TW200538405A - Method of cooling water treatment and treatment chemical - Google Patents

Abstract

With respect to open circulatory cooling water systems, the metal corrosion and scale fault can be simultaneously prevented. There is provided a method of treating cooling water, comprising adding a calcium carbonate precipitation inhibitor and a calcium carbonate dispersant to cooling water to thereby disperse calcium carbonate microparticles in the cooling water with the result that an anticorrosive coating is formed on the metal surface. By forming calcium carbonate acting on corrosion sites of metal in advance into dispersible microparticles and causing them to be present in cooling water, not only is the amount of supply to corrosion sites increased to thereby provide an anticorrosive film of calcium carbonate promptly, stably and certainly but also the dispersion thereof is promoted to thereby prevent excessive scale attachment and hence prevent scale fault. For attaining formation and dispersion of fine calcium carbonate microparticles, the calcium carbonate precipitation inhibitor capable of preventing the precipitation of calcium carbonate is used in combination with the calcium carbonate dispersant for effecting dispersion, within a given range of size, of calcium carbonate occurring in a water medium exceeding the limit of precipitation preventing capability of the calcium carbonate precipitation inhibitor so as to prevent any coarsening thereof.

Description

200538405 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a treatment method and a treatment agent for simultaneously preventing metal corrosion and scale obstacles of an open circulating cooling water system. [Prior art]

Metal parts such as heat exchangers, reaction flea, and piping made of carbon steel, copper, or steel alloy are installed in the open-loop cooling water system. Corrosion is caused by contact with the cooling water, and it is usually prevented by adding chemicals. Money processing. For example, in order to suppress the corrosion of heat exchangers, reaction flea and piping made of carbon steel, orthophosphate, hexametaphosphate, hydroxyethylene diphosphonate, and phosphonobutanetricarboxylic acid were added to the cooling water in the past. Phosphorus compounds such as salts. Moreover, heavy metal salts such as zinc salts or dichromates are sometimes added alone or in combination. However, the heavy use of such phosphorus compounds or heavy metal salts, especially the heavy metal salts, may cause significant environmental impacts due to the pollution of water quality, so its treatment or drainage treatment is highly valued. On the other hand, for the anti-money of copper and copper alloy materials, although nitrogen-containing or phosphorus-zinc-based drugs are mainly used, once cooling water with a large amount of nitrogen-containing drug tm or phosphorus is discharged into closed waters, Increasing the concentration of these substances in waters will cause problems such as red tides and environmental damage due to eutrophication. However, for water systems that do not contain scale inhibitors, high calcium hardness and magnesium alkalinity, it is known that although carbon steel is initially corroded, it is difficult to further corrode once it has suffered a certain degree of corrosion. It is thought that this is because the oxygen reduction reaction on the metal surface is activated by the corrosion reaction 200538405, generating hydroxide ions, and the pH of the metal surface is increased. Therefore, scales such as calcium carbonate are deposited and covered on the metal surface, so the oxygen supply amount is reduced. As a result, the corruption reaction was suppressed.

However, although the adhesion of scale on the metal surface can suppress the corrosion reaction, the adhesion of a large amount of scale causes a decrease in efficiency due to the hindered heat transfer in the heat exchanger or the reaction flea, which results in poor performance. In addition, in the piping system, the fluid passage becomes narrow due to scale, which causes the pump discharge pressure to increase, and various obstacles such as clogging of the piping may occur in a significant case. In order to prevent the precipitation of calcium carbonate, it is effective to add a phosphorus compound such as phosphonic acid or polyphosphoric acid or a maleic acid polymer. Adding these compounds in an open circulation cooling water system can generally prevent the precipitation of calcium carbonate and prevent scale and scale. Influence (for example, refer to JP 9-174092). However, when the water quality of the water system exceeds the limit of the calcium carbonate precipitation prevention performance of these compounds, the carbonic acid is approximately crystallized rapidly, causing scale disturbance. Moreover, when a filler compound or a zinc salt is used, the precipitation of calcium phosphate or zinc zinc phosphate also causes obstacles. Therefore, the water quality to which these compounds can be applied is limited, the upper limit of their concentration multiples are also limited, and their use is limited. SUMMARY OF THE INVENTION The object of the present invention is to provide a cooling water treatment method and method capable of preventing corrosion of metal equipment such as carbon steel, copper, copper alloy, and other metal equipment and equipment in an open circulating cooling water system, and scale obstacles, without causing the above problems. Treatment agent 0 The cooling water treatment method of the present invention is a cooling water treatment method that prevents corrosion of the scale of the cooling water system and prevents scale disturbance, and is characterized by adding a calcium carbonate precipitation inhibitor and carbonic acid to the cooling water. A dispersant is used to disperse the calcium carbonate particles in the cooling water to form a corrosion-resistant coating on the metal surface.

