, and the supernatant was removed by decantation. Thereto, 100 ml of water was added to obtain a clear polymer solution. The polymer solution was distilled off with a rotary evaporator under the conditions of 50 ° C. under reduced pressure to distill off xylene, and telomer No. 1 was removed. 55 parts by weight of a 30% by weight aqueous solution of maleic acid telomer which is 3B was obtained. The average molecular weight of the telomer was 500. Here, the telogen in the telomer is o-xylene, and the reaction molar ratio (t / m) of the telogen (t) consisting of o-xylene to the monomer (m) consisting of maleic acid is 5.5.

Telomer No. 1A-No. 13A, telomer No. 1B-No. An outline is shown in Table 2 for 3B.

3. Organic phosphinic acid compounds used in the test Organic phosphinic acid compound No. 1 shown below. 1D to organic phosphinic acid compound No. 1 6D corresponds to an organic phosphinic acid compound obtained by the reaction of hypophosphorous acid and / or a water-soluble hypophosphite with an unsaturated monomer not having a hydroxyl group; 1E is another organic phosphinic acid compound.

[Organic phosphinic acid compound No. 1D]
Telomer No. 35 g of water and 10.7 g of maleic anhydride were added to the same four-necked flask as in the production of 1A, 20 g of an aqueous sodium hydroxide solution (48% by weight) was gradually added to this, and sodium hypophosphite · monohydrate 11.6 g of object was added. This solution is heated to 80 ° C. under nitrogen gas flow, and an initiator solution in which 1.6 g of 35% hydrogen peroxide is dissolved in 5.5 g of water and 15.7 g of 80% acrylic acid are separately separated. It dripped over time. After completion of the dropwise addition, the reaction product was further heated at 80 ° C. for 2.5 hours and cooled, and then water was additionally charged to a total of 100 g to obtain organic phosphinic acid compound No. 1 of an aqueous reaction product solution. I got 1D. The active content of the organic phosphinic acid compound was 34.8% by weight, pH 5 and the conversion of organic phosphinic acid calculated by the measurement method described later was 95%, and the average molecular weight was 400.

[Organic phosphinic acid compound No. 2D]
98 g of maleic anhydride was dissolved in 138 g of water, to which was gradually added 81.7 g of an aqueous sodium hydroxide solution (48% by weight), and 30.8 g of sodium hypophosphite monohydrate was further added. The solution was heated to 100 ° C. under nitrogen gas flow, and 15.5 g of hydrogen peroxide solution (35% by weight) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction product was further heated at 100 ° C. for 2 hours to obtain organic phosphinic acid compound No. 1 I got 2D. The organic phosphinic acid compound contains poly-bis (1,2-dicarboxyethyl) phosphinic acid as a main component, and the active ingredient content is 35.4% by weight, pH 4.4, organic phosphine calculated by the measurement method described later The acid conversion was 90% and the average molecular weight was 420.

[Organic phosphinic acid compound No. 3D]
Telomer No. 34.5 g of water was added to the same four-necked flask as in the production of 1A, nitrogen gas bubbling and stirring were started, and the mixture was heated to 90 ° C. Then, while maintaining the liquid temperature at 90 ° C., the monomer solution, the initiator solution, and the hypophosphite solution were separately dropped continuously over 3 hours using three tube pumps. Here, a monomer solution was prepared by stirring and mixing 30 g of 80% acrylic acid, 16 g of 2-acrylamido-2-methylpropane sulfonic acid (= AMPS) and 6.5 g of 48% sodium hydroxide. The initiator solution was prepared by dissolving 1 g of sodium persulfate in 3 g of water. The hypophosphite solution was prepared by dissolving 3 g of sodium hypophosphite monohydrate in 8 g of water. After completion of dropwise addition of each solution, the mixture is heated at 90 ° C. for an additional hour, water is added to make the total amount 100 g, and organic phosphinic acid compound No. 1 is added. I got 3D. The active component content of the compounded monomer of the organic phosphinic acid compound was 40%, the conversion ratio of organic phosphinic acid calculated by the measurement method described later was 97%, the conversion of each monomer was 99% or more, and the average molecular weight was 1,000.

[Organic phosphinic acid compound No. 4D]
Belclene 500 (trade name, manufactured by BWA): An organic phosphinic acid compound having an average molecular weight of 400 by the reaction of hypophosphorous acid and acrylic acid.

[Organic phosphinic acid compound No. 5D]
Belsperse 164 (trade name, manufactured by BWA): An organic phosphinic acid compound having an average molecular weight of 1,600 by the reaction of hypophosphorous acid and acrylic acid.

[Organic phosphinic acid compound No. 6D]
Belclene 400 (trade name, manufactured by BWA): An organic phosphinic acid compound having a molecular weight of 4000 obtained by the reaction of hypophosphorous acid, acrylic acid and AMPS (weight ratio 73: 27).

[Organic phosphinic acid compound No. 1E]
In place of 2-acrylamido-2-methylpropanesulfonic acid (= AMPS), 44.5 parts by weight of a 40% by weight aqueous solution of sodium 3-allyloxy-2-hydroxy-1-propanesulfonic acid (= AHPS) was used. Organic phosphinic acid No. 1 In the same manner as in 3D, organic phosphinic acid compound No. 1 I got 1E. Here, 1E is an organic phosphinic acid compound having a hydroxyl group.

