JP2015213851A - Composition for water treatment and water treatment method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multifunctional composition for water treatment and a water treatment method that inhibit generation of scale including silica-based scale and inhibit the corrosion of a metal coming into contact with water in water systems of various types of water for irrigation and drainage, and have an effect of inhibiting slime generation.SOLUTION: A composition for water treatment contains one or two or more selected from a specific polyhydric alcohol and/or a derivative of a polyhydric phenol, and a fatty acid monoamide, and one or two or more selected from a polymer of a monoethylenically unsaturated carboxylic acid and an organic phosphorus compound.

Description

  The present invention relates to process water, cooling water, boiler water, washing water, various types of waste water for various manufacturing industries, inorganic deposits such as scale and earth and sand, microorganisms, The present invention relates to a composition for water treatment and a water treatment method for suppressing adhesion of organic deposits such as organic fouling and inhibiting corrosion of a metal in contact with water.

  In various drainage systems such as process water, cooling water, boiler water, washing water, air conditioning and chilled hot / cold water for district heating and cooling systems in various manufacturing industries such as pulp and paper manufacturing, automobile factories, and semiconductor manufacturing industries, Adherence troubles and corrosion troubles mainly composed of microorganisms are complicated.

  Since the scale causes serious obstacles to the operation of the apparatus such as a decrease in thermal efficiency and blockage in heat exchangers and pipes, countermeasures are regarded as important. Scale species produced in water systems include calcium carbonate, calcium sulfate, calcium sulfite, calcium phosphate, calcium silicate, magnesium silicate, iron silicate, magnesium hydroxide, zinc phosphate, zinc hydroxide, iron phosphate, amorphous Silica etc. are mentioned. In addition, viscous substances secreted by microorganisms may be mixed with earth and sand in the water, iron rust, and other organic substances to produce a mud called slime, which may cause many obstacles in operation and product quality.

  On the other hand, in recent years, in the cooling water system, circulation and reuse of water has become popular in order to reduce the amount of water used. In the cooling water circulation system, water is cooled by partially evaporating in the cooling water tower, so that the dissolved content of the cooling water system is concentrated and increased. As a result, not only will scale adherence increase, it will be a favorable situation for underwater microbial activity, and slime formation will increase. The adhesion of scale and slime brings about adverse effects such as poor water flow of the strainer in the water system, a decrease in the heat conduction of the heat exchanger, a decrease in the flow rate of the pipe, blockage of the pipe, and metal corrosion. In the pulp and paper manufacturing industry, a large amount of water was used to drain water, but the reuse of water in the pulp and paper manufacturing process has been promoted due to the response to the increase in wastewater treatment costs and the growing awareness of environmental conservation. . In particular, the papermaking process uses a wide variety of chemicals such as starch, sizing agent, yield improver, paper strength agent, latex resin, etc. Inviting, it is a favorable environment for scale adhesion and microbial growth. Scale and slime generated in such an environment adheres to the walls of tanks and pipes in the process, grows to a certain extent, peels off from the wall surface, mixes in the pulp slurry, and is made into paper. The paper strength is reduced, leading to paper breakage in the pressing process and the drying process, and also causing generation of coloring, spots, eyeballs, and the like, and the product value is significantly reduced.

  Conventionally, scale inhibitors, corrosion inhibitors, slime control agents, slime release agents, etc. have been added separately to suppress these various obstacles in water systems, but increasing the number of chemicals increases water treatment costs. In addition, the environmental load of drainage was increased, and the maintenance of chemicals was complicated.

  Therefore, treatment methods and treatment agents that have both the effects of scale inhibition and metal corrosion inhibition have been proposed. For example, 30-80% by weight of maleic anhydride, 10-40% by weight of ethyl acrylate, and 10-30% by weight of styrene or 1-decene are added to form a terpolymer, to precipitate a scale, disperse a suspended solid, and a metal. For preventing corrosion of metal (see Patent Document 1), prevention of corrosion of metal surface containing copolymer hydrolyzate of 80 to 90 mol% maleic anhydride and 10 to 20 mol% olefin having 5 to 12 carbon atoms An effective scale inhibitor (see Patent Document 2) is disclosed.

  However, these treatment methods and treatment agents are effective for calcium carbonate scale, but have no effect on silica-based scale. For this reason, it is necessary to use together the scale inhibitor with respect to a silica type scale separately.

  On the other hand, polyethylene glycol and phosphonic acid having a molecular weight of 1000 to 100,000 and / or a carboxyl having a molecular weight of 100,000 or less are considered to have a remarkable effect on both calcium-based scales represented by calcium carbonate scales and silica-based scales. Although a scale inhibitor containing an acid polymer (see Patent Document 3) is disclosed, this scale inhibitor did not exhibit a sufficient scale inhibitory effect in an aqueous system containing aluminum ions, iron ions, and zinc ions.

  Examples of the scale inhibitor for the silica-based scale include an acrylamide-based scale inhibitor (see Patent Document 4), a method using a quaternary ammonium salt (see Patent Document 5), and a method using a polyethyleneimine compound (Patent Document). 6), etc., but no silica-based scale inhibitor was effective. In addition, these scale inhibitors and methods have no effect of suppressing organic deposits such as microorganisms and organic fouling.

  In addition, in order to remove turbidity components in water, a method of adding an aluminum compound such as polyaluminum chloride, aluminum sulfate, or sodium aluminate is generally performed. Amorphous silica scale and aluminum silicate scale are deposited in a wide temperature range from high to high. However, an effective silica-based scale inhibitor has not yet been found even in the presence of such aluminum.

  In this way, process water, cooling water, boiler water, washing water for various manufacturing industries such as the pulp and paper manufacturing industry, the automobile industry, and the semiconductor manufacturing industry, and various types of wastewater such as air conditioning and district heating and cooling systems However, it has been desired to solve the various problems of scale, corrosion of metal in contact with water and slime by adding a single composition. However, effective inhibitors and methods for silica-based scale have been found. The composition was not obtained because it was not released.

Japanese Patent No. 2942991 Japanese Patent Publication No. 5-81320 JP-A-2-31894 Japanese Patent No. 1851103 JP-A-57-110398 Japanese Patent No. 2974378

  The subject of the present invention is not only calcium-based scales, but also silica-based scales for which effective production suppression methods have not been obtained in the past, as well as suppressing their generation, and also suppressing corrosion of metals in contact with water, It is another object of the present invention to provide a multifunctional water treatment composition and a water treatment method that have an effect of suppressing slime generation.

  As a result of intensive studies to solve the above-described problems, the present inventors have found that specific polyhydric alcohols and / or polyhydric phenols may be used even if they contain aluminum ions, iron ions, zinc ions, or the like in water. By applying to a target aqueous system a composition containing one or more selected from derivatives and fatty acid monoamides and a polymer of a monoethylenically unsaturated carboxylic acid and / or an organophosphorus compound, The technology is not effective enough, especially in the presence of aluminum ions etc. In the presence of an effective inhibitor, it has a remarkable inhibitory effect on silica-based scales, and on calcium-based scales etc. In addition to having an inhibitory effect, a synergistic effect on these scales can be obtained, corrosion of metals in contact with water can be suppressed, and slime generation can be suppressed at the same time. , These overall effect was reached the present invention that the entire deposit can be reduced greatly. The effect of the present invention, which can suppress the generation of scale containing silica-based scale by adding one composition, suppress the corrosion of metals that come into contact with water, and further suppress the generation of slime. Is an excellent and unexpected effect.

  That is, the invention according to claim 1 is a water treatment composition comprising the following component (a) and component (b) as active components, wherein component (a) is ethylene (A): Polyethylene other than glycol and / or polyhydric phenol ethylene oxide adduct, (B) polyglycidyl ether of polyhydric alcohol and / or polyhydric phenol, (C) polyglycidyl ether of polyhydric alcohol and / or polyhydric phenol (D) polyhydric alcohol and / or addition reaction product of polyhydric phenol and polyglycidyl ether, and (E) one or more compounds selected from fatty acid monoamides, (b) The components include (F) a polymer of monoethylenically unsaturated carboxylic acid and water-soluble salt thereof, (G) organic phosphonic acid and water-soluble salt thereof, (H) phosphonoca Bon an acid and one or water treatment composition is more water-soluble salts thereof, and (I) phosphino polycarboxylic acid and a compound selected from water-soluble salts thereof.