As described above, in order to suppress the corrosion of metal, although the method of forming a calcium carbonate anti-corrosion film on the surface of a metal part is effective, it is necessary to make about ions and carbonate ions in water directly generate the carbonic acid anti-residue film. It is slow, and its concentration is insufficient for sufficiently suppressing the corrosion of the metal corrosion site, so it is not practical. In addition, since the supply of plasma to the metal surface depends on the diffusion in water, it is easily affected by the flow rate or concentration in the system, and it is difficult to form the coating stably and reliably. In the present invention, the calcium carbonate acting on the corroded parts of the metal can exist in the cooling water in the form of dispersible particles in advance, and the supply amount to the rotten parts is increased, so that the calcium carbonate anticorrosive film is stably and reliably formed in the early stage. On the one hand, by increasing its dispersibility, it prevents the excessive adhesion of scale and prevents the obstacle of scale. In other words, in the present invention, in order to form the fine calcium carbonate particles, a combination of: a carbonic acid # 5 precipitation preventing agent for preventing the precipitation of calcium carbonate; and a calcium carbonate dispersing agent for exceeding The carbon dioxide & & anti-precipitation preventive agent has a carbon dioxide produced in water having a limit of precipitation prevention performance, and is not coarsened and dispersed in a particle size within a certain range. In the present invention, it is preferable to add 1 to 100 mg / L of calcium carbonate precipitation inhibitor and calcium carbonate dispersant to the cooling, respectively, while dispersing calcium carbonate particles at 5 to 100 mg / L, and cooling water, Saturation of hexa & solution calcium carbonate refers to at least one substance of fumaric acid, (2) polyacrylic acid, polymethacrylic acid, fumaric acid, polyacrylate, polymethylpropionate, itaconic acid At least one substance,

200538405 number reached 1.2 ~ 3.5. As the carbonic acid precipitation inhibitor used in the present invention, one selected from the following (1) phosphonic acid-based compounds, the following (2) meta-acid polymers, and the following fluorene carboxylic acid-based copolymers is preferred. More than two substances. > (1) hydroxyethylene dicarboxylic acid, 2-phosphonobutane · H4 · tricarboxylic acid, aminotrimethylenephosphonic acid, 1-phosphonic acid fluorene? Preparation of butane-1,2,3,4-tetrakidic acid and phosphonic acid polymaleic acid, polycoated polymaleic acid salt and poly (3) containing more than 50 mole% of white One or two or more carboxylic acid components selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, and salts thereof on the μ-based base, and a selection of 5 mol% or more A copolymer of one or two or more unsaturated hydrocarbon components in a group consisting of C4 to ci0 alkene, styrene, and dicyclopentadiene. The calcium carbonate dispersant used in the present invention is preferably from One or two or more selected from the following (4) acid-generating copolymer and the following (5) non-ionic polymer: (4) containing 30 mol% or more of acrylic acid, methacrylic acid, and butylene One or two or more carboxylic acid components selected from diacid, itaconic acid, and salts thereof, and 5 mol% or more of vinyl sulfonic acid, allyl sulfonic acid, phenethyl acid, isoamyl Copolymer of one or two or more unsaturated hydrocarbon components containing a continuous acid group selected from the group consisting of mono-Wakizaki acid, 3-propionyl-2-acrylic acid and salts thereof 6 200538405 (5) Polyacrylamide, polyvinyl alcohol, polyethylene glycol, polypropylene glycol and ethylene glycol-propylene glycol block copolymer. In the present invention, carbonic acid is used to prevent metal corrosion and scale formation. For this purpose, for example, it is preferable to use the following method (i) or (i) to precipitate and disperse calcium carbonate particles in cooling water. (I) Add calcium salts, bicarbonates, A method in which one or two or more substances selected from carbonates and alkali metal hydroxides are brought into contact with air to precipitate and disperse the calcium carbonate particles; (ii) raising the water temperature of the cooling water, A method for precipitating and dispersing the calcium carbonate particles.

