JP5680289B2 - Water treatment agent and water treatment method - Google Patents

Description

  The present invention effectively suppresses scale adhesion and corrosion suppression on the surface of metal materials in contact with water in various water systems such as industrial water systems, cooling water systems, hot water systems, boiler water systems, cleaning water, process water systems, and drainage systems. The present invention relates to a water treatment agent and a water treatment method.

  In various water systems such as a cooling water system, a hot water system, a boiler water system, a washing water, and a process water system, the metal material in contact with water is likely to be corroded or scaled. Therefore, conventionally, heavy metals such as chromate, zinc salt, molybdate, and various phosphorus compounds have been used as corrosion inhibitors and scale inhibitors. However, due to the recent emphasis on environmental issues, such as the release of highly toxic heavy metals such as chromate and zinc into the environment, eutrophication of lakes by phosphorus and the occurrence of red tides in closed waters, these compounds and Wastewater concentration regulations for heavy metals have been strengthened, and the trend is toward reducing emissions. Therefore, various methods using carboxylic acid polymers have been proposed as environmentally friendly treatment agents that replace conventional products.

  For example, a method using a 100: 40 to 100: 1 (molar ratio) copolymer hydrolyzate of a monoethylenically unsaturated monomer such as (meth) acrylic acid and its ester and maleic anhydride (see Patent Document 1) ), A method using a terpolymer of 30 to 80% by weight of maleic anhydride, 10 to 40% by weight of ethyl acrylate and 10 to 30% by weight of styrene or 1-decene (see Patent Document 2), maleic acid and isobutylene And the Langerian index is 1. Corrosion control method (see Patent Document 3) that manages 5 or more and the product of silica concentration and Ca hardness is 2000 or more, co-weight of 80 to 90 mol% maleic anhydride and 10 to 20 mol% olefin having 5 to 12 carbon atoms A method for inhibiting metal corrosion using a combined hydrolyzate (see Patent Document 4) is disclosed. However, in consideration of the influence on the surrounding environment, no method has yet been obtained that does not contain heavy metals and phosphorus and exhibits a satisfactory metal corrosion inhibition effect and scale inhibition effect.

Japanese Patent Publication No.54-29998 Japanese Patent No. 2942991 Japanese Patent Publication No. 4-33868 Japanese Patent Publication No. 5-81320

  The problem of the present invention is that it does not contain any environmental pollutants such as heavy metals and phosphorus, or has an excellent corrosion inhibition effect on metals that come into contact with water even when used at a very low concentration. An object of the present invention is to provide a water treatment agent and a water treatment method capable of effectively suppressing corrosion while suppressing.

  The present inventor made full use of the polymer synthesis technology and the corrosion inhibition effect of metal in contact with water and the evaluation technology of the scale inhibition effect, to determine the relationship between the composition of the polymer and the corrosion inhibition effect and scale inhibition effect of the metal in contact with water. As a result of intensive studies, the simultaneous use of itaconic acid polymer and maleic acid polymer significantly increases the scale prevention effect compared to the use of itaconic acid polymer or maleic acid polymer alone, and excellent corrosion inhibition. The inventors have found that the present invention is effective and have completed the present invention. In addition, the present inventor found that the maleic acid polymer and the itaconic acid polymer produced by the aqueous polymerization method are more effective in inhibiting the corrosion and the scale than the maleic acid polymer and the itaconic acid polymer produced by the organic solvent polymerization method. It was found that the effect is excellent.

That is, the invention according to claim 1 is effective in suppressing the corrosion and scale of the metal in contact with water, using a maleic acid polymer produced by an aqueous polymerization method and an itaconic acid polymer produced by an aqueous polymerization method. see containing as components, mixing weight ratio of the maleic acid-based polymer and said itaconic acid polymer is 10: 90-90: inhibiting water corrosion and scale of the metal in contact with water, which is a 10 A treatment agent ,
The maleic acid polymer is selected from a maleic acid homopolymer or a maleic acid copolymer containing less than 30% by weight of other monomers copolymerizable with maleic acid, and copolymerizable with the maleic acid. The other monomer is one or more selected from the group consisting of unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, and (meth) acrylamide,
The itaconic acid polymer is selected from an itaconic acid homopolymer or an itaconic acid copolymer containing less than 30% by weight of other monomers copolymerizable with itaconic acid, and copolymerizable with the itaconic acid. The other monomer is one or more selected from the group consisting of unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, and (meth) acrylamide. Water treatment agent to be suppressed (however, the water treatment agent is not used in combination with a sulfonic acid group-containing polymer) .

Billing invention according to claim 2, itaconic acid polymer produced by maleic acid-based polymer and an aqueous polymerization method produced by aqueous polymerization of 10: 90 to 90: Turkey be added to the 10 target water system in a weight ratio of A water treatment method for suppressing corrosion and scale of metal in contact with water, characterized by :
The maleic acid polymer is selected from a maleic acid homopolymer or a maleic acid copolymer containing less than 30% by weight of other monomers copolymerizable with maleic acid, and copolymerizable with the maleic acid. The other monomer is one or more selected from the group consisting of unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, and (meth) acrylamide,
The itaconic acid polymer is selected from an itaconic acid homopolymer or an itaconic acid copolymer containing less than 30% by weight of other monomers copolymerizable with itaconic acid, and copolymerizable with the itaconic acid. The other monomer is one or more selected from the group consisting of unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, and (meth) acrylamide. This is a water treatment method to be suppressed (however, this water treatment method does not add a sulfonic acid group-containing polymer in combination) .

  Since the water treatment agent and water treatment method of the present invention have an effect equal to or higher than the corrosion inhibition effect of conventional water treatment agents using heavy metals and phosphorus, environmental pollutants such as heavy metals and phosphorus are removed. It can be used at a very low concentration, or it can be used at a very low concentration, has no impact on the environment, and also has a scale control effect, which can greatly contribute to stable operation of the factory, reduction of maintenance costs for equipment and facilities, and safe operation.

Hereinafter, embodiments of the present invention will be described in detail.
The maleic acid polymer used in the present invention is a polymer containing maleic acid as a main constituent unit, and the polymer contains a maleic acid monomer, or a maleic monomer and other monomers copolymerizable with maleic acid. Produced by polymerization.

  The constituent ratio of maleic acid in the polymer is in the range of 70 to 100% by weight, but preferably in the range of 80 to 100% by weight. The maleic acid polymer of the present invention may be a maleic acid homopolymer or a maleic acid copolymer containing less than 30% by weight of other monomers copolymerizable with maleic acid.

The itaconic acid polymer used in the present invention is a polymer containing itaconic acid as a main constituent unit, and the polymer contains an itaconic acid monomer, or an itaconic acid monomer and another monomer copolymerizable with itaconic acid. Produced by polymerization.

  The composition ratio of itaconic acid in the polymer is in the range of 70 to 100% by weight, but preferably in the range of 80 to 100% by weight. The itaconic acid polymer of the present invention may be an itaconic acid homopolymer or an itaconic acid copolymer containing less than 30% by weight of other monomers copolymerizable with itaconic acid.