4. Organic phosphonic acid compounds used in the test Organic phosphonic acid compound No. 1 shown below. 1F to organic phosphonic acid compound No. 1 5F corresponds to the organic phosphonic acid compound which does not have a hydroxyl group and an amino group, and 5F corresponds to organic phosphonic acid compound No. 1 1G to organic phosphonic acid compound No. 1 3G is another organic phosphonic acid compound.

[Organic phosphonic acid compound No. 1F]
To 50 g of water, 17.9 g of maleic anhydride and 9.4 g of phosphorous acid were added, and 23.8 g of sodium hydroxide was gradually added while cooling. An initiator solution in which 4 g of sodium persulfate was dissolved in 7 g of water was added dropwise over 4 hours and 40 minutes while refluxing this solution at 105 ° C. under nitrogen flow. After completion of the dropwise addition, the solution temperature is further maintained for 45 minutes, followed by cooling and adding water to make the total amount 100 g. I got 1F. The organic phosphonic acid compound contains phosphonosuccinic acid and poly (1,2-dicarboxyethyl) phosphonic acid sodium salt having a polymerization degree of 2 as main components, and the molar ratio of maleic acid to phosphorous acid is 1.6, and the compounding monomer The active ingredient content was 30.6%, and the conversion of phosphorous acid to organic phosphonic acid calculated by the measurement method described later was 90%.

[Organic phosphonic acid compound No. 2F]
To 50 g of water, 15.7 g of maleic anhydride and 9.4 g of phosphorous acid were added, and 22 g of sodium hydroxide was gradually added while cooling. While maintaining the temperature of this solution at 95 ° C. under nitrogen flow, an initiator solution in which 4 g of sodium persulfate was dissolved in 7 g of water was added dropwise over 7 hours and 30 minutes. After completion of the dropwise addition, the heating is maintained for further 45 minutes, followed by cooling and water is added to make the total amount 100 g. I got 2F. The organic phosphonic acid compound contains phosphonosuccinic acid and poly (1,2-dicarboxyethyl) phosphonic acid sodium salt having a polymerization degree of 2 as main components, and the molar ratio of maleic acid to phosphorous acid is 1.4, compounded monomer The active ingredient content was 29.4%, and the conversion of phosphorous acid to organic phosphonic acid calculated by the measurement method described later was 90%.

[Organic phosphonic acid compound No. 3F]
27.6 g of diethyl hydrogen phosphite were heated to 120 ° C. under nitrogen bubbling. After 7.3 g of di-tert-butyl peroxide and 60 g of ethyl acrylate were simultaneously added dropwise over 4 hours, the liquid temperature was maintained at 120 ° C. for 2 hours. 100 g of water was added, and after distilling off the organic component under reduced pressure, 200 g of hydrochloric acid (18 wt%) was added and hydrolyzed under reflux for 16 hours. After distilling off water under reduced pressure, 45 g of polymeric phosphonic acid compound No. 1 I got 3F. The organic phosphonic acid compound contains poly (2-carboxyethyl) phosphonic acid as a main component.

[Organic phosphonic acid compound No. 4F]
BriCorr 288 (trade name, manufactured by SOLVAY): An organic phosphonic acid compound by the reaction of phosphorous acid and acrylic acid.

[Organic phosphonic acid compound No. 5F]
Kylest PH-430 (trade name, manufactured by Kylest Co., Ltd.): 2-phosphonobutane-1,2,4-tricarboxylic acid (abbreviation: PBTC).

[Organic phosphonic acid compound No. 1G]
Kylest PH-210 (trade name, manufactured by Kylest Co., Ltd.): 1-hydroxyethylidene-1,1-diphosphonic acid (abbreviation: HEDP). It is an organic phosphonic acid compound having a hydroxyl group.

[Organic phosphonic acid compound No. 2G]
Belcor 575 (trade name, manufactured by BWA): 2-hydroxyphosphonoacetic acid. It is an organic phosphonic acid compound having a hydroxyl group.

[Organic phosphonic acid compound No. 3G]
Kylest PH-320 (trade name, manufactured by Kylest Co., Ltd.): nitrilotris (methylene phosphonic acid) (abbreviation: NTMP), alias: aminotrimethylphosphonic acid (abbr .: ATMP). It is an organic phosphonic acid compound having an amino group.

  Organic phosphinic acid compound No. 1 1D to no. 6D and No. 1E, and organic phosphonic acid compound No. 1 1F to No. 5F and No. 1G to No. The outline of 3G is shown in Table 3.

[Method for measuring organic phosphinic acid conversion and organic phosphonic acid conversion]
[Organic phosphinic acid conversion rate]
10 μL of triethylamine, 200 μL of 3000 mg / L aqueous solution of mercuric chloride and 1 mL of ethanol are added to 1 mL of a 1% solution of the reaction product and heated at 110 ° C. for 20 minutes to convert unreacted hypophosphorous acid into phosphate ester The absorbance was measured by a hydrolyzable phosphorus determination method (JIS K 0101: 1998) by molybdenum blue (ascorbic acid reduction) spectrophotometry. The content of unreacted hypophosphorous acid in the reaction product solution was determined from a calibration curve of hypophosphorous acid prepared in advance. In addition, the content of total phosphoric acid in the reaction product solution is determined by the total phosphorus determination method (JIS K 0101: 1998) by molybdenum blue (ascorbic acid reduction) spectrophotometry, and the organic phosphinic acid conversion of hypophosphorous acid is calculated by the following equation. The rate was calculated.
J = (Jt-Jn) / Jt x 100
Here, J: conversion of hypophosphorous acid to organic phosphinic acid (%)
Jn: Content of unreacted hypophosphorous acid in reaction product (%)
Jt: Total phosphoric acid content in reaction product (%)