The cooling water treatment agent of the present invention contains 5 to 95% by weight of one or two selected from the (1) phosphonic acid-based compound, the (2) carboxylic acid polymer, and the (3) carboxylic acid-based copolymer. More than one calcium carbonate precipitation inhibitor, and 5 to 95% by weight of one or two or more carbonic acid dispersants selected from the above (4) carboxylic acid-based copolymer and the above (5) nonionic polymer, can be used in the present invention Invented cooling water treatment method. By adopting the cooling water treatment method and the treatment agent of the present invention, calcium carbonate of a suitable thickness can be produced stably and early on the metal surface in the cooling water system without causing scale disturbance, but can fully exert the anti-corrosion effect. The coating can reliably prevent scale problems while suppressing the metal corrosion. [Embodiment] The cooling water treatment method and treatment agent of the present invention will be described in detail below. In the cooling water treatment method of the present invention, a carbonate precipitation inhibitor and a calcium carbonate dispersant are added to the cooling water to disperse the calcium carbonate particles. In the cooling water, an anticorrosive coating is formed on the metal surface in the water system.

As the calcium carbonate precipitation inhibitor added to the cooling water, substances that have been used as calcium carbonate scale inhibitors in the past can be used, but preferably include the following (1) phosphonic acid-based compounds, and (2) ) The carboxylic acid polymer is one or two or more selected from the following (3) meta-acid copolymers. (1) hydroxyethylene dicarboxylic acid, 2-phosphonic acid butane-1,2,4-trichinic acid, aminotrimethylenephosphonic acid, phosphonic acid butane-anhydrotetracarboxylic acid and phosphine At least one of acid-based fumaric acid, (2) polyacrylic acid, polymethacrylic acid, polymaleic acid, polyitaconic acid, polyacrylate, polymethacrylate, polymaleic acid At least one of acid salt and polyitaconate. The molecular weight of these carboxylic acid polymers is preferably about 500 to 5000. (3) 40 mol% or more each, preferably from 50 to 90 mol%, selected from salts of propionyl methyl methacrylate, maleic acid, itaconic acid, and the like One or two or more carboxylic acid components, and more than 5 mol%, preferably 10 to 50 mol% of C4 to C10 alkenes (such as isobutene, butene, isoprene, etc.), styrene and A copolymer of one or more unsaturated hydrocarbon components selected from unsaturated hydrocarbon components such as dicyclopentadiene. The molecular weight of these carboxylic acid copolymers is preferably about 1,000 to 20,000. As the calcium carbonate dispersant, it is preferable to use a substance having a functional group which, when adsorbed on a carbonic acid group, orients a charged hydrophilic group such as a hydrocarbyl group and a hydrophobic group such as an ether toward the outside. Prevention of particle-to-particle approach; 200538405 Examples of the calcium carbonate dispersant include one or two or more selected from the following phosphonate copolymers (4) and non-ionic polymers (5) below. (4) one or two or more selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like Carboxylic acid component, and more than 5 mol%, preferably from 10 to 50 mol% from vinyl sulfonic acid, allyl dicarboxylic acid, styrene sulfonic acid, isoprene sulfonic acid, 3-allyl A copolymer of one or two or more kinds of unsaturated hydrocarbon components containing a sulfonic acid group selected from oxy-2-hydroxypropanesulfonic acid and salts thereof. The molecular weight of these acid-based copolymers is preferably about 1,000 to 20,000. (5) At least one of polypropylene amide, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, and ethylene glycol-propylene glycol block copolymer. The molecular weight of these non-ionic copolymers is preferably about 5,000 to 100,000. The amount of the calcium carbonate precipitation inhibitor and the calcium carbonate dispersant added in the cooling water is sufficient as long as the amount of the calcium carbonate precipitation inhibitor and the calcium carbonate dispersant is sufficient to obtain a sufficient effect. Iso's are generally 1 to 100 mg / L, preferably 5 to 50 mg / L as Θ, and the total amount of calcium carbonate precipitation inhibitor and calcium carbonate dispersant is about 10 to 100 mg / L. When the addition amount of the calcium carbonate precipitation inhibitor and the calcium carbonate dispersant is too small, a sufficient addition effect cannot be obtained, while too much is uneconomical, and the generation of calcium carbonate fine particles is often slowed down. In addition, especially in the case of a phosphorus compound, it is not preferable due to the problem of precipitation of calcium phosphate and the problem of drainage treatment. In the present invention, the necessary dispersion amount of the calcium carbonate particles dispersed in the cooling water varies depending on the type of metal for cooling and anti-corrosion objects, the water quality and temperature of the cooling water of the treatment objects, and it is generally about 1 to 1000 mg / liter, with 5 ~ 1QQ mg / 200538405 Examples 1 to 7 and Comparative Examples 1 to 1 4 The intermittent cooling water system evaluation test device shown schematically in Fig. 1 was used to check the corrosion prevention effect and scale prevention effect in the examples and comparative examples. . The water quality of the industrial water used in the test is shown in Table i below. The calcium carbonate precipitation inhibitor and calcium carbonate dispersant used are shown in Table 2 below.