  Examples of the maleic monomers include maleic acid and neutralized salts thereof, maleic anhydride, maleic esters and mixtures thereof. Examples of the neutralized salt include alkali metal salts (specifically, potassium salts, sodium salts, etc.) and ammonium salts, and one or more of these may be used.

As the copolymerizable other monomers and maleic acid, A acrylic acid, methacrylic acid, unsaturated carboxylic acids such as crotonic acid; (meth) acrylic acid alkyl esters, (meth) acrylamide is Agerare, Two or more of these may be used.

  Examples of the itaconic acid monomer include itaconic acid and neutralized salts thereof, itaconic anhydride, itaconic acid esters, and mixtures thereof. The neutralized salt is the same as that exemplified for the maleic monomer. The other monomer copolymerizable with itaconic acid is the same as the other monomer copolymerizable with maleic acid.

  The molecular weight of the maleic acid polymer used in the present invention is usually 300 to 5000, preferably 400 to 3000. If the molecular weight is out of this range, the corrosion inhibiting effect and the scale inhibiting effect are reduced, which is not preferable. The copolymer may be either a block or a random copolymer.

  The molecular weight of the itaconic acid polymer used in the present invention is usually 300 to 5000, preferably 400 to 3000. If the molecular weight is out of this range, the corrosion inhibiting effect and the scale inhibiting effect are reduced, which is not preferable. The copolymer may be either a block or a random copolymer.

  In addition, after the production of the maleic acid polymer, which will be described later, the itaconic acid polymer is produced with the maleic acid polymer still contained in the same reaction vessel, or vice versa. In the water treatment agent of the present invention in which the coalescence is produced in the same reaction vessel, the molecular weights of the maleic acid polymer and the itaconic acid polymer cannot be measured separately, and thus are measured as the average molecular weight of these mixtures. . That is, the weight average molecular weight of the mixture of the maleic acid polymer and the itaconic acid polymer is usually 300 to 3000, preferably 400 to 2000. If the molecular weight is out of this range, the corrosion inhibiting effect and the scale inhibiting effect are reduced, which is not preferable.

  The maleic acid polymer and itaconic acid polymer used in the present invention can be produced by known methods. That is, a maleic acid monomer or an itaconic acid monomer in an aqueous solution or an organic solvent such as xylene, toluene, isopropyl alcohol, hydrogen peroxide, benzoyl peroxide, persulfate, di-t-butyl peroxide, etc. In the presence of a polymerization initiator, it is produced by adding a polymerization regulator as necessary and heating. The maleic acid polymer is produced by, for example, adding 2 to 10% by weight of maleic anhydride to an aromatic solvent and heating / dissolving it, and 5 to 12% by weight of the polymerization initiator with respect to maleic anhydride. % And polymerizing at a temperature of 100 to 200 ° C. (Japanese Patent No. 2964154) is disclosed. As a method for producing an itaconic acid polymer, for example, a method of adding an initiator to an itaconic acid aqueous solution neutralized with a water-soluble base and maintaining the temperature at 80 to 120 ° C. (Japanese Patent Laid-Open No. 5-86129) is disclosed. Has been.

  If the solvent used in the production of these polymers is a non-aqueous organic solvent such as toluene or xylene, maleic anhydride or maleic esters instead of maleic acid, itaconic esters or itaconic anhydride instead of itaconic acid A monomer that is soluble in an organic solvent such as benzoyl peroxide and di-t-butyl peroxide is used, and a polymerization initiator that is soluble in an organic solvent is used. After producing a polymer containing an anhydride or ester, the organic solvent is removed by decantation or evaporation, and the ester or anhydride is hydrolyzed while heating by adding water to heat the desired water-soluble maleic acid-based polymer. A coalescence or itaconic acid polymer can be obtained. However, since polymerization in a non-aqueous solvent requires an organic solvent removal step and hydrolysis step, not only is the operation complicated, but the heating energy cost and solvent cost used in these steps are large. Not economical. In addition, when harmful organic solvents are released into the atmosphere, waste water, soil, etc., the impact on the environment of the human body cannot be ignored.

Therefore, in the manufacturing method of the maleic acid-based polymer and itaconic acid polymer used in the present invention, it prepared an aqueous polymerization method using no organic solvent. In the case of water-based polymerization using mainly water as a solvent, monomers that are soluble in water such as maleic acid, maleic anhydride, itaconic acid, itaconic anhydride are used, and hydrogen peroxide, persulfate, water-soluble azo It is produced using a polymerization initiator that is soluble in water, such as a system catalyst. However, in the aqueous polymerization method, the reactivity of maleic acid and itaconic acid is low, and the reaction rate of polymerization cannot be sufficiently increased as it is, and a considerable amount of unreacted maleic acid monomer or itaconic acid monomer remains, It is difficult to obtain sufficient corrosion inhibition effect and scale inhibition effect.

  Therefore, in order to synthesize maleic acid-based polymers and itaconic acid-based polymers by water-based polymerization with good yield, in the production of maleic acid-based polymers and itaconic acid-based polymers, together with monomers such as maleic acid and itaconic acid. It is preferable to add an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The amount of the alkali metal hydroxide used here is that the alkali metal hydroxide is added in a molar ratio of 0.2 to 2 with respect to the number of moles of unsaturated carboxylic acid such as maleic acid and itaconic acid. preferable. The alkali metal hydroxide is added all at once before the start of polymerization, or is added sequentially or all at once together with the polymerization initiator at the polymerization reaction stage, but is preferably added all at once before the start of polymerization.

  In the production of a maleic acid polymer or an itaconic acid polymer by an aqueous polymerization method, the blending amount of the monomer with respect to the total production charge is not particularly limited, but is usually in the range of 10 to 60% by weight. In addition, as the timing of monomer addition, itaconic acid monomers may be added together with water before the start of polymerization, or may be added sequentially or collectively at the polymerization reaction stage. It is preferable to add all together with water.

  As the polymerization initiator in the aqueous polymerization method, it is preferable to use hydrogen peroxide and persulfate in combination rather than using hydrogen peroxide, persulfate or the like alone. The amount of the polymerization initiator is peroxidized with respect to the production amount of the maleic acid polymer or itaconic acid polymer in order to synthesize the maleic acid polymer or itaconic acid polymer by the aqueous polymerization method with high yield. The range of 0.3 to 20% by weight of hydrogen and 0.1 to 5% by weight of persulfate is preferred. Moreover, it is preferable that the addition method of a polymerization initiator is dripped sequentially over about 15 minutes-6 hours rather than collectively adding at the time of a polymerization reaction start.