[Organic phosphonic acid conversion rate]
10 μL of triethylamine, 200 μL of 3000 mg / L aqueous solution of mercuric chloride and 1 mL of ethanol are added to 1 mL of a 1% solution of the reaction product and heated at 110 ° C. for 20 minutes to convert unreacted phosphorous acid into phosphate ester, Absorbance was measured by a hydrolyzable phosphorus determination method (JIS K 0101: 1998) by molybdenum blue (ascorbic acid reduction) spectrophotometry. The content of unreacted phosphorous acid in the reaction product solution was determined from a calibration curve of phosphorous acid prepared in advance. In addition, the content of total phosphoric acid in the reaction product solution is determined by the total phosphorus determination method (JIS K 0101: 1998) by molybdenum blue (ascorbic acid reduction) spectrophotometry, and the conversion of phosphorous acid to organic phosphonic acid by the following formula Was calculated.
J = (Jt-Jn) / Jt x 100
Where J: conversion of phosphorous acid to organic phosphonic acid (%)
Jn: Content of unreacted phosphorous acid in reaction product (%)
Jt: Total phosphoric acid content in reaction product (%)

5. Preparation of a microbicidal and algicidal composition used in the test [a microbicidal and algicidal composition 1]
An aqueous solution of 0.4 g of sodium bromide dissolved in 7.3 g of water is added to 25.4 g of an aqueous solution of sodium hypochlorite containing 12% of available chlorine (in terms of Cl ₂ ) for 10 minutes at room temperature (20 ° C.) The mixture was stirred to prepare a mixed solution of hypobromous acid and hypochlorous acid. Next, an aqueous solution of sodium sulfamate prepared by adding 8.6 g of water to 8.3 g of sulfamic acid and adding 13 g of 48% sodium hydroxide while cooling is added to the prepared mixed solution of hypobromous acid and hypochlorous acid After 48% sodium hydroxide was added so that the pH would be 13 or more, water was added to make the total amount 100 g, and stirring was carried out at room temperature (20 ° C.) for 10 minutes to prepare germicidal and algicidal composition 1. This microbicidal and algicidal composition 1 is a mixed solution of the (A) component and the (B) component prepared by a series of reactions, and the molar ratio of the components is (A) component: (B) component = 1: 9 It is.

[Fungicidal and algicidal composition 2 to 5]
According to the composition described in Table 4, the bactericidal and algicidal composition 2 to bactericidal and algicidal composition 5 were prepared in the same manner as the bactericidal and algicidal composition 1.

[Fungicidal and algicidal composition 6]
An aqueous solution of 2.1 g of sodium bromide dissolved in 5.3 g of water is added to 14.8 g of an aqueous solution of sodium hypochlorite containing 12% of available chlorine (in terms of Cl ₂ ) for 10 minutes at room temperature (20 ° C.) The solution was stirred to prepare a hypobromous acid solution. Then, 4.3 g of water was added to 4.1 g of sulfamic acid, and 6.5 g of 48% sodium hydroxide was added while cooling to add an aqueous solution of sodium sulfamate to the prepared hypobromous acid solution to obtain a room temperature (20 It stirred for 10 minutes at ° C, and the brominated sulfamic acid solution was prepared. Next, 5.6 g of water was added to 4.1 g of sulfamic acid, and 6.5 g of 48% sodium hydroxide was added while cooling and stirred at room temperature (20 ° C.) for 10 minutes to prepare an aqueous sodium sulfamate solution. The prepared aqueous solution of sodium sulfamate is added to 14.8 g of aqueous solution of sodium hypochlorite containing 12% of available chlorine (in terms of Cl ₂ ), and stirred for 10 minutes at room temperature (20 ° C.) to obtain a chlorinated sulfamic acid solution Obtained. The prepared brominated sulfamic acid solution and chlorinated sulfamic acid solution are mixed, 48% sodium hydroxide is added so that the pH is 13 or more, water is added to make the total amount 100 g, at room temperature (20 ° C.) for 10 minutes The mixture was stirred to prepare a microbicidal and algicidal composition 6. The microbicidal and algicidal composition 6 is a solution prepared by separately preparing the components (A) and (B) and mixing them, and the molar ratio of the components is (A) component: (B) component = 5: 5 It is.

[Fungicidal and algicidal composition 7]
An aqueous solution of 5.2 g of sodium bromide dissolved in 7.3 g of water is added to 30 g of an aqueous solution of sodium hypochlorite containing 12% of available chlorine (in terms of Cl ₂ ) and stirred at room temperature (20 ° C.) for 10 minutes An aqueous solution of hypobromous acid was prepared. Next, 8.6 g of water is added to 8.3 g of sulfamic acid, and 8.6 g of 48% sodium hydroxide is added while cooling to add an aqueous solution of sodium sulfamate prepared to the prepared aqueous solution of hypobromous acid to have a pH of 13 or more After 48% sodium hydroxide was added to the mixture, water was added to adjust the total amount to 100 g, and the mixture was stirred at room temperature (20 ° C.) for 10 minutes to prepare germicidal and algicidal composition 7 of component (A) alone.