（式中、Ｒ１およびＲ２は、それぞれ独立に水素、炭素数１〜２２のアルキル基又はアルケニル基、炭素数１〜２２のヒドロキシアルキル基又はヒドロキシアルケニル基から選択されるか、あるいはＲ１とＲ２が一緒になって環状アミドの構成単位となり、Ｒ３は炭素数８〜２２の飽和又は不飽和の脂肪酸残基である。） The invention according to claim 2 is the water treatment composition according to claim 1, wherein the (E) fatty acid monoamide of the component (a) is a compound represented by the general formula (1).

(Wherein R1 and R2 are each independently selected from hydrogen, an alkyl group or alkenyl group having 1 to 22 carbon atoms, a hydroxyalkyl group or hydroxyalkenyl group having 1 to 22 carbon atoms, or R1 and R2 are Together, they form a structural unit of a cyclic amide, and R3 is a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms.)

  The invention according to claim 3 is characterized in that the component (a) is a fatty acid monoamide represented by the general formula (1), and (c) a fatty acid monoamide solubilizer and (d) an alkali metal hydroxide. It is a composition for water treatment of Claim 2 containing this.

  The invention according to claim 4 is characterized by adding the following component (a) and component (b) below to the water system to be treated, and having the effects of scale inhibition, corrosion inhibition of metal in contact with water, and slime inhibition. A water treatment method, wherein (A) component is (A) polyhydric alcohol other than ethylene glycol and / or ethylene oxide adduct of polyhydric phenol, (B) polyglycidyl ether of polyhydric alcohol and / or polyhydric phenol (C) hydrolyzate of polyglycidyl ether of polyhydric alcohol and / or polyhydric phenol, (D) addition reaction product of polyhydric alcohol and / or polyhydric phenol and polyglycidyl ether, and (E) fatty acid monoamide 1 type or 2 types or more of selected compounds, (B) component is a polymer of (F) monoethylenically unsaturated carboxylic acid and its water A compound selected from the group consisting of: (G) organic phosphonic acid and its water-soluble salt, (H) phosphonocarboxylic acid and its water-soluble salt, and (I) phosphinopolycarboxylic acid and its water-soluble salt. Or it is the water treatment method which is 2 or more types.

  In the present invention, it is found that the combined use of the component (A) and the component (B) provides not only a simple additive effect of the silica-based scale inhibitory effect and the calcium-based scale inhibitory effect but also a remarkable synergistic effect. It was done. It has also been found that this combined use exerts the effect of inhibiting corrosion and slime of metals that come into contact with water. It is a great advantage of the present invention that these multiple effects can be obtained by adding one composition to the water system to be treated.

  By applying the composition for water treatment and the water treatment method of the present invention to a water system to be treated, scales including silica-based scales, corrosion of metals in contact with water, and slime can be suppressed, so scales, corrosion products, and slimes In addition, deposits including earth and sand can be significantly reduced. For this reason, the complicated chemical injection management which adds various chemical | medical agents separately becomes unnecessary, can reduce the water treatment cost and can be economical, and can reduce the environmental load of waste_water | drain.

It is a systematic diagram which shows the test apparatus used for the Example.

  The processing target water system of the present invention includes process water of various manufacturing industries such as pulp and paper manufacturing industry, automobile factory, semiconductor manufacturing industry, cooling water, boiler water, washing water, air conditioning and cold / hot water for temperature control of district air conditioning systems, etc. Includes various drainage systems.

  The scale in the present invention includes various scales such as a calcium-based scale, a magnesium-based scale, and a silica-based scale that are generated in various waste water systems. Conventionally, silica-based scales that could not effectively suppress precipitation include general silica scales in which silica in water alone precipitates as amorphous silica, and the reaction between silica in water and polyvalent metal ions reacts Silicate scales that precipitate as metal silicates are included. Here, the silicate includes all types of polyvalent metal silicates such as magnesium silicate, calcium silicate, aluminum silicate, iron silicate, and zinc silicate. The water treatment composition of the present invention has an excellent inhibitory effect on these silica-based scales.

  In the present invention, the corrosion of the metal in contact with water is the corrosion on the metal surface in contact with water among the iron-based metal and copper-based metal used in the equipment, equipment and piping installed in the water system to be treated. Specifically, metal corrosion on the water flow side of the heat exchanger, the inside of the water flow piping, the inner surface of the water tank or the water tank, the inside of the water scrubber, and the like can be mentioned.

  The slime in the present invention includes an aggregate of microorganisms and dead bodies generated in the water system of various wastewaters, a secretion of microorganisms, an aggregate of suspended substances and sediment components collected by the microorganism, and the like. It is attached or deposited on the water side surface of equipment or piping.

  The component (a) used in the present invention includes (A) a polyhydric alcohol other than ethylene glycol and / or an ethylene oxide adduct of polyhydric phenol, (B) a polyglycidyl ether of polyhydric alcohol and / or polyhydric phenol, (C) hydrolyzate of polyglycidyl ether of polyhydric alcohol and / or polyhydric phenol, (D) addition reaction product of polyhydric alcohol and / or polyhydric phenol and polyglycidyl ether, and (E) fatty acid monoamide Is done.

  The (A) component (A) polyhydric alcohol and / or polyhydric phenol ethylene oxide adduct used in the present invention is, for example, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3- Propanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (= neopentyl glycol), 2-ethyl-1, 3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, cyclohexane-1,4-dimethanol, poly Tetramethylene ether glycol, p-xylene glycol, pentaerythritol Sorbitol, sorbitan, dipentaerythritol, glycerin, diglycerin, polyglycerin, sucrose, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 2,2-bis (4-hydroxyphenyl) methane (= Bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (= bisphenol C), 2,2-bis ( 4-hydroxyphenyl) butane (= bisphenol B), 1,1-bis (4-hydroxyphenyl) cyclohexane (= bisphenol Z), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (= bisphenol AP) ), Bis (4-hydroxyphenyl) sulfone = Bisphenol S), 2,2-bis (4-hydroxycyclohexyl) propane, hydroquinone, resorcin, catechol, bis (4-hydroxyphenyl) ether, 1,1,2,2-tetraxy (4-hydroxyphenyl) ethane, etc. Or an ethylene oxide adduct of a mixture thereof. Here, a part of ethylene oxide may be replaced with propylene oxide within a range that does not affect the scale suppression effect.

  The number of moles of ethylene oxide (EO) added in the ethylene oxide adduct of polyhydric alcohol and / or polyhydric phenol other than (A) ethylene glycol of component (A) used in the present invention is usually in the range of 1-30. , Preferably in the range of 2-20.

  In order to obtain a sufficient scale inhibiting effect in the (A) polyhydric alcohol other than ethylene glycol and / or an ethylene oxide adduct of polyhydric phenol used in the present invention, the polyhydric alcohol used and / or Alternatively, it is preferable that the polyhydric phenol molecule does not have a hydrophobic group having a large carbon number, and specifically, the hydrophobic group preferably has 10 or less carbon atoms.

  More preferable examples of (A) polyhydric alcohols other than ethylene glycol and / or polyhydric phenol ethylene oxide adducts used in the present invention include pentaerythritol, glycerin, trimethylolethane, trimethylolpropane, It is selected from ethylene oxide adducts of polyhydric alcohols having 3 or more hydroxyl groups such as sorbitol and sorbitan.

  As the (A) component (A) polyhydric alcohol and / or polyhydric phenol ethylene oxide adduct used in the present invention, those commercially available can be used as they are. For example, ethylene oxide adducts of glycerin are trade names of UNIOX G-450 and G-750 from NOF Corporation, and ethylene oxide adducts of trimethylolpropane are TMP-30 and TMP-60 from Nippon Emulsifier Co., Ltd. Under the trade name, pentaerythritol ethylene oxide adduct is a product name of PNT-40 from Nippon Emulsifier Co., Ltd., ethylene oxide adduct of neopentyl glycol is a trade name of NGE-04 from Yokkaichi Synthesis Co., Ltd., and ethylene oxide of bisphenol A The adduct is commercially available from NOF Corporation under the trade name UNIOR DA-400 or DA-700.