Installation Table 1 Industrial water quality, PH 7.4 Electrical conductivity (mS / m) 33 ___ Μ Test (mg / Las CaC03) 80 ^ __ Total hardness (mg / Las CaC03) —120 ___ Approximate hardness (mg / Las CaC03) 80 __ silicon dioxide (mg / L) 25 ^ 2_ calcium carbonate precipitation inhibitor A-maleic acid / acrylic acid / styrene copolymer (Molar ratio 60.25: 15, molecular weight 10000) B -—- ^ maleic acid / isobutylene copolymer (molar ratio 1: 1, eight weight 14000) polyacrylic acid (molecular weight 2000) 'D polymaleic acid (molecular weight 60 ^^' Η amine Trimethylenephosphonic acid '-F hydroxyethylenephosphonic acid G 2-phosphonic acid butane-1,2,4-tricarboxylic acid ^' '-------- 12 200538405 carbonic acid Dispersant a Polyvinyl alcohol (molecular weight 20000) b Polyethylene glycol (molecular weight 12000) c Acrylic acid / vinyl sulfonic acid copolymer (Molar ratio 75: 25, molecular weight 5000) d Acrylic acid / allylic sulfonic acid copolymer (Molar ratio 70: 30, molecular weight 3000) e Acrylic acid / styrene sulphonic acid copolymer (Molar ratio 80: 20, molecular weight 8000) f Acrylic acid / 3 · propanthoxy-2-hydroxypropanesulfonic acid copolymer ( Morse ratio 80: 20, points Amount 3000) g • Acrylic acid / hydroxymethacrylate / isoprenesulfonic acid copolymer (Molar ratio 70: 10: 20, molecular weight 13000)

In the evaluation test device shown in FIG. 1, circulating cooling water is supplied from the cooling tower 1 to the heat exchanger 3 by means of a circulating pipe 2 having a pump P1, and the return water is returned to the cooling tower 1 through the pipe 4. 5 is an introduction pipe for make-up water , 6 is an introduction pipe of an aqueous solution of sodium hypooxygenate, 7 is an introduction pipe of a medicine shown in Table 3, and 8 is a flow pipe, each of which has pumps P2, P3, and P4 * p5. The heat exchanger 3 is a steam-heated tube water-through heat exchanger provided with three carbon steel tubes with an outer diameter of 19 mm, a length of 1,500 mm, and a thickness of 2 3 $ meters. . 9 is a pipeline piping with a valve 9a. The operating conditions of this evaluation test device are as follows. [Operating conditions] Retained water volume: 350 liters of circulating water volume · 80 liters / minute (including cooling tower water circulation of heat exchanger pipes) 13 200538405 Flowing water volume: 4 · 5 ~ 9 · 5 liters / hour ( (According to the concentration multiple leaf) Make-up water: industrial water make-up water volume: 24 ~ 29 liters / hour (according to the concentration multiple) flow rate · 0.3 m / s concentration multiple: as shown in Table 3 heat exchanger inlet water temperature: 30 ° C Outlet water temperature of the heat exchanger: 50 ° C (steam heating)