[Fungicidal and algicidal composition 8]
Hypochlorous acid containing 12% of available chlorine (in terms of Cl ₂ ) in an aqueous solution of sodium sulfamate prepared by adding 8.8 g of water to 8.3 g of sulfamic acid and adding 12.9 g of 48% sodium hydroxide while cooling After adding 30 g of sodium aqueous solution and adding 48% sodium hydroxide so that pH is 13 or more, water is added to make the total amount 100 g and stirred for 10 minutes at room temperature (20 ° C.), only component (B) A microbicidal and algicidal composition 8 was prepared.

6. Preparation of Water Treatment Agent Composition Used for Testing [Water Treatment Agent Composition 1]
After adding 5 g of water and 5 g of 48% sodium hydroxide to 1 g of 1,2,3-benzotriazole (= azole compound No. 1H) and stirring at room temperature (20 ° C.) for 10 minutes, the prepared microbicidal and algicidal composition is prepared Add 80 g of 2 and add 48% sodium hydroxide so that the pH is 13 or more, add water and make the total amount 100 g, stir at room temperature (20 ° C) for 10 minutes, and add water treatment agent composition 1 Prepared.

[Water treatment agent composition 2 to 51]
According to the composition described in Tables 6-10, it prepared by the same method as water treatment agent composition 1, and obtained water treatment agent composition 2-51.

7. Test Method Stability test, corrosion test, scale inhibition test, bactericidal test and algal growth inhibition test were carried out with respect to the microbicidal and algicidal composition and the water treating agent composition.

[Temporal stability test]
Place the bactericidal and algicidal composition or water treatment composition shown in Tables 4 to 10 in a light-shielded constant temperature bath at 40 ° C., and immediately after preparation, after 30 days from preparation, and after 60 days from preparation The content was measured, and with respect to the water treatment agent composition containing an azole compound, the azole residual rate after 60 days from the preparation was measured to evaluate the stability over time. The results are shown in Tables 4 and 6-9.

The effective halogen content and the azole residual ratio used for evaluation were measured by the following method.
[Effective halogen content]
(1) 1.0 g of N, N-diethyl-p-phenylenediamine sulfate, 1.0 g of disodium ethylenediaminetetraacetic acid dihydrate and 36.4 g of monosodium dihydrogen phosphate and monohydrogen phosphate Mix 61.6 g of disodium in a mortar to make a DPD diluted powder.
(2) 1 to 2 g of a microbicidal and algicidal composition or a water treatment composition is weighed and this is designated as A (g). Ion-exchanged water is added to this, and the total volume is adjusted to 100 mL to prepare a solution of a microbicidal and algicidal composition or a water treatment composition.
(3) Add 0.5 g of DPD diluted powder to a 200 mL tall beaker.
(4) 100 mL of ion-exchanged water and 1 mL of a solution of the microbicidal and algicidal composition or water treatment composition are added and stirred to dissolve DPD diluted powder.
(5) Add 1 g of potassium iodide and dissolve it, and let it stand for 2 minutes to make it color red.
(6) Immediately titrate with 2.82 mmol / L ferrous ammonium sulfate solution. The end point is the point where the red color becomes colorless. The titer at this time is B (mL).
(7) Determine the effective halogen content by the following equation.
Effective halogen content (% Cl ₂ ) = B / A
Here, the effective halogen content is the sum of free chlorine, free bromine, combined chlorine, and combined bromine.
[Azole residual rate]
The residual ratio of the azole compound of the water treatment agent composition shown in Tables 6 to 9 is the residual concentration after 60 days with respect to the concentration of the azole compound after 0 days (immediately after preparation) after storage under light shielding at 40 ° C. for 60 days. It showed by a ratio and calculated | required by the following formula. The measurement of the azole compound was performed under the following conditions using a Tosoh liquid chromatograph (8020 series).
Column: TSKSEL ODS-80TS (made by Tosoh Corporation)
Eluent: Acetonitrile 20% solution Eluent flow rate: 1.0 mL / min
Detector: Multi-wavelength detector Measuring wavelength: 275 nm
Azole residual ratio (%) = B / A x 100
B = concentration of azole compound 60 mg after preparation (mg / L)
Azole compound concentration (mg / L) after A = 0 days (immediately after preparation)

[Corrosion test, scale prevention test and sterilization test]
The method of the corrosion test and the scale prevention test was based on the on-site test method of JIS G 0593-2002 "corrosion and scale prevention evaluation test method of water treatment agent". Also, the bactericidal test was evaluated by the average value of the number of general bacteria in the circulating water in the corrosion test and the scale inhibition test.
It was based on the on-site test method of JIS G0593-2002 "corrosion of water treatment agent and scale prevention evaluation test method". The outline of the test apparatus is shown in FIG.
As a heat transfer tube, a stainless steel pipe SUS304 (JIS G3448) having an outer diameter of 12.7 mm and a length of 510 mm, a carbon steel pipe STKM11A (JIS G3445) and an aluminum brass pipe C6871 (JIS H3100) were used.
The water volume of the entire system including the water tank 2 and the piping was 62 L, and the water temperature of the water tank 2 was controlled by the water temperature control device 9 so as to be 35 ° C. The heat flux of the heat exchanger 7 is controlled by the circulation pump 3 while being controlled by the flow rate adjustment valve 5 so that the flow rate is 210 L / h corresponding to the linear flow velocity of 0.3 m / s in the test heat transfer pipe evaluation unit. Is 35 kW / m ² . The cooling tower 1 used was an induced draft countercurrent contact type having a cooling capacity of 1.8 cooling tons. The temperature difference between circulating water at the inlet and outlet of the cooling tower was 15 ° C., and the amount of evaporated water was 4.1 L / h.