  The (B) polyhydric alcohol and / or polyglycidyl ether of polyhydric phenol used in the present invention is, for example, a compound obtained by reaction of polyhydric alcohol and / or polyhydric phenol with epihalohydrin. The production method thereof is disclosed in, for example, JP-A-61-178974. Examples of the polyhydric alcohol and / or polyhydric phenol used here include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, and 2-methyl. -1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (= neopentyl glycol), 2-ethyl-1,3-propanediol, 1 , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, cyclohexane-1,4-dimethanol, polytetramethylene ether glycol, p Xylene glycol Pentaerythritol, sorbitol, sorbitan, dipentaerythritol, glycerin, diglycerin, polyglycerin, sucrose, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 2,2-bis (4-hydroxyphenyl) Methane (= bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (= bisphenol C), 2,2 -Bis (4-hydroxyphenyl) butane (= bisphenol B), 1,1-bis (4-hydroxyphenyl) cyclohexane (= bisphenol Z), 1,1-bis (4-hydroxyphenyl) -1-phenylethane ( = Bisphenol AP), bis (4-hydro Cyphenyl) sulfone (= bisphenol S), 2,2-bis (4-hydroxycyclohexyl) propane, hydroquinone, resorcin, catechol, bis (4-hydroxyphenyl) ether, 1,1,2,2-tetraxy (4-hydroxy) Phenyl) ethane alone or a mixture thereof may be mentioned, or an adduct of ethylene oxide and / or propylene oxide may be used. The epihalohydrin used here is selected from, for example, epibromohydrin, epichlorohydrin, epiiodohydrin, β-methylepibromohydrin, β-methylepichlorohydrin, and the like.

  The polyglycidyl ether of (B) polyhydric alcohol and / or polyhydric phenol of component (A) used in the present invention is, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol Diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl Ether, hydroquinone diglycidyl ether, bisphenol A diglycidyl Ether and the like.

  Preferred examples of (B) polyhydric alcohol and / or polyglycidyl ether of polyhydric phenol used in the present invention are ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether. is there.

  As the (B) polyhydric alcohol and / or polyglycidyl ether of polyhydric phenol used in the present invention, commercially available ones can be used as they are. For example, ethylene glycol diglycidyl ether is a trade name of Denasel EX-810 (epoxy equivalent 113) or Denacol EX-811 (epoxy equivalent 132) from Nagase Chemitex Co., Ltd., and diethylene glycol diglycidyl ether is Nagase Chemitex Co., Ltd. The product name is Denacol EX-850 (epoxy equivalent 122) or Denacol EX-851 (epoxy equivalent 150), and polyethylene glycol diglycidyl ether is Denasel EX-821 (epoxy equivalent 185), Denacol EX from Nagase ChemteX Corporation. -830 (epoxy equivalent 268), Denacol EX-832 (epoxy equivalent 284), Denacol EX-841 (epoxy equivalent 372), Denacol EX-861 (epoxy equivalent 551) It is commercially available respectively under the trade name that.

  The hydrolyzate of polyglycidyl ether of (C) polyhydric alcohol and / or polyhydric phenol of component (A) used in the present invention is obtained by adding water and alkali to polyglycidyl ether of polyhydric alcohol and / or polyhydric phenol. It can obtain by adding and heating. As the polyglycidyl ether of the polyhydric alcohol and / or polyhydric phenol used here, the compounds mentioned as the polyglycidyl ether of the (B) polyhydric alcohol and / or polyhydric phenol can be used.

  Preferred examples of the hydrolyzate of polyglycidyl ether of (C) polyhydric alcohol and / or polyhydric phenol of component (A) used in the present invention include hydrolyzate of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether A hydrolyzate of polyethylene glycol diglycidyl ether.

  As the polyhydric alcohol and / or polyhydric phenol used in the addition reaction product of (D) polyhydric alcohol and / or polyhydric phenol and polyglycidyl ether of component (a) used in the present invention, the above (B) Use of the compounds mentioned as polyhydric alcohols and / or polyhydric phenols used in the preparation of polyhydric alcohols and / or polyglycidyl ethers of polyhydric phenols, or the adducts of these compounds with ethylene oxide and / or propylene oxide In addition, as the polyglycidyl ether to be used, the compounds listed as the polyglycidyl ether of (B) polyhydric alcohol and / or polyhydric phenol can be used, but polybasic acid such as diglycidyl phthalate can be used. Polyglycidyl ether may be used.

  The addition reaction product of (D) polyhydric alcohol and / or polyhydric phenol and polyglycidyl ether of component (a) used in the present invention includes, for example, polyglycidyl ether added to polyhydric alcohol and / or polyhydric phenol. It can be obtained by heating to 30 to 200 ° C. in the presence of an acid catalyst. Examples of the acid catalyst include Lewis acid catalysts such as boron trifluoride diethyl ether, zinc borofluoride, potassium borofluoride, tin borofluoride, aluminum chloride, and tin chloride.

  (D) Polyhydric alcohol and / or polyhydric phenol and polyglycidyl ether for preparing an addition reaction product of (D) polyhydric alcohol and / or polyhydric phenol and polyglycidyl ether used in the present invention A preferable reaction ratio is a range of 0.5 to 2 epoxy equivalents of polyglycidyl ether with respect to 1 mol of polyhydric alcohol and / or polyhydric phenol. If this reaction ratio is deviated, sufficient scale inhibiting performance may not be obtained, and the reaction product may gel, which is not preferable.

  Preferred examples of the addition reaction product of (D) polyhydric alcohol and / or polyhydric phenol and polyglycidyl ether of component (a) used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, sorbitol, Addition product of one or more selected from pentaerythritol, glycerin, trimethylolethane, and trimethylolpropane and one or more selected from ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether It is.

  The component (A) fatty acid monoamide (E) used in the present invention is a fatty acid primary to tertiary amide composed of an aliphatic hydrocarbon chain group and one carboxylic acid group, and the fatty acid is linear. Alternatively, it may be branched, saturated or unsaturated, and may be a cyclic amide.

（式中、Ｒ１およびＲ２は、それぞれ独立に水素、炭素数１〜２２のアルキル基又はアルケニル基、炭素数１〜２２のヒドロキシアルキル基又はヒドロキシアルケニル基から選択されるか、あるいはＲ１とＲ２が一緒になって環状アミドの構成単位となり、Ｒ３は炭素数８〜２２の飽和又は不飽和の脂肪酸残基である。） A more preferred example of the component (A) (E) fatty acid monoamide used in the present invention is a compound represented by the following general formula (1).

(Wherein R1 and R2 are each independently selected from hydrogen, an alkyl group or alkenyl group having 1 to 22 carbon atoms, a hydroxyalkyl group or hydroxyalkenyl group having 1 to 22 carbon atoms, or R1 and R2 are Together, they form a structural unit of a cyclic amide, and R3 is a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms.)

  A preferred fatty acid residue in the (E) fatty acid monoamide of the component (A) used in the present invention is a substituted or unsubstituted residue of a fatty acid present in vegetable oil or animal oil. The vegetable oil and animal oil are tall oil, palm oil, soybean oil, cottonseed oil, coconut oil, corn oil, peanut oil, canola oil, safflower oil, sunflower oil, babas oil, castor oil, linseed oil, olive oil, tung oil, beef tallow, You can choose from pork fat and fish fat. The fatty acid obtained here is usually a mixture of saturated or unsaturated fatty acids having different carbon numbers.