  Further, in the aqueous polymerization method, it is preferable to add a redox catalyst together with the polymerization initiator. Preferred redox catalysts are reducible cations, including metal ions obtained from iron, zinc, cobalt, molybdenum, chromium, nickel, vanadium and cesium and combinations thereof. Preferred metal ions are ferrous ammonium sulfate, ferrous sulfate, ferrous chloride, cobalt salts (eg, cobalt sulfate hexahydrate), vanadium salts and combinations thereof. The amount of the redox catalyst is preferably in the range of 0.001 to 0.5% by weight in terms of metal with respect to the production charge.

  If any of the amount of the alkali metal hydroxide, the amount of the polymerization initiator, or the amount of the metal catalyst is out of the above range, the monomer reaction rate is not sufficiently increased, and a considerable amount of unreacted monomer remains. Therefore, it is difficult to obtain a sufficient corrosion inhibiting effect and scale inhibiting effect.

  Regardless of the polymerization method, the molecular weight of the maleic acid polymer or itaconic acid polymer can be adjusted by appropriately changing the amount of polymerization initiator, polymerization temperature, polymerization time, monomer concentration, and the like. Alternatively, the molecular weight can be adjusted by adding a polymerization regulator and changing its concentration. As the polymerization regulator, secondary compounds such as isopropyl alcohol and 2-butyl alcohol, and known compounds such as bisulfite and sulfite can be used.

  The temperature of the polymerization reaction varies depending on the polymerization method, the type of polymerization initiator, the type of solvent, etc., but is usually controlled to a reflux temperature or a temperature lower than the reflux temperature, and is usually in the range of 40 to 200 ° C. The preferred reaction temperature is in the range of 60-140 ° C. If the reaction temperature is too low, a sufficient reaction rate cannot be obtained, and conversely, if the reaction temperature is too high, a decarboxylation reaction of the polymer occurs and the corrosion inhibition effect and the scale inhibition effect are lowered. .

  In the polymerization reaction of itaconic acid in the aqueous polymerization method, it is preferable to add an antifoaming agent because foaming is likely to occur when the ratio of itaconic acid is high. The antifoaming agent used here is a polyethylene glycol type nonionic surfactant having a cloud point of 20 ° C. or higher, such as polyoxyethylene polyoxypropylene glycol, higher alcohol ethylene oxide adduct, higher alcohol ethylene oxide / propylene oxide adduct, This is preferable because separation in an aqueous solution does not occur at room temperature.

  As a method for preparing the water treatment agent of the present invention, there is a method in which a maleic acid polymer and an itaconic acid polymer are produced and prepared in the same reaction vessel. That is, after the maleic acid polymer is produced, the itaconic acid polymer is produced with the maleic acid polymer contained in the same reaction vessel, and the water treatment of the present invention which is a mixture of two kinds of polymers. The agent may be prepared directly. After the production of the itaconic acid polymer, the maleic acid polymer is produced with the itaconic acid polymer still contained in the same reaction vessel, and the mixture of the two polymers. The water treatment agent of the present invention may be prepared directly. The water treatment agent thus prepared can be diluted with water as needed for handling.

  As another method for preparing the water treatment agent of the present invention, there is a method in which a separately prepared maleic acid polymer and itaconic acid polymer are mixed. In this method, the aqueous solution of the maleic acid polymer and the aqueous solution of the itaconic acid polymer are only stirred and mixed at room temperature until they are uniform, and the order of mixing them is not particularly limited. The blending weight ratio of the maleic acid polymer and the itaconic acid polymer in this water treatment agent is in the range of 90:10 to 10:90, preferably in the range of 70:30 to 30:70, The water treatment agent thus prepared can be diluted with water as needed for handling, or a water treatment agent in a diluted form can be prepared by adding water during preparation of the water treatment agent. .

  In the water treatment method of the present invention, a method of adding a water treatment agent containing a maleic acid polymer and an itaconic acid polymer as active ingredients to the target aqueous system, and the maleic acid polymer and the itaconic acid polymer to the target aqueous system. There is a method of adding separately, and when added separately, the weight ratio of (maleic acid polymer) :( itaconic acid polymer) is in the range of 90:10 to 10:90, preferably It is in the range of 70:30 to 30:70.

  The amount of the water treatment agent of the present invention added to the water system varies depending on the target water system conditions, particularly water quality, temperature, etc., but is generally a maleic acid polymer and an itaconic acid system blended in the water treatment agent. The total active ingredient concentration of the polymer is 1 to 1,000 mg / L, preferably 5 to 500 mg / L, more preferably 10 to 100 mg / L. In addition, when maleic acid polymer and itaconic acid polymer are added separately to the aqueous system, the amount of each added varies depending on the target aqueous system conditions, particularly water quality, temperature, etc. The total active ingredient concentration of the system polymer and the itaconic acid system is 1 to 1,000 mg / L, preferably 5 to 500 mg / L, and more preferably 10 to 100 mg / L.

  In the addition of the water treatment agent to the target water system of the present invention, or the separate addition of the maleic acid polymer and the itaconic acid polymer to the target water system, scale and corrosion of the target water system occur using a chemical injection pump. Add to the place where the stirring is good, upstream of the place where When the target water system is a circulating water system, it can be added to any place in the water system, but it is generally easy to add to a place where the circulating water tank is well stirred.

  Since the water treatment agent and the water treatment method of the present invention have the effect of preventing precipitation and adhesion to various scales such as calcium carbonate, calcium sulfate, magnesium silicate, and silica, they can be applied to water quality with severe scale properties.

  The water quality to which the water treatment agent and the water treatment method of the present invention are applied has a pH of 6 or more, preferably in the range of 8 to 9.5, and from the viewpoint of corrosion inhibition, pH, Ca hardness, M alkalinity. In addition, a scaled water quality having a high silica concentration is preferred. Here, specifically, the scaleable water quality means that the Retner index: RI is 6.0 or less, preferably 5.0 or less, and it is preferable to adjust the water quality of the aqueous system so that RI is in this range.

Here, RI is an index indicating the precipitation tendency of calcium carbonate, and is calculated by the following equation.
RI = 2 × pHs−pH
Moreover, pH is the pH of circulating water, and pHs is the saturated pH of calcium carbonate shown by Formula (1).

here,
pK2: second dissociation constant of carbonic acid pKs: solubility product of calcium carbonate pCa = -log [Ca hardness] (mg-CaCO3 / L)
pA = -log [M alkalinity] (mg-CaCO3 / L)
μ: Ionic strength, calculated by the following formula.
μ = [electric conductivity] (μS / cm) × 0.0000175

  An open circulating cooling water system has a large number of heat exchangers, and the operating conditions are constantly changing. Therefore, it is difficult to accurately grasp the temperature distribution in the system. Therefore, the temperature used for the calculation of the present invention is 40 ° C., which is a typical temperature of the outlet water of the heat exchanger in the open circulating cooling water system. The pK2 at 40 ° C. is 10.2, and the pKs is 8.5. pCa, pA, and μ can be determined by measuring the Ca hardness, M alkalinity, and electrical conductivity of the circulating water by the method described in JIS K0101 (Industrial Water Test Method) and substituting it into the above formula.