The average water quality of make-up water 12 is pH 7, electric conductivity: 18 mS / m, Ca hardness: 43 mg-CaCO ₃ / L, Mg hardness: 18 mg-CaCO ₃ / L, M alkalinity: 42 mg-CaCO ₃ / L, chloride The ion content was 13 mg / L, the sulfate ion was 18 mg / L, and the silica was 12 mg / L.
Supplement water is filled in the water tank 2 as initial treatment, and 300 mg / L of the microbicidal and algicidal composition shown in Table 5 or 400 mg / L of the water treatment composition shown in Table 10 and sodium hexametaphosphate (average condensation degree 40 Was added at 12.5 mg / L) and the circulation pump 3 was operated and then circulated at normal temperature for 48 hours. (2) Component telomer No. After adding 40 mg / L of 3A as an active ingredient, start the heat load of the heat exchanger 7 and start blowdown from the time of reaching the specified concentration so that the Ca hardness in circulating water becomes 270 mg-CaCO ₃ / L The conductivity was controlled automatically. Specifically, the conductivity of the circulating water is continuously measured by the conductivity measuring cell 4, and the concentration degree set using the conductivity controller 11 based on the input signal of the conductivity is measured. The blowdown pump 10 was controlled to have a corresponding electrical conductivity. In conjunction with the blow-down pump 10, the water treatment agent injection device 13 is operated at the same time, and the bactericidal and algicidal composition shown in Table 5 is added at a dose of 200 mg / hour from the treatment agent tank not shown in FIG. The water treatment agent composition shown in Table 10 was added to the water tank 2 so as to be L, or so that the addition amount was 250 mg / L. The test period was 30 days. The average water quality of the circulating water during the test period pH 8.8, Ca hardness 270mg-CaCO ₃ / L, M alkalinity 280mg-CaCO ₃ / L, the enrichment was 6.3 times.
After completion of the test, the test heat transfer tube was removed, and the scale deposition rate in the stainless steel tube and the corrosion rate in the carbon steel tube and the aluminum brass tube were measured according to the method of JIS G0593-2002. Moreover, the number of general bacteria in circulating water was measured according to the method of JIS K 0102. In addition, when evaluating only a sterilization test, all the heat transfer tubes used stainless steel pipes.

[Alga growth inhibition test]
The algicidal effect of the microbicidal and algicidal composition and the water treatment agent composition was evaluated by the algal growth inhibition test. The test method of the algal growth inhibition test is as follows.
The algae collected from the cooling tower was ground with a mortar, placed in an Erlenmeyer flask containing MC medium, put in a silicon stopper, and allowed to stand for several weeks on a window exposed to sunlight to prepare a culture solution of algae.
[Method of preparing MC medium]
In ion-exchanged water, 1.25 g of potassium nitrate, 1.25 g of magnesium sulfate heptahydrate, and 1.25 g of potassium dihydrogenphosphate were dissolved, 1 mL of Fe metal mixture and 1 mL of A5 metal mixture were added to make up to 1 L. Here, the Fe metal mixed solution was prepared by dissolving 1 g of ferrous sulfate heptahydrate in ion exchange water and measuring to 500 mL, and then adding 2 drops of concentrated sulfuric acid. The A5 metal mixture contains 2.86 g of boric acid, 2.50 g of manganese sulfate heptahydrate, 0.222 g of zinc sulfate heptahydrate, 0.079 g of copper sulfate pentahydrate, sodium molybdate dihydrate 0. It was prepared by dissolving 025 g in ion exchange water and measuring to 1 L.
80 mg / L of the microbicidal and algicidal composition shown in Table 5 is added to the MC medium adjusted to pH 8.3 in another flask, or 100 mg of the water treatment composition shown in Table 10 is added 100 mL of the test solution to which 1 L was added was added. Each of the flasks was inoculated with 1 mL of the culture solution, sealed with silicon, and allowed to stand outdoors for 14 days in a sunny outdoor environment.
Fourteen days later, the chlorophyll a concentration in the test solution was measured in accordance with JIS K 0400-080-10: 2000 "Measurement of water quality-biochemical parameters-spectrophotometric determination of chlorophyll a concentration". That is, no. 6 Filter after filtration with filter paper, dry the filter paper that has captured algae, put the filter paper in a stoppered bottle containing 20 mL of ethanol, heat at 75 ° C for 5 minutes, and leave it in a cool dark place for 24 hours to Chlorophyll a was extracted. Absorbance A665 at 665 nm and absorbance A750 at 750 nm of the extract were measured using ethanol as a control using a 10 mm colorimetric cell. After adding 0.03 mL of 4 N hydrochloric acid to 10 mL of another extract and leaving it to stand for 15 minutes, the absorbance Aa665 at 665 nm and the absorbance Aa750 at 750 nm are similarly measured.
The concentrations (μg / L) of chlorophyll a (ρc) and pheophytin (ρp) in the extract were calculated from the following formula.
c c = (A-Aa) x 29.6
ρ p = Aa × 20.8
here,
A = A ₆₆₅ -A ₇₅₀
Aa = Aa ₆₆₅ -Aa ₇₅₀
The algal growth inhibition rate was calculated by the following equation based on the measured concentrations of chlorophyll a and pheophytin.
Algae growth inhibition rate _{(%) = (Z 0 -Z} ) / Z 0 × 100
Z: Total concentration of chlorophyll a and pheophytin when drug is added Z ₀ : Total concentration of chlorophyll a and pheophytin when drug is not added