  Examples of (E) fatty acid monoamide of component (A) used in the present invention include caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid Amides, hydroxystearic acid amides, palmitoleic acid amides, oleic acid amides, linoleic acid amides, erucic acid amides, undecylenic acid amides, arachidonic acid amides, vaccenic acid amides, and saturated or unsaturated fatty acids such as vegetable and animal oil fatty acids Saturated fatty acid amide; N-monomethyl oleic acid amide, N-monoethyl linoleic acid amide, N-monoisopropyl stearic acid amide, N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N Oleyl stearic acid amide, N-stearyl erucic acid amide, N- (2-hydroxypropyl) lauric acid amide (= lauric acid-N-isopropanolamide), N- (2-hydroxyethyl) stearic acid amide, N- (2 -Hydroxyethyl) linoleic acid amide, N- (2-hydroxypropyl) stearic acid amide, N- (hydroxyoleyl) palmitic acid amide, N- (hydroxystearyl) stearic acid amide, N- (hydroxystearyl) oleic acid amide, N- (hydroxyoleyl) stearic acid amide, N- (hydroxystearyl) erucic acid amide, and N-substituted amides of saturated or unsaturated fatty acids such as vegetable and animal oil fatty acids; N, N-dimethyl stearic acid amide, N, N-dimethyl oleate N, N-dimethyllinoleic acid amide, N, N-dimethyllinolenic acid amide, N, N-dimethylricinoleic acid amide, N, N-dimethylarachidonic acid amide, N, N-dimethyleicosapentaenoic acid amide, N, N -Dimethyldocosahexaenoic acid amide, N, N-diethyloleic acid amide, N, N-dipropyloleic acid amide, N, N-oleic acid ethyllauric acid amide, N-methyl-N-hydroxyethyllauric acid amide, N- Ethyl-N-hydroxyethyl myristic acid amide, N-ethyl-N-hydroxyethyl stearic acid amide, lauric acid-N, N-diethanolamide, oleic acid-N, N-diethanolamide, linoleic acid-N, N-diethanolamide Stearic acid-N, N-diisopropanolamide, N, N-di (hydroxyoleyl) palmitic acid amide, N, N-di (hydroxystearyl) stearic acid amide, N, N-di (hydroxystearyl) oleic acid amide, N, N-di (hydroxyoleyl) stearic acid amide, N, N-di (hydroxystearyl) erucic acid amide, and N, N-substituted amides of saturated or unsaturated fatty acids such as vegetable oil fatty acids and animal oil fatty acids; dodecanoylmorpholine, N-stearamid-3-methylpiperidine, N- Examples thereof include cyclic amides of saturated or unsaturated fatty acids such as stearamide morpholine, N-stearamid-3,5-dimethylpiperidine, 1-hexadecoylhexahydro [1H] azepine, hexadecoyl-3-methylpiperidine and the like.

  More preferable examples of the component (A) (E) fatty acid monoamide used in the present invention include N, N-dimethyloleic acid amide, N, N-dimethyllinoleic acid amide, N, N-dimethyllinolenic acid amide, N , N-dimethylricinoleic acid amide, N, N-dimethylarachidonic acid amide, N, N-dimethyleicosapentaenoic acid amide, N, N-dimethyldocosahexaenoic acid amide, N, N-dimethylerucic acid amide, N, N-diethyl Oleic acid amide, N, N-dipropyl oleic acid amide, lauric acid-N, N-diethanolamide, oleic acid-N, N-diethanolamide, and N, N- of unsaturated fatty acids such as vegetable and animal oil fatty acids Substituted amide.

  The component (A) (E) fatty acid monoamide used in the present invention can be produced by reacting an appropriate fatty acid with an amine using a known technique. For example, in the case of tall oil fatty acid dimethylamide, a slightly excess molar amount (1.1 mol) of dimethylamine is mixed and reacted with the tall oil fatty acid fraction (1.0 mol). In the case of vegetable oils in which fatty acids are present as triglycerides (eg, soybean oil, palm oil), 3.3 mol of dimethylamine is reacted with 1.0 mol of vegetable oil. The mixture is gradually heated to 170 ° C. in a sealed container under a pressure not exceeding 0.7 MPa and the reaction is carried out for 8 hours. Excess amine is removed in the aqueous phase formed during the reaction. When triglycerides are included, excess amine is present in the glycerin phase that is removed after the reaction. The water produced by the reaction can be distilled off or incorporated into the product formulation. A method for synthesizing a diethanolamide of a fatty acid is, for example, by mixing diethanolamine and a fatty acid or fatty acid mixture in a 1: 1 molar ratio and then heating the mixture at reflux temperature for several hours under vacuum to remove water. Manufactured.

  As the (E) fatty acid monoamide of the component (A) used in the present invention, a commercially available product can be used as it is. For example, lauric acid amide is diamond Y, palmitic acid amide is diamond KP, stearic acid amide is diamond AP-1, behenic acid amide is diamond BH, hydroxystearic acid amide is diamond KH, oleic acid amide is diamond Mid O-200 and erucic acid amide are commercially available from Nippon Kasei Co., Ltd. under the trade name Diamid L-200. Beef tallow fatty acid diethanolamide is Stahome T, lauric acid diethanolamide is Stahome DL, coconut oil fatty acid diethanolamide is Stahome F and DF, oleic acid diethanolamide is Stahome DO, coconut oil fatty acid monoethanolamide is Stahome MF, Lauric acid isopropanolamide is commercially available from NOF Corporation under the trade name Stahome LIPA. Coconut oil fatty acid-N-methyl-N-ethanolamide is commercially available from Kao Corporation under the trade name Aminone C-11S. N, N-dimethyloleic acid amide is commercially available under the trade names such as Texnol ODM from Nippon Emulsifier Co., Ltd. or Nikka Amide MBO from Nippon Kasei Co., Ltd. Products containing dimethylamide of tall oil fatty acid are commercially available from Bachman Laboratories, Inc. under trade names such as DMAD, SPI-2400, DMXS, and SADA.

  The component (b) used in the present invention comprises (F) a polymer of monoethylenically unsaturated carboxylic acid and its water-soluble salt, (G) organic phosphonic acid and its water-soluble salt, (H) phosphonocarboxylic acid And water-soluble salts thereof, and (I) phosphinopolycarboxylic acids and water-soluble salts thereof.

  The polymer (F) monoethylenically unsaturated carboxylic acid and water-soluble salt thereof as component (b) used in the present invention are a homopolymer of monoethylenically unsaturated carboxylic acid and water-soluble salt thereof, Copolymers of different monoethylenically unsaturated carboxylic acids and their water-soluble salts, one or more monoethylenically unsaturated carboxylic acids and one or more monoethylenically unsaturated monomers not containing a carboxylic acid group And a water-soluble salt thereof.

  Examples of the monoethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, and water-soluble salts thereof.

  Examples of the homopolymer of monoethylenically unsaturated carboxylic acid include acrylic acid polymer, methacrylic acid polymer, maleic acid polymer, hydrolyzate of maleic anhydride polymer, itaconic acid polymer, fumaric acid Examples of the copolymer of two or more different monoethylenically unsaturated carboxylic acids include a copolymer of acrylic acid and maleic acid, a copolymer of acrylic acid and itaconic acid, and maleic acid and itacone. Examples thereof include an acid copolymer, a copolymer of maleic acid and fumaric acid, a terpolymer of acrylic acid, itaconic acid and maleic acid, and a terpolymer of acrylic acid, itaconic acid and fumaric acid.

  In addition, in a copolymer of at least one monoethylenically unsaturated carboxylic acid and at least one monoethylenically unsaturated monomer that does not contain a carboxylic acid group, the monoethylenically unsaturated group that does not contain a carboxylic acid group Examples of monomers include 2-acrylamido-2-methylpropane sulfonic acid, 3-allyloxy-2-hydroxy-1-propane sulfonic acid, styrene sulfonic acid, sulfoalkyl (meth) acrylate ester, sulfoalkyl (meth) Monoethylenically unsaturated sulfonic acids such as allyl ether, sulfopheno (meth) allyl ether, (meth) allyl sulfonic acid and vinyl sulfonic acid; sulfonated products of conjugated dienes such as butadiene, isoprene, cyclooctane diene and cyclopentane diene; acrylic Acid ester or methacrylate ester; acrylic N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N, N-diethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, acryloylmorpholine, N-alkoxymethyl N-alkyl-substituted or unsubstituted acrylamide or methacrylamide such as acrylamide and diacetone acrylamide; acrylic acid ester or methacrylic acid ester such as methyl acrylate, ethyl acrylate, propyl acrylate, cyclohexyl acrylate, alkoxy polyethylene glycol acrylate; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polyethylene glycol acrylate, polyethylene Recall-hydroxy substituted alkyl acrylate or methacrylate such as polypropylene glycol acrylate; hydroxy substituted allyl ether such as allyl glycol, 3-allyloxy-1,2-propanediol, polyethylene glycol allyl ether, polypropylene glycol allyl ether; monomethyl maleate, malee Maleic acid monoesters or diesters such as dimethyl acid and ethyl maleate; itaconic acid monoesters or diesters such as itaconic acid monomethyl, dimethyl itaconate and ethyl itaconate; ethylene, propylene, isopropylene, butylene, isobutylene, hexene, 2- Olefins having 2 to 8 carbon atoms such as ethylhexene, pentene, isopentene, octene, isooctene; Examples thereof include vinyl alkyl ethers such as tellurium and vinyl ethyl ether; vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, and styrene.