  The method of adjusting the aqueous RI is usually achieved by increasing the concentration of the aqueous system and increasing the Ca hardness and the concentration and pH of the M alkalinity component contained in the makeup water. However, when the Ca hardness or M alkalinity component concentration contained in the makeup water is sufficiently small, or when it is difficult to increase the concentration, it may be difficult to reduce the RI of the aqueous system to 6 or less. In such a case, a sufficient corrosion inhibitory effect can be exhibited by adding a small amount of zinc, a phosphoric acid compound, or an alkaline compound together with the maleic acid polymer and the itaconic acid polymer of the present invention. For example, by adding about 0.2 to 3 mg / L of a zinc compound in terms of zinc, a sufficient corrosion inhibiting effect can be exhibited even when the RI is corrosive water quality of 6 or more. Alternatively, by adding an alkaline compound so that the aqueous RI is 6 or less, or 5 or less, when the Ca hardness or M alkalinity component concentration in the makeup water is low, or when it is difficult to increase the concentration However, a sufficient corrosion inhibiting effect can be exhibited.

  Alkaline compounds used here are alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; calcium oxide or calcium hydroxide; carbonates and bicarbonates of alkali metals such as sodium carbonate and potassium carbonate. .

  At the start of the aqueous operation, it is preferable to use a condensed phosphate together with the maleic acid polymer and the itaconic acid polymer of the present invention. The condensed phosphate is a phosphate having a condensation degree of 2 or more, but pyrophosphate (condensation degree 2), tripolyphosphate (condensation degree 3), tetrapolyphosphate (condensation degree 4), hexametaphosphate, etc. Can be used. Generally, what is marketed under the trade name of sodium hexametaphosphate is a chain condensed phosphate having an average condensation degree of 10 or more, but a more preferable condensed phosphate has an average condensation degree of 30 to 100. It is a chain condensed phosphate. The addition amount of the condensed phosphate at the start of the aqueous operation is usually 3 to 200 mg / L, preferably 5 to 100 mg / L.

The water quality of the treated water system (target water system) to which the water treatment agent and the water treatment method of the present invention are applied is not particularly limited, but usually pH 6.0 to 12.0, electric conductivity is 5000 μS / cm or less, Ca hardness Or Mg hardness is 0 to 1000 mg CaCO ₃ / L, M alkalinity is 0 to 500 mg CaCO ₃ / L, silica is 0 to 250 mg / L, chloride ion is 0 to 3000 mg / L, sulfate ion is 0 to 3000 mg / L, all Iron is 10 ppm or less, preferably 3 ppm or less, aluminum is 3 mg / L or less, turbidity or suspended substance concentration is 100 degrees or less, preferably 20 degrees or less, the stability index of the ritner is 3.0 or more, the saturation index of Langeria Is in the range of 3.0 or less.

  Although the temperature of the to-be-processed water system to which the water treatment agent and water treatment method of this invention are applied is not specifically limited, Usually, it is the range of 0-300 degreeC. Moreover, although the flow rate of the to-be-processed water system to which the water treatment agent and water treatment method of this invention are applied is not specifically limited, Usually, it is the range of 0.1-5.0 m / s.

The half-life of the water system to be treated to which the water treatment agent and the water treatment method of the present invention are applied is not particularly limited, but is usually 300 hours or less. Where the half time is the formula:
Half time [h] = (Retained water amount [m ³ ] / Blowdown water amount [m ³ /h])×0.693
Indicated by

  Along with the maleic acid polymer and the itaconic acid polymer of the present invention, another type of compound known as a corrosion inhibitor, a scale inhibitor, a scale dispersant, a microbial disorder inhibitor, an oxygen scavenger, a pH adjuster, a cleaning agent. You may use together well-known compounds, such as a can agent, a feed / condensate anticorrosive agent, and an antifoamer.

  The compounds as corrosion inhibitors that are preferably used in combination are organic phosphonic acid, phosphonocarboxylic acid, phosphinopolycarboxylic acid, sulfonic acid group-containing polymer, phosphoric acid or phosphate, and molybdate.

  The organic phosphonic acid is an organic compound having one or more phosphono groups in the molecule, specifically, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid. , Diethylenetriaminepentamethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, and the like, preferably 1-hydroxyethylidene-1,1-diphosphonic acid.

  The phosphonocarboxylic acid is an organic compound having one or more phosphono groups and one or more carboxyl groups in the molecule. Specifically, 2-phosphonobutane-1,2,4-tricarboxylic acid, hydroxyphosphonic acid is used. Nonacetic acid, phosphonopolymaleic acid, phosphonic succinic acid and the like can be mentioned, and 2-phosphonobutane-1,2,4-tricarboxylic acid and phosphonopolymaleic acid are preferable. Here, phosphonocarboxylic acid is commercially available from Rhodia under the trade name BRICORRR288 and from BWA under the trade name BELCOR585. The phosphonocarboxylic acid can be produced, for example, by heating phosphorous acid and monoethylenically unsaturated carboxylic acid in a neutral to alkaline aqueous solvent in the presence of a free radical initiator (for example, special (See Kaihei 4-334392). The phosphonocarboxylic acid can be obtained by reacting a reaction product of hypophosphorous acid with a carbonyl compound or an imine compound with an unsaturated carboxylic acid in the presence of a reaction initiator (see Japanese Patent No. 3284318). ).

  The phosphinopolycarboxylic acid is a compound having one or more phosphino groups and two or more carboxyl groups in the molecule. Specifically, it is a bis-- obtained by reacting acrylic acid and hypophosphorous acid. Poly (2-carboxyethyl) phosphinic acid, bis-poly (1,2-dicarboxyethyl) phosphinic acid obtained by reacting maleic acid with hypophosphorous acid, reacting maleic acid with acrylic acid and hypophosphorous acid Bis-poly [2-carboxy- (2-carboxymethyl) obtained by reacting poly (2-carboxyethyl) (1,2-dicarboxyethyl) phosphinic acid, itaconic acid and hypophosphorous acid Ethyl] phosphinic acid, acrylic acid, a reaction product of 2-acrylamido-2-methylpropanesulfonic acid and hypophosphorous acid, etc., preferably acrylic acid The reaction product of maleic acid and hypophosphorous acid is the reaction product of itaconic acid and maleic acid and hypophosphorous acid. The preparation of phosphinopolycarboxylic acid is usually carried out by heating hypophosphorous acid and monoethylenically unsaturated carboxylic acid in an aqueous solvent in the presence of a free radical initiator, for example, JP-B-54-29316. No. 5, JP-B-5-57992 and JP-B-6-47113. Further, phosphinopolycarboxylic acids are commercially available from Bio Labs under trade names such as BELCLENE500, BELPERSE164, and BELCLENE400.