Temperature difference of water temperature △ t: 20eC Sodium acid addition amount: Continuous injection to make the residual chlorine concentration in the cooling water reach 0.3 ~ 0.5 mg / liter of the added amount of the agent. Pharmacy. The above operation was performed for 30 days, and the corrosion rate (carbon steel) was measured once / day with a corrosion meter. The calcium hardness analysis in the cooling water was performed once a week. The Millipore filter (millipore niter) of 0.1 micron was used to pass through the cooling water, and the approximate hardness of the filtrate was determined by titration. In addition, the calcium hardness of the portion captured by the screening program was boiled by adding hydrochloric acid and then measured by atomic absorption method. After 30 days of operation, the test tube was taken out of the heat exchanger, and it was cut at intervals of 20 cm after drying to evaluate adhesion and corrosion holes. The attachment of the test tube was removed with a metal brush, and the scale adhesion speed was calculated from the dry weight and the area of the tube. The test tube after the attachment was removed was pickled with hydrochloric acid added with a corrosion inhibitor, and the corrosion product was removed. The depth of the hole on the surface of the test tube was measured with a depth gauge to determine its maximum value. The calcium hardness of the filtrate, the calcium hardness of the filtering and capturing part, and the corrosion rate of the tube in the heat exchanger are shown in Table 3 and Table 6 below. Among them, the measured values of the exhaustion rate, the calcium hardness of the filtrate, and the calcium hardness of the filtering and capturing part, and the average value of this period are not used. ffib η * Calcium hardening product, Table 3 also records the value of the concentration factor of the make-up water (industrial water), deducting the calcium hardness of the filtrate and filtering to capture the calcium content of the filter + i X The difference between and is used as an indicator of the tendency to scale. The saturation index of calcium carbonate dissolved in cooling water is shown in Table 3. Fortunately, the amount of calcium carbonate particles with a particle size of 0 · i ~ ^ 0 micron dispersed in the cooling water is calculated from the calcium hardness of the 0.1 micron filter capture part. 0 ~ 30 mg / l 0

15 200538405

Table 3 Example of cooling water quality Calcium carbonate precipitation inhibitor Calcium carbonate dispersant Refrigerant hardness (CaC03) in cooling water 5 mg / Las Evaluation of dissolution in cooling water Species concentration (mg / L) Species concentration (mg / L) 0.1 micron The 0.1-micron filtrate of the filtrate captures the saturation index of carbonic acid # 5, which has a tendency to scale. * 4 Corrosion rate (m dd) Corrosion hole depth (m τη / month) Scale adhesion rate (mg / c m2 / month) Example 1 3 times industrial water Concentrated water A 30 a 40 210 30 0 1.44 2.3 0.17 4.7 2 B 5 b 20 230 10 0 1.57 3.4 0.13 2.8 3 C 10 c 5 230 5 5 1.57 3.9 0.15 3.4 4 4 times industrial water concentrated water D 20 d 20 300 15 5 1.96 2.7 0.21 9.8 5 E 6 e 20 315 5 0 2.03 2.3 0.17 3.6 6 F 6 f 15 310Π 5 5 2.01 1.8 0.16 2.1 7 X t water 5 times concentrated water G 14 g 25 380 15 5 2.31 1.0 0.20 5.5 Comparative example 1 Industrial water 3 times concentrated water A 80 213 0 27 1.45 16.0 0.38 4.3 2 B 20 240 0 0 1.63 4.0 0.25 5.2 3 C 20 230 5 * 1 5 L60 8.9 0.47 37.6 4 Industrial water 4 times concentrated water D 40 310 0 10 2.01 7.2 0.37 38.0 * 3 5 E 30 316 0 4 2.0 4 1.8 0.30 24.3 · 2 6 F 20 310 0 10 2.01 1.6 0.28 27. Γ2 7 Industrial water 5 times concentrated water G 40 376 0 24 2.30 1.9 0.26 11.7 ”8 Industrial water 3 times concentrated water a 80 155 0 85 0.99 60.5 0.44 38.0 9 b 40 160 0 80 1.04 43.2 0.52 27.6 1 0 c 20 200 0 40 1.37 13.8 0.34 6.0 1 1 4 times concentrated water for industrial use d 40 250 0 70 1.69 14.6 0.38 4.2 1 2 e 30 180 0 140 1.21 28.0 0.42 15.6 1 3 f 30 250 0 70 1.69 5.9 0.36 1.4 1 4 Industrial water 5 times concentrated water g 40 230 0 170 1.57 8.3 0.32 2.3 * 1 The catcher of the transition device is the gel of polymer and calcium ion * 2 The component is calcium phosphate * 3 The main component of the attachment is magnesium silicate * 4 The calcium hardness of the make-up water (industrial water) x the concentration multiple of one (calcium hardness of the filtrate + calcium hardness of the filter capture) shows that the invention can simultaneously prevent cooling Gold 16 200538405 in the water system is a scum and scale barrier. [Brief Description of the Drawings] Fig. 1 is a system diagram showing an outline of an intermittent cooling water system evaluation test device used in Examples and Comparative Examples. [Description of main component symbols]