  Preferred examples of the polymer (F) monoethylenically unsaturated carboxylic acid (F) used in the present invention and water-soluble salts thereof include acrylic acid polymers, maleic acid polymers, itaconic acid polymers, and the like. Homopolymer of monoethylenically unsaturated carboxylic acid and water-soluble salt thereof; copolymer of acrylic acid and maleic acid, copolymer of acrylic acid and itaconic acid, copolymer of maleic acid and itaconic acid, maleic acid and Two or more different monoethylenically unsaturated carboxylic acids such as a copolymer of fumaric acid, a terpolymer of acrylic acid, itaconic acid and maleic acid, a terpolymer of acrylic acid, itaconic acid and fumaric acid Copolymer and water-soluble salt thereof; copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid and 3-allyloxy-2-hydroxy-1-propanesulfuric acid Copolymers of acrylic acid and monoethylenically unsaturated sulfonic acids, such as copolymers of acid, copolymers of acrylic acid and conjugated diene sulfonates, and water-soluble salts thereof; acrylic acid and N, N-dimethylacrylamide copolymer A copolymer of acrylic acid and N-alkyl-substituted acrylamide, such as a polymer, a copolymer of acrylic acid and acryloylmorpholine, a copolymer of acrylic acid and N-tert-butylacrylamide, and a water-soluble salt thereof; Copolymers of hydroxy-substituted alkyl acrylates or methacrylates such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and water-soluble salts thereof; acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-hydroxy Copolymerization of propyl acrylate Copolymers of acrylic acid, monoethylenically unsaturated sulfonic acid and hydroxy-substituted alkyl acrylate and water-soluble salts thereof; Copolymerization of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and N-tert-butylacrylamide Copolymers of acrylic acid, monoethylenically unsaturated sulfonic acid and N-alkyl-substituted acrylamide, and water-soluble salts thereof; such as copolymers of acrylic acid, N, N-dimethylacrylamide and 2-hydroxypropyl acrylate Copolymer of acrylic acid, N-alkyl-substituted acrylamide and hydroxy-substituted alkyl acrylate and water-soluble salt thereof; acrylic acid and monoethylene such as a copolymer of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and vinyl alcohol Unsaturated sulfonic acid and vinyl alcohol Cole copolymer and water-soluble salt thereof; acrylic acid, monoethylenically unsaturated sulfonic acid and N-vinylpyrrolidone, such as a copolymer of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and N-vinylpyrrolidone And a water-soluble salt thereof. Examples of water-soluble salts of these polymers include sodium salts, potassium salts, and ammonium salts.

  The (F) monoethylenically unsaturated carboxylic acid polymer (component) and water-soluble salt thereof used in the present invention are produced by a method known as radical polymerization. That is, a target polymer can be produced by adding a polymerization initiator such as an azo compound or a peroxide to a monomer solution containing a monoethylenically unsaturated carboxylic acid and heating. For example, methods for producing maleic acid polymers and itaconic acid polymers are disclosed in Japanese Patent No. 2964154, Japanese Patent Application Laid-Open No. 2011-45860, Japanese Patent Application Laid-Open No. 2011-45861, and the like. Itaconic acid homopolymers are usually polymerizable ethylenic compounds described in Takayuki Otsu and Kiichi Takemoto's "Vinyl Polymerization Experimental Method" (Kyoritsu Shuppan) (1960), pages 137 to 175 and Japanese Patent No. 3884090. It can be produced according to the radical polymerization method of the compound.

  The molecular weight of the polymer (F) monoethylenically unsaturated carboxylic acid (F) used in the present invention and the water-soluble salt thereof is preferably 300 to 100,000 as the weight average molecular weight or number average molecular weight. Preferably it is the range of 500-20,000.

  The component (G) organic phosphonic acid and water-soluble salt thereof used in the present invention are organic compounds having one or more phosphono groups in the molecule and water-soluble salts thereof. -Hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid and their water-soluble salts, etc., preferably 1 -Hydroxyethylidene-1,1-diphosphonic acid and water-soluble salts thereof. Examples of water-soluble salts of these organic phosphonic acids include sodium salts, potassium salts, and ammonium salts.

  The component (B) (H) phosphonocarboxylic acid and water-soluble salt thereof used in the present invention are organic compounds having one or more phosphono groups and one or more carboxyl groups in the molecule, and water-soluble salts thereof. Specific examples thereof include 2-phosphonobutane-1,2,4-tricarboxylic acid, hydroxyphosphonoacetic acid, phosphonopolymaleic acid, phosphonic succinic acid and water-soluble salts thereof, preferably 2-phosphonobutane. -1,2,4-tricarboxylic acid, phosphonopolymaleic acid and their water-soluble salts. Examples of water-soluble salts of these phosphonocarboxylic acids include sodium salts, potassium salts, and ammonium salts.

  The component (H) phosphonocarboxylic acid and water-soluble salt thereof used in the present invention, for example, liberate phosphorous acid and monoethylenically unsaturated carboxylic acid in a neutral to alkaline aqueous solvent. It can be produced by heating in the presence of a radical initiator (for example, see JP-A-4-334392). It can also be produced 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, for example, Japanese Patent No. 3284318). Phosphonocarboxylic acid is commercially available from Rhodia under the trade name BRICORRR288 and from BWA under the trade name BELCOR585.

  The component (I) phosphinopolycarboxylic acid and water-soluble salt thereof used in the present invention are compounds having one or more phosphino groups and two or more carboxyl groups in the molecule, and water-soluble salts thereof. Specifically, bis-poly (2-carboxyethyl) phosphinic acid obtained by reacting acrylic acid and hypophosphorous acid, and bis-poly (1 obtained by reacting maleic acid and hypophosphorous acid , 2-dicarboxyethyl) phosphinic acid, poly (2-carboxyethyl) (1,2-dicarboxyethyl) phosphinic acid, itaconic acid and hypochlorous acid obtained by reacting maleic acid, acrylic acid and hypophosphorous acid. Bis-poly [2-carboxy- (2-carboxymethyl) ethyl] phosphinic acid obtained by reacting phosphoric acid, acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid And reaction products of hypophosphorous acid and water-soluble salts thereof, preferably a reaction product of acrylic acid, maleic acid, and hypophosphorous acid, a reaction product of itaconic acid, maleic acid, and hypophosphorous acid, and their It is a water-soluble salt. Examples of water-soluble salts of these phosphinopolycarboxylic acids include sodium salts, potassium salts, and ammonium salts.

  Preparation of the component (I) phosphinopolycarboxylic acid and its water-soluble salt used in the present invention is usually carried out by converting hypophosphorous acid and monoethylenically unsaturated carboxylic acid into free radicals in an aqueous solvent. This is carried out by heating in the presence of an initiator, and is disclosed in, for example, Japanese Patent Publication No. 54-29316, Japanese Patent Publication No. 5-57992 and Japanese Patent Publication No. 6-47113. Further, phosphinopolycarboxylic acids are commercially available from Biolabs under trade names such as BELCLENE500, BELPERSE164, and BELCLENE400.