  The sulfonic acid group-containing polymer is a polymer of monoethylenically unsaturated sulfonic acid, a copolymer of monoethylenically unsaturated sulfonic acid and monoethylenically unsaturated carboxylic acid, or monoethylenically unsaturated sulfonic acid and monopolymer. A copolymer of an ethylenically unsaturated carboxylic acid and another copolymerizable monoethylenically unsaturated monomer. Monoethylenically unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, conjugated diene sulfonated products such as butadiene sulfonic acid and isoprene sulfonic acid, styrene sulfone One or more of acid, sulfoalkyl (meth) acrylate ester, sulfoalkyl (meth) allyl ether, sulfopheno (meth) allyl ether, (meth) allylsulfonic acid, and the like are used. As the monoethylenically unsaturated carboxylic acid, one or more of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like are used. Other copolymerizable monoethylenically unsaturated monomers include (meth) acrylic acid esters (meth) acrylic acid alkyl esters, (meth) acrylic acid hydroxyl alkyl esters; (meth) acrylamides (meth) ) Acrylamide, N-alkyl substituted (meth) acrylamide; olefins having 2 to 8 carbon atoms such as ethylene, propylene, isopropylene, butylene, isobutylene, hexene, 2-ethylhexene, pentene, isopentene, octene, isooctene, etc .; vinyl alkyl ether Vinyl methyl ether, vinyl ethyl ether; maleic acid alkyl ester and the like, and one or more of them are used.

  Among the aforementioned sulfonic acid group-containing polymers, a copolymer of monoethylenically unsaturated sulfonic acid and monoethylenically unsaturated carboxylic acid, or monoethylenically unsaturated sulfonic acid and monoethylenically unsaturated carboxylic acid and other copolymers. A copolymer with a polymerizable monoethylenically unsaturated monomer is preferred, and a more preferred specific compound is a copolymer of 2-acrylamido-2-methylpropanesulfonic acid and (meth) acrylic acid, 3- Examples include copolymers of allyloxy-2-hydroxy-1-propanesulfonic acid and (meth) acrylic acid, and copolymers of conjugated diene sulfonated products and (meth) acrylic acid.

  The molecular weight of the sulfonic acid group-containing polymer is usually 1,000 to 100,000, preferably 4,000 to 20,000 as a weight average molecular weight.

  In the case where copper or a copper alloy is present in a part of the water-system equipment targeted by the water treatment agent and water treatment method of the present invention, it is preferable to use an azole compound in combination. Examples of the azole compound include tolyltriazole, benzotriazole, substituted benzotriazole, mercaptobenzothiazole and the like.

  Although microbial damage as well as corrosion and scale are major obstacles in water systems, it is particularly preferable to use a microbial damage inhibitor together with the water treatment agent and the water treatment method of the present invention because microbial damage cannot be prevented. Examples of microbial disorder inhibitors used in combination include sodium hypochlorite, calcium hypochlorite, liquefied chlorine, bromine chloride, reaction products of hypochlorite and bromide, chloroisocyanuric acids, chlorodimethylhydantoic acids, bromo Compounds that dissolve in water, such as dimethylhydantoic acids and chlorobromodimethylhydantoic acids, to form hypochlorous acid and / or hypobromite; hydrazine; 2-methylisothiazolin-3-one, 2-methyl-4-chloroisothiazoline -3-one, 2-methyl-5-chloroisothiazolin-3-one, 2-methyl-4,5-dichloroisothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-n-octyl- 4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline Isothiazoline compounds; organic bromine compounds such as 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-3-nitrilopropionamide; methylenebisthiocyanate Bis- (1,4-dibromoacetoxy) -2-butene, benzyl bromoacetate, sodium bromide, α-bromocinnamaldehyde, 2-pyridinethiol-1-oxide sodium, bis (2-pyridinethiol-1- Oxide) zinc, 2- (4-thiazolyl) benzimidazole, hexahydro-1,3,5-tris- (2-hydroxyethyl) -S-triazine, bis (trichloromethyl) sulfone, dithiocarbamate, 3,5-dimethyl Rutetrahydro-1,3,5,2H-thiadiazine- -Thion, bromoacetic acid ethylthiophenyl ester, α-chlorobenzoaldoxime acetate, 2,4,5,6-tetrachloroisophthalonitrile, 1,2-dibromo-2,4-dicyanobutane, 3-iodo- Examples include 2-propenylbutylcarbamate, salicylic acid, sodium salicylate, p-oxybenzoic acid ester, and p-chloro-m-xylenol.

In the water treatment agent and the water treatment method of the present invention, the microbial disorder inhibitor preferably used in combination is a compound that generates hypochlorous acid and / or hypobromite, but the amount added is free halogen concentration (free The sum of chlorine and free bromine) is usually 0.05 to ₂ mg / L (in terms of Cl ₂ ).

  In the water treatment agent and water treatment method of the present invention, the form of corrosion targeted is not particularly limited, but overall corrosion, pitting corrosion, crevice corrosion, oxygen concentration cell corrosion, stress corrosion cracking, galvanic corrosion, microbial corrosion, flow induction Local corrosion, erosion corrosion, cavitation corrosion, decomponent corrosion, dezincification corrosion, etc. are included.

  The water treatment agent and the water treatment method of the present invention have a scale-inhibiting effect, but the type of scale to be used is not particularly limited, and carbonate scales such as calcium carbonate and magnesium carbonate; calcium sulfate, barium sulfate, strontium sulfate Sulfate scales such as; phosphate scales such as calcium phosphate, zinc phosphate, iron phosphate, aluminum phosphate; silicates such as magnesium silicate, calcium silicate, aluminum silicate, iron silicate, zinc silicate Scale; amorphous silica scale; magnesium hydroxide; aluminum hydroxide; iron oxide, iron hydroxide, and the like.

  Metals that form a passivated film such as stainless steel and titanium are prone to pitting corrosion and stress corrosion cracking due to crevice corrosion at the scale adhering portion, but in the water treatment agent and water treatment method of the present invention, By preventing scale adhesion, it is possible to indirectly prevent corrosion of a metal that forms a passivation film such as stainless steel or titanium.

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

(Production Example 1) Production Example of Maleic Acid Polymer by Aqueous Polymerization Method Maleic anhydride 40 parts by weight (0.40 mol) in a 500 mL four-necked flask equipped with a glass reflux tube, a nitrogen vent tube, a dropping funnel and a stirrer Then, 0.02 part by weight of ferrous sulfate heptahydrate and 60 parts by weight of water were added, and 11.9 parts by weight (0.10 mol) of 48% potassium hydroxide aqueous solution was added thereto. A cooling tube, a stirrer, a thermometer, a nitrogen introduction tube, and a dropping funnel were attached to the flask, and nitrogen was continuously bubbled while stirring during the entire reaction process. After the liquid was heated to 90 ° C., a solution prepared by dissolving 8 parts by weight of 35% hydrogen peroxide and 0.3 part by weight of sodium persulfate in 12 parts by weight of water was added dropwise over 120 minutes while maintaining the temperature at 90 ° C. After completion of the dropping, 0.02 part by weight of ferrous sulfate heptahydrate was added all at once, and further heated at 90 ° C. for 2 hours to obtain an aqueous solution of a maleic acid polymer having a weight average molecular weight of 1100. As a result of measuring residual monomers by high performance liquid chromatography, the reaction rate of maleic acid was 90%.