8. Test results (1) Stability over time of microbicidal and algicidal composition (Examples 1 to 6 and Comparative Examples 1 and 2)
The temporal stability test of the microbicidal and algicidal composition was conducted. Table 4 shows the results of the formulation and test.

From the results of Comparative Examples 1 and 2 shown in Table 4, the expected effective halogen content according to the combination of the (A) component and the (B) component is (2.1 + 2.3) / 2 = 2. 2% and likewise after 60 days it is 0.85%.
However, in the microbicidal and algicidal composition of the present invention containing both the (A) component and the (B) component shown in Examples 1 to 6, the effective halogen content after 30 days and 60 days is expected. In addition, the effective halogen content of the bactericidal and algicidal composition (comparative examples 1 and 2) of the component (A) alone and the component (B) alone is also greatly exceeded. The remarkable synergistic effect of the microbicidal and algicidal composition of the present invention containing both the component and the component (B) was clearly shown.
Further, among the bactericidal and algicidal composition of the present invention, the effective halogen content value of the composition having a molar ratio of 1: 9 to 5: 5 of the component (A) and the component (B) is high, and It has been shown that the content molar ratio of the component A) to the component (B) is particularly preferable.
On the other hand, although the microbicidal and algicidal compositions of Example 3 and Example 6 have the same content molar ratio of 5: 5, the composition 3 of Example 3 includes the components (A) and (B) in series. The composition 6 of Example 6 is prepared by separately preparing the components (A) and (B) and mixing them. From the results of Table 4, it is shown that there is no difference in the temporal stability due to the preparation method in the bactericidal and algicidal composition of the present invention, since there is no difference in the temporal stability of the two.

(2) The bactericidal and algicidal effect of the bactericidal and algicidal composition (Examples 7 to 12 and Comparative Examples 3 and 4)
The bactericidal test and the algal growth inhibition test were implemented using the microbicidal and algicidal agent compositions 1 to 8 which passed the 60-day stability test. Table 5 shows the results of the formulation and test.

  From the results in Table 5, it was shown that the bactericidal effect and the algal growth inhibitory effect of the microbicidal and algicidal composition are correlated with the effective halogen content value after 60 days shown in Table 4. Therefore, the remarkable synergetic effect by including both the component (A) and the component (B) in the bactericidal and algicidal composition revealed in the temporal stability is a bactericidal effect and an algal growth inhibitory effect (= kill Algal effect).

(3) Stability over time of the water treatment agent composition containing an azole compound (Examples 13 and 14 and Comparative Examples 5 to 8)
The temporal stability test of the water treatment agent compositions 1 and 2 in which an azole compound was further added to the microbicidal and algicidal composition 2 was carried out. Table 6 shows the results of the formulation and test.

  The temporal stability of the water treatment agent compositions 1 and 2 was evaluated at two points, the effective halogen content and the azole residual rate after 60 days. The azole compound used was 1H or 2H. From the results in Table 6, it became clear that the temporal stability of the example is superior to that of the comparative example, regardless of whether the compounded azole compound is 1H or 2H. That is, in the water treatment agent composition containing the azole compound, by combining the component (A) and the component (B) together, the azole compound is more than the case of the component (A) alone or the component (B) alone. A marked synergetic effect was shown to suppress degradation and increase the residual rate.

(4) Stability over time of the water treatment agent composition containing an azole compound and telomer (Examples 15 to 30 and Comparative Examples 9 and 10)
The temporal stability test of the water treatment agent compositions 7 to 22 in which telomers were further added to the water treatment agent composition 1 obtained by adding the azole compound 1H to the microbicidal and algicidal composition 2 was carried out. Table 7 shows the results of the formulation and test. As a control, Example 13 of the water treatment agent composition 1 in which the azole compound 1H was blended in the microbicidal and algicidal composition 2 and the telomer was not blended was described.