  The most preferable example of the component (b) used in the present invention is at least one selected from maleic acid polymer, itaconic acid polymer, organic phosphonic acid, and phosphonocarboxylic acid, and acrylic acid 30 to 80 wt. Copolymer of 20 to 70% by weight of monoethylenically unsaturated sulfonic acid, 30 to 80% by weight of acrylic acid, 20 to 70% by weight of monoethylenically unsaturated sulfonic acid and 1 to 40% by weight of hydroxy-substituted alkyl acrylate Copolymer, 30 to 80% by weight of acrylic acid, 20 to 70% by weight of monoethylenically unsaturated sulfonic acid and 1 to 40% by weight of N-alkyl-substituted acrylamide, 30 to 80% by weight of acrylic acid and monoethylene Copolymer of 20 to 70% by weight of unsaturated sulfonic acid and 1 to 40% by weight of vinyl alcohol, and 30 to 80% by weight of acrylic acid and monoethylenic Unsaturated sulfonic acids 20-70% by weight is one or more combinations selected from N- vinylpyrrolidone from 1 to 40 wt% of the copolymer.

  In the composition for water treatment of the present invention, the blending ratio of the component (A) and the component (B) is usually in the range of 1:99 to 70:30 as a weight ratio. If it is out of this range, a sufficient inhibitory effect on the deposit may not be exhibited. A preferable blending ratio of the component (A) and the component (B) is in the range of 5:95 to 50:50 as a weight ratio.

  The water treatment composition of the present invention can be produced in various forms known in the art depending on the application. For example, it can be produced in liquid form as an aqueous solution, dispersion, emulsion or suspension, dispersion or suspension in a non-aqueous solvent, or a solution by dissolving in an organic solvent. It can also be prepared in solid form, for example as a powder or tablet, using means known in the art. However, dispersions, emulsions or suspensions have problems with long-term stability, and the use of organic solvents increases the environmental load such as COD and BOD of drainage, and in solid form, continuously with respect to the water system to be treated. Since it is difficult to supply stably, neither is preferable. For this reason, the water treatment composition of the present invention is most preferably an aqueous solution.

  When preparing the water treatment composition of the present invention as an aqueous solution, (A) as component (A) a polyhydric alcohol other than ethylene glycol and / or an ethylene oxide adduct of a polyhydric phenol, (B) a polyhydric alcohol And / or polyglycidyl ether of polyhydric phenol, (C) hydrolyzate of polyglycidyl ether of polyhydric alcohol and / or polyhydric phenol, and (D) polyhydric alcohol and / or polyhydric phenol and polyglycidyl ether When using 1 type, or 2 or more types of the compound selected from an addition reaction material, there is no restriction | limiting in particular in a preparation method, It prepares by mixing and dissolving (a) component and (b) component in water. Although there is no restriction | limiting also in a mixing order, Usually, (a) component and (b) component are thrown into the water under stirring. In addition, although the water to be used can be selected from clean industrial water, softened water, pure water, etc., from the viewpoint of not containing a hardness component, softened water or pure water is preferable, and further, it does not contain silicate ions. Pure water is most preferred.

  On the other hand, since the (E) fatty acid monoamide of component (a) has very low solubility in water, an aqueous solution of several mg / L can be prepared, but an aqueous solution with a content economically applicable to the water system of the actual device. There was a problem that it was difficult to obtain a solution. As a result of studying a solution to this problem, the present inventors have found that (c) in addition to the fatty acid monoamide and the component (b) shown in the general formula (1) as the component (b), By further adding a solubilizer and (d) alkali metal hydroxide, the water treatment composition of the present invention can be prepared as an aqueous solution having an economically applicable formulation and excellent product stability. I found.

  Examples of the solubilizer of the fatty acid monoamide used as the component (c) in the present invention include aromatic sulfonic acids having 6 to 9 carbon atoms such as benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid and the like. And water-soluble salts thereof; alkanesulfonic acids having 6 to 9 carbon atoms such as 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-nonanesulfonic acid, and water-soluble salts thereof; hexanoic acid, n-octanoic acid, 2- Saturated or unsaturated fatty acids having 6 to 8 carbon atoms such as ethylhexanoic acid and sorbic acid and water-soluble salts thereof; aromatic carboxylic acids having 5 to 10 carbon atoms such as benzoic acid, salicylic acid and tert-butylbenzoic acid; Dimer acid having 18 to 36 carbon atoms and water-soluble salt thereof; 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) ) Phosphoric acid esters having 6 to 16 carbon atoms such as phosphate, dibutyl phosphate and cresyl phosphate and water-soluble salts thereof; Phosphonic acids having 6 to 16 carbon atoms such as octylphosphonic acid and phenylphosphonic acid; 2-ethylhexylimino dipropion Acid, polybasic acids such as alkyliminodiacetic acid such as 2-ethylhexyliminodiacetic acid or alkyliminodipropionic acid and water-soluble salts thereof; 1,2,3-benzotriazole, 4-methylbenzotriazole, 5-methylbenzo Benzotriazoles such as triazole, alkyl-substituted-1,2,3-benzotriazole, halo-substituted-1,2,3-benzotriazole derivatives, halo-substituted-1,2,3-methylbenzotriazole; lower aliphatic alcohols, Examples include urea and nicotinamide. Other, known compounds as solubilizers can be used. These solubilizers may be used as a mixture of two or more.

  The benzotriazoles mentioned as the solubilizer of the fatty acid monoamide of the component (c) used in the present invention are also known as corrosion inhibitors for copper and copper alloys, and generally 4-methylbenzotriazole and 5-methyl A mixture of benzotriazoles is commercially available as tolyltriazole.

  The dimer acid mentioned as the solubilizing agent of the fatty acid monoamide of the component (c) used in the present invention is a dimer obtained by thermal polymerization of two unsaturated fatty acids, and is usually polymerized 2 It is a compound having the total carbon number of one unsaturated fatty acid and having two carboxyl groups. Here, as the unsaturated fatty acid, for example, tall oil fatty acid, soybean oil fatty acid, palm oil fatty acid, rice bran oil fatty acid and other plant-derived or animal-derived unsaturated fatty acid, acrylic acid or esters of these unsaturated fatty acids, etc. 3-24 unsaturated fatty acids and the like are used. In the reaction product, trimeric trimer acid and monomer monomer acid coexist as impurities as well as main component dimer acid. Further, the molecular structure of the reaction product is not clear, and it is generally marketed as a mixture of various isomers under the name dimer acid. The dimer acid as the solubilizer of the fatty acid monoamide of the component (c) used in the present invention may be either one obtained by thermally polymerizing the same kind of unsaturated fatty acid or one obtained by thermally polymerizing a different kind of unsaturated fatty acid. Examples of the former include dimer acid having 36 carbon atoms and trimer acid having 54 carbon atoms obtained by thermal polymerization of oleic acid and linoleic acid, or mixtures thereof. Examples of the latter include oleic acid and linoleic acid. The compound which thermally polymerized higher unsaturated fatty acids, such as an acid, and acrylic acid is mentioned. As the dimer acid, a hydrogenated residual unsaturated double bond may be used.

  The most preferable example of the dimer acid as the solubilizer of the fatty acid monoamide of the component (c) used in the present invention is a dimer acid obtained by thermally polymerizing a higher unsaturated fatty acid such as linoleic acid and acrylic acid. A compound obtained by polymerizing an oil fatty acid and acrylic acid in the presence of iodine is commercially available under the trade name DIACID 1550 (manufactured by Meadwestvaco, available from Harima Kasei) or LATOL 1550 (manufactured by Actrachem). A method for producing DIACID 1550 is disclosed in, for example, Japanese Patent Application Laid-Open No. 49-66659, and the composition thereof is mainly 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid and 6-carboxy- The dimer acid having 21 carbon atoms composed of 4-hexyl-2-cyclohexene-1-octanoic acid is about 60 to 70%, the unreacted unsaturated fatty acid having 18 carbon atoms is about 20 to 25%, and the carbon number is 36. Of dimer acid is said to contain 5-10%.

  Preferred examples of the fatty acid monoamide solubilizer of the component (c) used in the present invention are 2-ethylhexanoic acid, 1-octanesulfonic acid, xylenesulfonic acid, sorbic acid, cresyl phosphate, 2-ethylhexyl acid. Phosphate, dimer acid having 18 to 36 carbon atoms, 1,2,3-benzotriazole, tolyltriazole and water-soluble salts thereof. Here, cresyl phosphate is commercially available from Dow Chemical Company under the trade names TRITON H-66 and TRITON H-55.