(Production Example 2) Production Example of Itaconic Acid Polymer by Aqueous Polymerization Method In the same four-necked flask as in Production Example 1, itaconic acid 40 parts by weight (0.3 mol), ferrous sulfate heptahydrate 0.02 weight Part and 60 parts by weight of water were added, and 11.9 parts by weight (0.1 mol) of a 48% aqueous potassium hydroxide solution was added thereto. A cooling tube, a stirrer, a thermometer, a nitrogen introduction tube, and a dropping funnel were attached to the flask, and nitrogen was continuously bubbled while stirring during the entire reaction process. After the liquid was heated to 90 ° C., a solution prepared by dissolving 8 parts by weight of 35% hydrogen peroxide and 0.3 part by weight of sodium persulfate in 12 parts by weight of water was added dropwise over 120 minutes while maintaining the temperature at 90 ° C. After completion of the dropwise addition, 0.02 part by weight of ferrous sulfate heptahydrate was added all at once, and further heated at 90 ° C. for 2 hours to obtain an aqueous solution of an itaconic acid polymer having a weight average molecular weight of 1100. As a result of measuring the residual monomer by high performance liquid chromatography, the reaction rate of itaconic acid was 99%.

(Production Example 3) Production example of maleic acid polymer and itaconic acid polymer by water-based polymerization method (Preparation of water treatment agent for producing two types of polymers in the same reaction vessel)
To the same four-necked flask as in Production Example 1, 20 parts by weight (0.20 mol) of maleic anhydride, 0.02 parts by weight of ferrous sulfate heptahydrate and 60 parts by weight of water were added, and 48% hydroxylation was added thereto. 11.9 parts by weight (0.10 mol) of an aqueous potassium solution was added. A cooling tube, a stirrer, a thermometer, a nitrogen introduction tube, and a dropping funnel were attached to the flask, and nitrogen was continuously bubbled while stirring during the entire reaction process. After the liquid was heated to 90 ° C., a solution prepared by dissolving 8 parts by weight of 35% hydrogen peroxide and 0.3 parts by weight of sodium persulfate in 12 parts by weight of water was dropped over 40 minutes while maintaining the temperature at 90 ° C. After the addition, 20 parts by weight of itaconic acid (0.15 mol) and 0.02 part by weight of ferrous sulfate heptahydrate were added all at once, 8 parts by weight of 35% hydrogen peroxide and 0.3 parts by weight of sodium persulfate. A solution obtained by dissolving a part in 12 parts by weight of water was added dropwise over 40 minutes while maintaining the temperature at 90 ° C. After completion of the dropwise addition, the mixture was further heated at 90 ° C. for 2 hours to obtain an aqueous solution having a weight-average molecular weight of 1100 maleic acid polymer and itaconic acid polymer in a blending weight ratio of 54:46. As a result of measuring the residual monomer by high performance liquid chromatography, the reaction rate of maleic acid was 97% and the reaction rate of itaconic acid was 98%.

(Production Example 4) Production Example of Maleic Acid Polymer by Solvent Polymerization Method Into the same four-necked flask as in Production Example 1, 10 g of maleic anhydride and 90 g of o-xylene were placed, heated to 140 ° C. and dissolved with stirring. An initiator solution prepared by dissolving 0.3 g of di-tert-butyl peroxide in 10 g of xylene was added dropwise over 15 minutes while maintaining 140 ° C. under nitrogen gas flow. After completion of the dropping, 140 ° C. was maintained for 90 minutes under nitrogen gas flow. When the polymer precipitated at the bottom of the flask, the supernatant was removed by decantation, and then 100 ml of water was added to obtain a transparent polymer solution. The polymer solution was put in a rotary evaporator and heated at 50 ° C. under reduced pressure to distill off xylene, thereby obtaining an aqueous solution of a maleic acid polymer having a weight average molecular weight of 500.

Production Example 5 Production Example of Itaconic Acid Polymer by Solvent Polymerization A dimethyl itaconate polymer was obtained in the same manner as in Production Example 4 except that dimethyl itaconate was used instead of maleic anhydride. Hydrochloric acid was added thereto, the ester was hydrolyzed while refluxing for 18 hours under boiling, and then hydrochloric acid was distilled off to obtain an itaconic acid polymer having a weight average molecular weight of 1000.

(Production Example 6) Production Example of Maleic Acid-Acrylic Acid Copolymer by Aqueous Polymerization Method Maleic anhydride 20 parts by weight (0.20 mol), ferrous sulfate heptahydrate in the same 4-necked flask as in Production Example 1 0.03 part by weight of the product and 40 parts by weight of water were added, and 23.8 parts by weight (0.20 mol) of a 48% aqueous potassium hydroxide solution was added thereto. A cooling tube, a stirrer, a thermometer, a nitrogen introduction tube, and a dropping funnel were attached to the flask, and nitrogen was continuously bubbled while stirring during the entire reaction process. After the liquid was heated to 90 ° C., 4.1 parts by weight (0.057 mol) of acrylic acid was dissolved in 10 parts by weight of water, 16 parts by weight of 35% hydrogen peroxide and 0.6 parts by weight of sodium persulfate. Each of the solutions dissolved in 24 parts by weight of water was put into separate dropping funnels and dropped over 2 hours while maintaining at 90 ° C. After completion of the dropwise addition, 0.02 part by weight of ferrous sulfate heptahydrate was added, and then maintained at 90 ° C. for 2 hours, and a maleic acid- acrylic acid (weight ratio 85:15) copolymer having a weight average molecular weight of 2,000. Got.

(Production Example 7) Production Example of Itaconic Acid-Methyl Acrylate Copolymer by Aqueous Polymerization Method In the same four-necked flask as in Production Example 1, itaconic acid 40 parts by weight (0.3 mol), methyl acrylate 4 parts by weight ( 0.047 mol), 0.02 part by weight of ferrous sulfate heptahydrate and 60 parts by weight of water were added, and 8.3 parts by weight (0.1 mol) of a 48% sodium hydroxide aqueous solution was added thereto. A cooling tube, a stirrer, a thermometer, a nitrogen introduction tube, and a dropping funnel were attached to the flask, and nitrogen was continuously bubbled while stirring during the entire reaction process. After the liquid was heated to 90 ° C., a solution prepared by dissolving 8 parts by weight of 35% hydrogen peroxide and 0.3 part by weight of sodium persulfate in 12 parts by weight of water was added dropwise over 120 minutes while maintaining the temperature at 90 ° C. After completion of the dropwise addition, 0.02 part by weight of ferrous sulfate heptahydrate was added all at once, and further heated at 90 ° C. for 2 hours to give itaconic acid-methyl acrylate having a weight average molecular weight of 2000 (weight ratio 91: 9). An aqueous solution of the copolymer was obtained.