1 Cooling tower 2 Circulation piping 3 Heat exchanger 4 piping 5 Make-up water introduction piping 6 Sodium hypochlorite aqueous solution introduction piping 7 Medicament introduction piping 8 Flow piping 9 Pipe piping 9a Valves P1 ~ P5 pumps

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Claims (1)

200538405 The scope of patents applied for and read: ·; · '·: /: /:-'. ^ Νν;,;:-;-:: ^ ···: · ν · :; Η;; Λ ^ Γ-:: ^; · 1 · A cooling water treatment method, which prevents corrosion of metals in the cooling water system while preventing scale disturbance, and is characterized by adding a calcium carbonate precipitation inhibitor and ten carbonate to the cooling water. A dispersant disperses the carbonated # 5 fine particles in the cooling water to form an anticorrosive coating on the metal surface. 2. The cooling water treatment method according to item 1 of the scope of the patent application, wherein i ~ 100 mg / L of calcium carbonate precipitation inhibitor and carbonic acid dispersant are added to the cooling water, respectively, so that the calcium carbonate particles are reduced by 5 to 〇OOmg / L dispersion while making the saturation index of calcium carbonate dissolved in this cooling water is 12 ~ 35. 18 200538405 more than one carboxylic acid component, and more than 5 mol% of one or two or more unsaturated hydrocarbon components selected from the group consisting of alkenes, styrene and dicyclopentadiene Copolymer. 4. The cooling water treatment method according to any one of claims 1 to 3 in the scope of Shenyin's patent, wherein the calcium carbonate dispersant is obtained from the following (4) carboxylic acid copolymer and the following (5) nonionic polymerization One or two or more selected from a group of objects, (4) One or two or more carboxylic acid components selected from the group consisting of valproic acid, methacrylic acid, maleic acid, itaconic acid, and the salts thereof in an amount of 30 mol% or more And more than 5 mol% from ethynylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, 3-allyl-2-hydroxypropanesulfonic acid and the like One or two or more copolymers of unsaturated smoke components containing a tank acid group selected from the group consisting of salts, (5) Polyacrylamide, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, and ethylene glycol- At least one of propylene glycol block copolymers. 5. The cooling water treatment method according to any one of claims 1 to 4 in the scope of patent application, wherein the cooling water is added with a group selected from the group consisting of about salt, bicarbonate, acid salt, and metal hydroxide. One or two or more substances are brought into contact with air to precipitate and disperse the carbonic acid dance particles. 6. The cooling water treatment method according to any one of claims 1 to 5, wherein the calcium carbonate particles are precipitated and dispersed by raising the water temperature of the cooling water. 19 200538405 7 · A cooling water treatment agent, which contains 5 to 95% by weight of 0 / 〇 from the following (1) phosphonic acid-based compound, the following (2) carboxylic acid polymer, and the following (3) One or two or more calcium carbonate precipitation inhibitors selected from the group consisting of acid copolymers, and 5 to 95% by weight of the following (4) carboxylic acid copolymers and (5) nonionic One or two or more acid-breaking # 5 dispersants selected from the group consisting of polymers, (1) hydroxyethylene dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, aminotrimethylenephosphonic acid, 1-phosphonobutane-1,2,3 At least one of 4,4-tetracarboxylic acid, and phosphonic fumaric acid, (2) polyacrylic acid, polyacrylic acid, polymaleic acid, polyitaconic acid, polyacrylate, polymethyl At least one of the acrylic acid salt, polymaleic acid salt, and polyitaconate salt, (3) contains 40 moles. One or two or more carboxylic acid components selected from the group consisting of acrylic acid, fluoracrylic acid, maleic acid, itaconic acid, and salts thereof, with a content of 5 mole% or more from C4 to A copolymer of one or two or more unsaturated hydrocarbon components selected from the group consisting of olefins, styrene and dicyclopentadiene of C10, (4) containing 30 mol% or more of acrylic acid, methacrylic acid, One or two or more carboxylic acid components selected from the group consisting of maleic acid, itaconic acid, and salts thereof, and more than 5 mol% of vinyl sulfonic acid, allyl sulfonic acid, and styrene One or two or more selected from the group consisting of sulfonic acid, isoprenesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, and their salts Copolymer, 20 200538405 (5) At least one of polypropylene amide, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, and ethylene glycol-propylene glycol block copolymer. a ύ% twenty one