  The most preferable examples of the fatty acid monoamide solubilizer of the component (c) used in the present invention are 2-ethylhexanoic acid, 1-octanesulfonic acid, xylenesulfonic acid, sorbic acid, cresyl phosphate, 2-ethylhexyl. Acid phosphate, one or more selected from dimer acids having 18 to 36 carbon atoms and water-soluble salts thereof, and one selected from 1,2,3-benzotriazole, tolyltriazole and water-soluble salts thereof It is a combination with the above.

  The blending amount of the component (c) in the water treatment composition of the present invention varies depending on the type of fatty acid monoamide represented by the general formula (1) as the component (a) to be used. This is the amount necessary to obtain. Generally, the smaller the blending amount of water in the composition, the smaller the necessary amount of component (c).

  As the alkali metal hydroxide as the component (d) in the water treatment composition of the present invention, one or more selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide are used. (D) It is preferable to adjust the blending amount of the alkali metal hydroxide of the component so that the product pH of the water treatment composition of the present invention is 12 or more, and more preferably the pH is 12.5 or more. It is adjusted to become. When the product pH of the composition for water treatment of the present invention is less than 12, sufficient product stability as an aqueous solution may not be obtained.

  When the fatty acid monoamide represented by the general formula (1) is used as the component (a) of the water treatment composition of the present invention, the components (c) and (d) are further added to the component (b). Thus, it became possible to prepare a one-part aqueous solution containing up to about 10% by weight of the fatty acid monoamide represented by the general formula (1) as the component (a). The preparation method is not particularly limited, and is prepared by mixing and dissolving the components (a), (b), (c) and (d) in water. Although there is no restriction | limiting also in a mixing order, Usually, (b) component is thrown in after mixing (b) component, (c) component, and (d) component with stirring water. When the final product pH of the composition for water treatment is lower than 12.5, the component (d) is added and prepared so as to be 12.5 or higher. In addition, although the water to be used can be selected from clean industrial water, softened water, pure water, and the like, since it does not contain a hardness component, softened water or pure water is preferable, and further, it does not contain silicate ions. Pure water is most preferred.

  In the water treatment method of the present invention, the effects of the present invention can be obtained even if the components (a) and (b) are separately added to the water system to be treated, but the present invention is a multifunctional composition. By adding the water treatment composition of the invention alone to the water system to be treated, it is possible to eliminate troublesome chemical administration that separately adds a plurality of various chemicals. In addition, also when adding said (I) component and (B) component separately with respect to a process target water system, the mixing ratio of (I) component and (B) component in the composition for water treatment of this invention, Likewise, the weight ratio is usually in the range of 1:99 to 70:30. If it is out of this range, a sufficient inhibitory effect on the deposit may not be exhibited. A preferable addition ratio of the component (a) to the component (b) is in the range of 5:95 to 50:50 as a weight ratio.

  The addition concentration of the composition for water treatment of the present invention is not constant depending on the situation of the water system to be treated, but is usually 1 in terms of the effective component conversion of the components (a) and (b) with respect to the water water to be treated. It is added to a concentration of ˜1000 mg / L, preferably in the range of 2 to 100 mg / L. If the addition amount is less than 1 mg / L, the deposit suppression effect may not be sufficient, and if the addition amount is 1000 mg / L or more, it is not possible to improve the deposit suppression effect to meet the increase in the addition concentration. Furthermore, since the COD in the waste water from the water system to be treated becomes high, it is not preferable.

  The addition of the composition for water treatment of the present invention is usually continuously infused into the treatment target water system using a chemical injection pump so as to maintain the total active ingredient concentration in the treatment target water system water. If the total active ingredient concentration can be maintained, intermittent injection can be selected.

  The concentration of the water treatment composition in the water to be treated is calculated from the measurement result of the mixed monoethylenically unsaturated carboxylic acid or phosphorus compound in water. In general, the monoethylenically unsaturated carboxylic acid concentration is measured by turbidimetry, and the phosphorus compound concentration is determined by subtracting the inorganic phosphoric acid concentration from the total phosphoric acid concentration after measuring the total phosphoric acid concentration and the inorganic phosphoric acid concentration. The organic phosphoric acid concentration is determined and converted to the concentration of the water treatment composition.

  In the water treatment method of the present invention, by further using a nonionic surfactant in addition to the water treatment composition of the present invention, an effect of improving the deposit suppressing effect can be obtained. In particular, the combined use of the component (A) (E) fatty acid monoamide and the nonionic surfactant is preferred.

（式中、Ｒ４は炭素数８〜２２、好ましくは１０〜１８の炭化水素基であり、直鎖であっても分岐鎖であってもよく、炭化水素基としては１級又は２級の高級アルコール、高級脂肪酸、高級脂肪酸アミドを原料とするものが挙げられる。−Ｘ−は−Ｏ−、−ＣＯＯ−、−ＣＯＮＨ−等の官能基を表し、ＥＯはエチレンオキシド、ＰＯはプロピレンオキサイド、ｎ及びｍは平均付加モル数を表し、ｎは３〜２０、好ましくは５〜１８、ｍは０〜６、好ましくは０〜３である。Ｒ５は水素原子、又は炭素数１〜６のアルキル基又はアルケニル基から選択され、好ましくは水素原子、又は炭素数１〜３のアルキル基又はアルケニル基である。また、一般式（２）において、−Ｘ−が−Ｏ−かつｍが０かつＲ５が水素のとき、ノニオン界面活性剤はアルコールエトキシレートであり、この場合において、Ｒ４の直鎖又は分岐鎖状のアルキル基又はアルケニル基の炭素数は１０〜２２、好ましくは１０〜２０、より好ましくは１０〜１８である。また、一般式（２）において−Ｘ−が−ＣＯＯ−のとき、ノニオン界面活性剤は脂肪酸エステル型ノニオン界面活性剤である。この場合において、Ｒ４の直鎖又は分岐鎖状のアルキル基又はアルケニル基の炭素数は９〜２１、好ましくは１１〜２１である。Ｒ４は不飽和結合を有していてもよい。また、この場合において、Ｒ５は、好ましくは炭素数１〜３のアルキル基である。）一般式（２）で表されるノニオン界面活性剤は、随意に１種単独で用いても２種以上を併用してもよい。 As said nonionic surfactant, the nonionic surfactant represented by following General formula (2) is preferable.

(In the formula, R 4 is a hydrocarbon group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, which may be linear or branched, and the hydrocarbon group is a primary or secondary higher group. Examples include alcohols, higher fatty acids, higher fatty acid amides as raw materials, -X- represents a functional group such as -O-, -COO-, -CONH-, EO is ethylene oxide, PO is propylene oxide, n and m represents an average added mole number, n is 3 to 20, preferably 5 to 18, m is 0 to 6, preferably 0 to 3. R5 is a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, or Selected from an alkenyl group, preferably a hydrogen atom, an alkyl group or an alkenyl group having 1 to 3 carbon atoms, and in the general formula (2), -X- is -O-, m is 0, and R5 is hydrogen. The nonionic surfactant is In this case, the carbon number of the linear or branched alkyl group or alkenyl group of R4 is 10 to 22, preferably 10 to 20, and more preferably 10 to 18. In the formula (2), when -X- is -COO-, the nonionic surfactant is a fatty acid ester type nonionic surfactant, and in this case, carbon of R4 linear or branched alkyl group or alkenyl group. The number is 9 to 21, preferably 11 to 21. R4 may have an unsaturated bond, and in this case, R5 is preferably an alkyl group having 1 to 3 carbon atoms.) The nonionic surfactant represented by the general formula (2) may optionally be used alone or in combination of two or more.