Production Example 8 Production Example of Itaconic Acid-acrylamide Copolymer by Aqueous Polymerization Method In the same four-necked flask as in Production Example 1, itaconic acid 40 parts by weight (0.3 mol), acrylamide 5.4 parts by weight (0. 076 mol), 0.02 part by weight of ferrous sulfate heptahydrate and 60 parts by weight of water were added, and 8.3 parts by weight (0.1 mol) of a 48% sodium hydroxide aqueous solution was added thereto. A cooling tube, a stirrer, a thermometer, a nitrogen introduction tube, and a dropping funnel were attached to the flask, and nitrogen was continuously bubbled while stirring during the entire reaction process. After the liquid was heated to 90 ° C., a solution prepared by dissolving 8 parts by weight of 35% hydrogen peroxide and 0.3 part by weight of sodium persulfate in 12 parts by weight of water was added dropwise over 120 minutes while maintaining the temperature at 90 ° C. After completion of the dropwise addition, 0.02 part by weight of ferrous sulfate heptahydrate was added all at once, and further heated at 90 ° C. for 2 hours, so that itaconic acid-acrylamide having a weight average molecular weight of 2000 (weight ratio 88:12) A combined aqueous solution was obtained.

(Production Example 9) Production Example of Maleic Acid Polymer by Aqueous Polymerization Method After heating the solution to 100 ° C, 40 parts by weight of 35% hydrogen peroxide and 1.5 parts by weight of sodium persulfate were dissolved in 12 parts by weight of water. An aqueous solution of a maleic acid polymer having a weight average molecular weight of 400 was obtained in the same manner as in Production Example 1, except that the solution was added dropwise over 120 minutes while maintaining the temperature at 100 ° C.

(Production Example 10) Production Example of Maleic Acid Polymer by Aqueous Polymerization Method After heating the solution to 80 ° C, 6 parts by weight of 35% hydrogen peroxide and 0.5 parts by weight of sodium persulfate were dissolved in 12 parts by weight of water. An aqueous solution of a maleic acid polymer having a weight average molecular weight of 3000 was obtained in the same manner as in Production Example 1 except that the solution was added dropwise over 240 minutes while maintaining the temperature at 80 ° C.

(Production Example 11) Production Example of Itaconic Acid Polymer by Aqueous Polymerization Method After heating the solution to 100 ° C., 30 parts by weight of 35% hydrogen peroxide and 1.2 parts by weight of sodium persulfate were dissolved in 12 parts by weight of water. An aqueous solution of an itaconic acid polymer having a weight average molecular weight of 400 was obtained in the same manner as in Production Example 1, except that the solution was added dropwise over 120 minutes while maintaining the temperature at 100 ° C.

(Production Example 12) Production Example of Itaconic Acid Polymer by Aqueous Polymerization Method After heating the solution to 80 ° C, 6 parts by weight of 35% hydrogen peroxide and 0.5 parts by weight of sodium persulfate were dissolved in 12 parts by weight of water. An aqueous solution of an itaconic acid polymer having a weight average molecular weight of 3000 was obtained in the same manner as in Production Example 1, except that the solution was added dropwise over 120 minutes while maintaining the temperature at 80 ° C.

(Production Example 13) Production example of maleic acid polymer and itaconic acid polymer by aqueous polymerization method (preparation of water treatment agent for producing two kinds of polymers in the same reaction vessel)
To the same four-necked flask as in Production Example 1, 20 parts by weight (0.20 mol) of maleic anhydride, 0.02 parts by weight of ferrous sulfate heptahydrate and 60 parts by weight of water were added, and 48% hydroxylation was added thereto. 11.9 parts by weight (0.10 mol) of an aqueous potassium solution was added. A cooling tube, a stirrer, a thermometer, a nitrogen introduction tube, and a dropping funnel were attached to the flask, and nitrogen was continuously bubbled while stirring during the entire reaction process. After heating the liquid to 100 ° C., a solution prepared by dissolving 20 parts by weight of 35% hydrogen peroxide and 0.8 part by weight of sodium persulfate in 12 parts by weight of water was added dropwise over 40 minutes while maintaining the temperature at 100 ° C. After completion of dropping, 20 parts by weight of itaconic acid (0.15 mol) and 0.02 part by weight of ferrous sulfate heptahydrate were added all at once, and 20 parts by weight of 35% hydrogen peroxide and 0.8 parts by weight of sodium persulfate were added. A solution obtained by dissolving a part in 12 parts by weight of water was added dropwise over 40 minutes while maintaining the temperature at 100 ° C. After completion of dropping, the mixture was further heated at 100 ° C. for 2 hours to obtain an aqueous solution having a weight ratio of maleic acid polymer having a weight average molecular weight of 400 and itaconic acid polymer of 54:46.

(Production Example 14) Production example of maleic acid polymer and itaconic acid polymer by water-based polymerization method (Preparation of water treatment agent for producing two polymers in the same reaction vessel)
To the same four-necked flask as in Production Example 1, 20 parts by weight (0.20 mol) of maleic anhydride, 0.02 parts by weight of ferrous sulfate heptahydrate and 60 parts by weight of water were added, and 48% hydroxylation was added thereto. 11.9 parts by weight (0.10 mol) of an aqueous potassium solution was added. A cooling tube, a stirrer, a thermometer, a nitrogen introduction tube, and a dropping funnel were attached to the flask, and nitrogen was continuously bubbled while stirring during the entire reaction process. After the liquid was heated to 80 ° C., a solution prepared by dissolving 6 parts by weight of 35% hydrogen peroxide and 0.5 part by weight of sodium persulfate in 12 parts by weight of water was added dropwise over 80 minutes while maintaining the temperature at 80 ° C. After the addition, 20 parts by weight of itaconic acid (0.15 mol) and 0.02 part by weight of ferrous sulfate heptahydrate were added all at once, and 6 parts by weight of 35% hydrogen peroxide and 0.5 parts by weight of sodium persulfate were added. A solution prepared by dissolving a part in 12 parts by weight of water was added dropwise over 80 minutes while maintaining the temperature at 100 ° C. After the completion of the dropwise addition, the mixture was further heated at 80 ° C. for 2 hours to obtain an aqueous solution having a weight-average molecular weight of 2000 maleic acid polymer and itaconic acid polymer of 54:46.

(Example 1-5, 7-14, Comparative Example 1 to 7)
The polymers shown in Table 1 were used in the following corrosion inhibition test so that the active ingredient concentrations of the polymers shown in Table 1 were added separately.

(Example 6 )
48 parts by weight of the maleic acid polymer of Production Example 1 and 52 parts by weight of the itaconic acid polymer of Production Example 2 were added and mixed by stirring until uniform, and the blending weight ratio of the maleic acid polymer and the itaconic acid polymer was 50: 50 water treatment agents-1 were obtained. This water treatment agent-1 was used in the following corrosion inhibition test so that the active ingredient concentrations of the polymers shown in Table 1 were added.