According to the results in Table 7, the effective halogens of the water treatment agent compositions 7 to 22 (Examples 15 to 30) containing telomers as compared with the water treatment agent composition 1 (Example 13) not containing telomers The content value was maintained high, and the azole residual rate after 60 days was also high, and it was clearly shown that the stability with time of the water treatment agent composition is improved by incorporating the telomer.
Among them, the results of the water treatment agent compositions 7 to 19 (Examples 15 to 27) in which telomers 1A to 13A are blended are the water treatment agent compositions 20 to 22 (Examples 28 to 25) in which telomers 1B to 3B are incorporated. It is superior to the result of 30), and among telomers, telomer which is a telogen selected from the group consisting of sulfite, water-soluble sulfite and amine thiol and an unsaturated monomer having no hydroxyl group is blended. Was shown to be particularly preferred.
Moreover, the water treatment agent composition 23 (comparative example 9) which mix | blended telomer 1A further with the water treatment agent composition 3 which mix | blended the azole compound 1H with (A) component was shown in Table 6 about the result of water treatment As compared with the result of the agent composition 3 (comparative example 5), the effective halogen content value and the azole residual rate were almost the same, and no improvement in temporal stability due to telomer blending was observed. Similarly, the results of water treatment agent composition 24 (comparative example 10) in which telomer 1A was further incorporated in water treatment agent composition 5 in which azole compound 1H was incorporated in component (B), the water shown in Table 6 As compared with the result of the treatment agent composition 5 (comparative example 7), the effective halogen content value and the azole residual rate were almost the same, and no improvement in temporal stability due to telomer blending was observed.
From this result, the temporal stability improvement effect by blending telomer with the water treatment agent composition is the effect obtained by including both the (A) component and the (B) component in the water treatment agent composition. It became clear that there was.

(5) Stability over time of the water treatment agent composition containing an azole compound and an organic phosphoric acid compound (Examples 31 to 45 and Comparative Examples 11 to 14)
The temporal stability test of the water treatment agent compositions 25 to 39 in which the organic phosphoric acid compound was further added to the water treatment agent composition 1 where the azole compound 1H was added to the bactericidal and algicidal composition 2 was conducted. Table 8 shows the results of the formulation and test. Among the organic phosphoric acid compounds, 1D to 6D and 1E are organic phosphinic acid compounds, and 1F to 5F and 1G to 3G are organic phosphonic acid compounds. In addition, as a control, Example 13 of the water treatment agent composition 1 which mix | blended the azole compound 1H with the microbicidal and algicidal composition 2, and did not mix | blend an organic phosphoric acid compound was described.

  According to the results in Table 8, water treatment agent compositions 25 to 39 (Example 31) containing an organic phosphoric acid compound as compared to the water treatment agent composition 1 (Example 13) not containing an organic phosphoric acid compound The effective halogen content value of ~ 45) is maintained high, and the azole residual rate after 60 days is also high, and it is clearly shown that the temporal stability of the water treatment agent composition is improved by blending the organic phosphoric acid compound. The

  Among the organic phosphinic acid compounds, organic phosphinic acid compounds 1D to 6D obtained by the reaction of hypophosphorous acid and / or a water-soluble hypophosphite and an unsaturated monomer having no hydroxyl group are blended. The result of the water treatment agent composition 25 to 30 (Examples 31 to 36) is superior to the result of the water treatment agent composition 31 (Example 37) in which the other organic phosphinic acid compound 1E is blended. Among organic phosphonic acid compounds, the results of water treatment agent compositions 32 to 36 (Examples 38 to 42) containing organic phosphonic acid compounds 1F to 5F having no hydroxyl group and no amino group. However, it is superior to the results of water treatment agent compositions 37 to 39 (Examples 43 to 45) in which 1G to 3G which are other organic phosphonic acid compounds are blended. From this, among the organic phosphinic acid compounds, organic phosphinic acid compounds obtained by the reaction of hypophosphorous acid and / or water-soluble hypophosphite and an unsaturated monomer having no hydroxyl group are blended. In particular, it has been shown that among the organic phosphonic acid compounds, an organic phosphonic acid compound having no hydroxyl group and no amino group is particularly preferable.

In addition, results of water treatment agent compositions 40 and 42 (comparative examples 11 and 13) in which organic phosphoric acid compounds 1D and 1F are further added to water treatment agent composition 3 in which azole compound 1H is added to component (A) Compared with the result of water treatment agent composition 3 (comparative example 5) shown in Table 6, there is no big difference in the effective halogen content value and the azole residual rate, and the improvement of the temporal stability by the organic phosphoric acid compound formulation is recognized It was not done. Similarly, results of water treatment agent compositions 41 and 43 (comparative examples 12 and 14) in which organic phosphoric acid compounds 1D and 1F are further added to the water treatment agent composition 5 in which the azole compound 1H is blended with the component (B) There is no significant difference in the effective halogen content value and the azole residual ratio as compared with the results of the water treatment agent composition 5 (comparative example 7) shown in Table 6, and the improvement of the temporal stability by the organic phosphoric acid compound formulation is I was not able to admit.
From this result, the improvement effect on the temporal stability by blending the organic phosphoric acid compound into the water treatment agent composition is obtained by including both the (A) component and the (B) component in the water treatment agent composition. Was found to be

(6) Stability over time of the water treatment agent composition containing an azole compound, telomer and organic phosphoric acid compound (Examples 46 and 47 and Comparative Examples 15 to 18)
A temporal stability test was conducted on water treatment agent compositions 46 and 47 in which a telomer and an organic phosphoric acid compound were further added to the water treatment agent composition 1 in which the azole compound 1H was added to the microbicidal and algicidal composition 2. Table 9 describes the results of the formulation and test. The organic phosphoric acid compound 4D is an organic phosphinic acid compound, and the organic phosphoric acid compound 4F is an organic phosphonic acid compound. As a control, Example 13 of the water treatment agent composition 1 in which the azole compound 1H was blended in the microbicidal and algicidal composition 2 and the telomer and the organic phosphoric acid compound were not blended was described.