( Comparative Example 8)
41 parts by weight of maleic acid polymer of Production Example 4 and 59 parts by weight of itaconic acid polymer of Production Example 5 were added and mixed by stirring until uniform, and the blending weight ratio of maleic acid polymer and itaconic acid polymer was 50: 50 water treatment agents-2 were obtained. This water treatment agent-2 was used in the following corrosion inhibition test so that the active ingredient concentrations of the polymers shown in Table 1 were added.

(Comparative Example 9 )
In the following corrosion inhibition test, it is a blank in which the polymer of the present invention, the water treatment agent, and other water treatment agents are not added at all.

(Corrosion suppression test)
According to JIS K0100-1990 industrial water corrosion test method (rotation method), a low carbon steel (JIS G 3141SPCC-SB) specimen having dimensions of 50 × 30 × 1 mm and a surface area of 0.316 dm ² is degreased with acetone, dried and weighed. Was measured. Next, the polymer combinations or water treatment agents shown in Table 1 were added to the test water so that the active ingredient concentrations of the polymers shown in Table 1 were added. The water quality of the test solution was pH: 8.8, M alkalinity: 300 ppm, calcium hardness: 300 ppm, chloride ion: 212 ppm, and Ritsner index (40 ° C.): 4.5. According to JIS K0100-1990 industrial water corrosion test method (rotation method), 500 mL of the test solution is put into a reflux condenser and a flask with a stirrer and kept in a constant temperature bath at 40 ° C., and the test piece is defined in the test method. The motor of the corrosion test apparatus was attached to a holder of a rotating shaft, immersed in a flask containing a test solution at 40 ° C., and the test piece was continuously rotated at a linear velocity of 0.3 m / sec for 3 days. After 3 days, remove the test piece, remove the corrosive products and scale deposits on the surface with a brush under running water, dry it, measure the weight of the test piece, and calculate the corrosion rate (mdd) using the following formula. did.
Corrosion rate (mdd) = (weight loss of test piece: mg) / [(test piece surface area: dm ² ) × (test days: days)]
Moreover, the test piece was observed with the scanning electron microscope, and the adhesion state of the scale crystal was confirmed. The results are shown in Table-1.

Acrylic acid polymers of Comparative Examples 3, 4, and 5 (molecular weight 2500): BAKA-made SOKALAN PA20 (trade name, main component is polyacrylic acid) was used as it was.
Maleic anhydride-ethyl acrylate-styrene copolymer of Comparative Example 6 (49:25:26 wt%): synthesized by the method described in Example 1 of Japanese Patent No. 2942991.

From the results of Examples 1 to 5 in Table 1, the corrosion of metals in contact with water by adding maleic acid polymer and itaconic acid polymer to the target aqueous system in a weight ratio of 10:90 to 90:10. It was found that the scale can be effectively suppressed. Further, from the results of Example 1 and Comparative Example 7 , a combination of a maleic acid polymer and an itaconic acid polymer produced by an aqueous polymerization method was combined with a maleic acid polymer and an itaconic acid produced by an organic solvent polymerization method. It was found that the corrosion inhibitory effect was superior to the combination of the series polymers. On the other hand, by comparing the results of Example 1 and Example 6 , even if the maleic acid polymer and the itaconic acid polymer are separately added to the target aqueous system, a water treatment agent in which both polymers are blended in advance. It was found that the same effect can be obtained even if prepared and added to the target aqueous system. From the results of Example 7 , it was found that the same effect can be obtained even when a water treatment agent prepared by producing two kinds of polymers in the same reaction vessel as the water treatment agent. Further, from the results of Examples 8 to 10, a copolymer containing maleic acid as a main constituent unit instead of a maleic acid homopolymer, and itaconic acid as a main constituent unit instead of an itaconic acid homopolymer are included. It was found that the same corrosion inhibiting effect and scale inhibiting effect can be obtained even when the copolymer is used. From the results of Examples 1, 11 and 12 , and Examples 7 , 13 and 14 , a combination of maleic acid-based polymer and itaconic acid-based polymer having various molecular weights, or two kinds of polymers having various average molecular weights. It has been found that even a mixture mixture can provide an excellent corrosion inhibiting effect and scale inhibiting effect.

In Table 1, Comparative Examples 1 to 3 using a maleic acid polymer, an itaconic acid polymer, or an acrylic acid polymer alone, a combination of a maleic acid polymer and an acrylic acid polymer, and an itaconic acid heavy polymer Itaconic acid system shown in Examples 1 to 14 in Table 1 even when compared with the results of Comparative Examples 4 and 5 using a combination of a polymer and an acrylic acid polymer, and Comparative Example 6 which is a conventional technique It has been found that the water treatment agent and the water treatment method of the present invention using a polymer and a maleic acid polymer at the same time have a particularly excellent corrosion inhibition effect and scale inhibition effect.

The present invention can be open-circulating cooling water system, a closed circulating cooling water system, a transient cooling water system, a boiler water system, circulating cold water, be used for corrosion inhibition and scale inhibition of metals in aqueous systems, such as circulating heating water .

Claims (2)

Look containing itaconic acid based polymer produced by maleic acid-based polymer and an aqueous polymerization method produced by aqueous polymerization, as the active ingredient having the effect of suppressing corrosion and scale of the metal in contact with water, the maleic acid-based A water treatment agent for inhibiting corrosion and scale of metal in contact with water, characterized in that the blending weight ratio of the polymer and the itaconic acid polymer is 10:90 to 90:10 ,
The maleic acid polymer is selected from a maleic acid homopolymer or a maleic acid copolymer containing less than 30% by weight of other monomers copolymerizable with maleic acid, and copolymerizable with the maleic acid. The other monomer is one or more selected from the group consisting of unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, and (meth) acrylamide,
The itaconic acid polymer is selected from an itaconic acid homopolymer or an itaconic acid copolymer containing less than 30% by weight of other monomers copolymerizable with itaconic acid, and copolymerizable with the itaconic acid. The other monomer is one or more selected from the group consisting of unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, and (meth) acrylamide. Water treatment agent to be suppressed (however, the water treatment agent is not combined with a sulfonic acid group-containing polymer). Itaconic acid-based polymer produced by maleic acid-based polymer and an aqueous polymerization method produced by aqueous polymerization of 10: 90 to 90: contact with water, characterized in the Turkey be added to the subject aqueous 10 weight ratio of A water treatment method that suppresses corrosion and scale of metal ,
The maleic acid polymer is selected from a maleic acid homopolymer or a maleic acid copolymer containing less than 30% by weight of other monomers copolymerizable with maleic acid, and copolymerizable with the maleic acid. The other monomer is one or more selected from the group consisting of unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, and (meth) acrylamide,
The itaconic acid polymer is selected from an itaconic acid homopolymer or an itaconic acid copolymer containing less than 30% by weight of other monomers copolymerizable with itaconic acid, and copolymerizable with the itaconic acid. The other monomer is one or more selected from the group consisting of unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, and (meth) acrylamide. Water treatment method to suppress (however, this water treatment method does not add a sulfonic acid group-containing polymer in combination).