  According to the results in Table 9, water treatment agent compositions 44 and 45 containing telomer and organic phosphoric acid compound as compared to water treatment agent composition 1 (Example 13) not containing telomer and organic phosphoric acid compound The effective halogen content value of (Examples 46 and 47) is maintained high, and the azole residual rate after 60 days is also high, and the temporal stability of the water treatment agent composition is improved by blending the telomer and the organic phosphoric acid compound. It was clearly stated that it would improve.

Further, results of water treatment agent compositions 46 and 47 (comparative examples 15 and 16) in which telomer and organic phosphoric acid compound are further added to water treatment agent composition 3 in which azole compound 1H is added to component (A), Compared with the result of water treatment agent composition 3 (comparative example 5) shown in Table 6, there is no big difference in the effective halogen content value and the azole residual rate, and the improvement of the temporal stability by telomer and organic phosphoric acid compound combination is I was not able to admit. Similarly, results of water treatment agent compositions 48 and 49 (comparative examples 17 and 18) in which telomer and organic phosphoric acid compound are further added to water treatment agent composition 5 in which azole compound 1H is compounded to component (B) are shown. Compared with the result of water treatment agent composition 5 (comparative example 7) shown in Table 6, the effective halogen content value and the azole residual rate are almost the same, and the temporal stability is improved by the combination of telomer and organic phosphoric acid compound. Was not recognized.
From this result, the temporal stability improvement effect by blending the telomer and the organic phosphoric acid compound into the water treatment agent composition is that both the (A) component and the (B) component are contained in the water treatment agent composition. It became clear that it was the effect obtained by

(7) Bactericidal and algicidal effect, anticorrosive effect and scale preventing effect of water treatment agent composition (Examples 48 to 50 and Comparative Examples 19 to 24)
The water treatment agent compositions 1, 9 and 45 subjected to the 60-day stability test were subjected to the sterilization test, the algal growth inhibition test, the corrosion test and the scale inhibition test. The water treatment agent composition 1 is a composition obtained by adding the azole compound 1H to the microbicidal and algicidal composition 2 containing the (A) component and the (B) component, and the water treatment agent composition 9 is the water treatment agent composition The water treatment composition 45 is a combination of the water treatment composition 1 with the telomer and the organic phosphoric acid compound. Further, the water treatment agent composition 3 is a composition obtained by adding the azole compound 1H to the microbicidal and algicidal composition 7 containing only the component (A), and the water treatment agent composition 50 is added to the water treatment agent composition 3 Further, telomer is added, and the water treatment composition 47 is a combination of the water treatment composition 3 with telomer and an organic phosphate compound. Further, the water treatment agent composition 5 is a composition obtained by adding the azole compound 1H to the microbicidal and algicidal composition 8 containing only the (B) component, and the water treatment agent composition 51 is added to the water treatment agent composition 5 Further, telomer is added, and the water treatment composition 49 is a combination of the water treatment composition 5 with telomer and an organic phosphate compound.
In addition, the water treatment agent composition 3, 50, 47, 5, 51, 49 all tested the composition which passed through the 60-day stability test. Table 10 describes the results of the formulation and test.

  From the results of the examples and comparative examples in Table 10, even if the water treatment agent composition subjected to the 60-day stability test is applied, all of the bactericidal and algicidal effects, the anticorrosion effects and the scale preventing effects are all of the present invention. It was shown that the effect of the water treatment composition was maintained high. That is, by comparing the formulations of the water treatment agent compositions of the example and the comparative example, the remarkable synergistic effect due to the inclusion of both the (A) component and the (B) component in the water treatment agent composition The effect and the algal growth inhibitory effect (= algicidal effect), the anticorrosion effect and the scale prevention effect are also specified.

  From the results in Tables 4 to 10, the microbicidal and algicidal composition and the water treatment agent composition of the present invention can be stored for a long time because they have high stability over time, and can maintain high bactericidal and algicidal effect over a long period of time Therefore, it was revealed that stable and excellent slime control effect can be obtained, and furthermore, the anticorrosion effect and the scale prevention effect can be maintained high over a long period of time.

The microbicidal and algicidal composition of the present invention can be used for killing harmful bacteria and preventing adhesion of algae in various drainage systems such as process water, cooling water and washing water of various manufacturing industries. Furthermore, the water treatment agent composition of the present invention can be used to suppress the bactericidal effect, corrosion and scale damage of metals.

Claims (6)

  A microbicidal and algicidal composition comprising (A) a brominated sulfamic acid compound and (B) a chlorinated sulfamic acid compound, wherein the pH of the composition is 13 or more. object.   The molar ratio of the (A) brominated sulfamic acid compound and the (B) chlorinated sulfamic acid compound is (A) :( B) = 5: 5 to 1: 9. The microbicidal and algicidal composition as described.   A water treatment agent composition comprising the microbicidal and algicidal composition according to claim 1 and (2) further containing an azole compound, wherein the pH of the composition is 13 or more. Water treatment composition.   The water treatment agent composition according to claim 3, further comprising (2) telomer and / or (3) an organic phosphoric acid compound.   A method of sterilizing and algicidally treating a drainage system and a process water system comprising adding the bactericidal and algicidal composition according to claim 1 or 2 in water. A water treatment method for a drainage system and a process water system, comprising adding the water treatment agent composition according to claim 3 into water.

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