  Specific examples of the nonionic surfactant include, for example, those obtained by adding 12 to 15 mol of ethylene oxide to a synthetic alcohol having 12 to 13 carbon atoms, those obtained by adding 12 to 15 mol of ethylene oxide to natural alcohol, and hexanol. 10 mol of ethylene oxide added to 1 mol of C12 alcohol obtained by subjecting to gerbet reaction (trade name: ISOFOL12-10EO, manufactured by CONDEA), 15 mol of ethylene oxide added to lauric acid methyl ester, C12 alkene obtained by trimerizing butene is subjected to oxo process and 7 mole equivalent ethylene oxide is added to C13 alcohol (trade name: Lutensol TO7, manufactured by BASF), and pentanol is subjected to gerbet reaction. C obtained 7 alcohol equivalent of 7 moles of ethylene oxide (trade name: Lutensol XL70, manufactured by BASF), 6 mole equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to the garvet reaction (trade name: Lutensol XA60 (manufactured by BASF), secondary alcohol having 12 to 14 carbon atoms added with 9 mol equivalent or 15 mol equivalent ethylene oxide (trade name: Softanol 90 or Softanol 150, manufactured by Nippon Shokubai Co., Ltd.) , Coconut fatty acid methyl (lauric acid / myristic acid = 8/2) added with 15 moles of ethylene oxide using an alkoxylation catalyst, methyl laurate with 15 moles of ethylene oxide using an alkoxylation catalyst, and 3 moles of propylene alcohol The thing which added the xoxide etc. are mentioned. Or, polyoxyethylene (addition mole number 1-20) sorbitan fatty acid (carbon number 10-22) ester, polyoxyethylene (addition mole number 1-20) sorbit fatty acid (carbon number 10-22) ester, polyoxyethylene ( Addition mole number 1-20) glycol fatty acid (C10-C22) ester, glycerin fatty acid (C10-C22) ester, alkyl (C10-C22) glycoside, etc. are mentioned.

  The addition amount of the nonionic surfactant to the water system to be treated is preferably a weight ratio of 1/20 to 1/2 with respect to the component (A) of the water treatment composition of the present invention. If it is less than this range, there may be cases where a sufficient synergistic effect for suppressing deposits may not be obtained, and if this range is exceeded, an improvement in the synergistic effect for suppressing deposits can not be expected that is commensurate with the increase in the amount added. The foaming property of water becomes large, which is not preferable. In addition, also when mix | blending the said nonionic surfactant with the composition for water treatment of this invention, the compounding quantity is 1 / 20-1 / 2 weight with respect to (I) component mix | blended with this composition. A ratio is preferred.

  In the water treatment method of the present invention, known compounds such as corrosion inhibitors, microbial disorder inhibitors, and antifoaming agents may be used in combination.

  Examples of the corrosion inhibitor include benzotriazoles, polymerized phosphates, orthophosphoric acid, molybdates, tungstates, nitrites and the like. When copper or a copper alloy is present in the water system to be treated, it is preferable to use benzotriazoles together. Examples of benzotriazoles include 1,2,3-benzotriazole and 1,2,3-methylbenzotriazole. Alkyl-substituted-1,2,3-benzotriazole, halo-substituted-1,2,3-benzotriazole derivatives, halo-substituted-1,2,3-methylbenzotriazole, and the like.

  Examples of microbial disorder inhibitors include sodium hypochlorite, calcium hypochlorite, liquefied chlorine, chlorinated isocyanuric acids, chlorinated dimethylhydantoins, etc., dissolved in water and hypochlorous acid and / or hypochlorous acid. Compound that generates bromic acid; reaction product of hypochlorous acid and / or compound that generates hypobromite and sulfamic acid (salt); 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- Isothiazoline compounds such as 4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline; Organic bromide compounds such as roethanol, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-3-nitrilopropionamide; methylene bis-thiocyanate, bis (1,4-dibromoacetoxy) 2-butene, benzyl bromacetate, sodium bromide, α-bromocinnamaldehyde, 2-pyridinethiol-1-oxide sodium, bis (2-pyridinethiol-1-oxide) zinc, 2- (4-thiazolyl) benz Imidazole, hexahydro-1,3,5-tris- (2-hydroxyethyl) -S-triazine, bis (trichloromethyl) sulfone, dithiocarbamate, 3,5-dimethyltetrahydro-1,3,5,2H-thiadiazine- 2-thione, bromoacetic acid ethylthiophenyl ester, α Chlorbenzoaldoxime acetate, 2,4,5,6-tetrachloroisophthalonitrile, 1,2-dibromo-2,4-dicyanobutane, 3-iodo-2-propenylbutylcarbamate, salicylic acid, sodium salicylate, paraoxy Examples include benzoic acid esters and p-chloro-m-xylenol.

The most preferred microbial disorder inhibitor is a compound that generates hypochlorous acid and / or hypobromite, and the total concentration of free residual chlorine and free residual bromine is 0.02 to 1.0 mg / L (in terms of Cl _2). It is preferable to add to the water to be treated so that

  In addition, when a metal that forms a passivation film such as stainless steel or titanium is used in the water system to be treated, pitting corrosion and stress corrosion cracking due to crevice corrosion at the scale adhesion portion are likely to occur. However, corrosion of metals such as carbon steel, stainless steel, copper alloy and titanium can be indirectly prevented by suppressing deposits using the water treatment composition of the present invention.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to a following example. In addition, various modifications may be included in the present invention as long as those skilled in the art can easily conceive without departing from the scope of the claims.

  For the following scale inhibition test (1), scale inhibition test (2), (A) water treatment composition stability test using (E) fatty acid monoamide as component, and water treatment composition performance test The following compounds were as follows:

(Compound used in Examples)
(A) Component (A) Polyethylene alcohol other than ethylene glycol and / or polyhydric phenol ethylene oxide adduct A-1: polyoxyethylene glyceryl ether (molecular weight 450, EO addition mole number 8.1) (trade name: UNIOX G-450, manufactured by NOF Corporation)
A-2: Pentaerythritol polyoxyethylene ether (molecular weight 330, EO addition mole number 4.4) (trade name: PNT-40, manufactured by Nippon Emulsifier Co., Ltd.)
A-3: Trimethylolpropane tripolyoxyethylene ether (molecular weight 270, EO addition mole number 3.1) (trade name: TMP-30, manufactured by Nippon Emulsifier Co., Ltd.)

(A) Polyglycidyl ether of component (B) polyhydric alcohol and / or polyphenol B-1: ethylene glycol diglycidyl ether (epoxy equivalent 113) (trade name: Denacol EX-810, Nagase Chemitex Co., Ltd.) Made)
B-2: Polyethylene glycol diglycidyl ether (epoxy equivalent 268) (trade name: Denacol EX-830, manufactured by Nagase ChemteX Corporation)

(A) Hydrolyzate of polyglycidyl ether of component (C) polyhydric alcohol and / or polyhydric phenol C-1: ethylene glycol diglycidyl ether (epoxy equivalent 132) (trade name: Denacol EX-811, Nagase Chemitech A 1: 9 mixture of 1 mol / L-sodium hydroxide was heated at 90 ° C. for 4 hours to obtain a hydrolyzate C-1 of ethylene glycol diglycidyl ether.

(I) Component (D) Polyhydric alcohol and / or addition reaction product of polyhydric phenol and polyglycidyl ether D-1: 1 mol of triethylene glycol and 2 epoxy equivalents of ethylene glycol diglycidyl ether (Denacol EX-811) ) Is added to a test tube, 2% zinc borofluoride as a catalyst is added to triethylene glycol, and heated at 60 ° C. for 3 hours to obtain an addition reaction product D-1 of triethylene glycol and ethylene glycol diglycidyl ether. It was.
D-2: 1 mol of polyethylene glycol (average molecular weight 200) and 1 epoxy equivalent of polyethylene glycol diglycidyl ether instead of 1 mol of triethylene glycol and 2 epoxy equivalents of ethylene glycol diglycidyl ether (Denacol EX-811) (Epoxy equivalent 185) (Product name: Denacol EX-821 manufactured by Nagase Chemitex Co., Ltd.) In the same manner as D-1, addition reaction of polyethylene glycol (average molecular weight 200) and polyethylene glycol diglycidyl ether Product D-2 was obtained.

(A) Component (E) Fatty acid monoamide E-1: Palmitic acid amide (trade name: Diamid KP, manufactured by Nippon Kasei Co., Ltd.)
E-2: Stearic acid amide (trade name: Diamid AP-1, manufactured by Nippon Kasei Co., Ltd.)
E-3: Oleic acid amide (trade name: Diamond O-200, manufactured by Nippon Kasei Co., Ltd.)
E-4: Erucamide (trade name: Diamid L-200, manufactured by Nippon Kasei Co., Ltd.)
E-5: Lauric acid-N, N-diethanolamide (trade name: Stahome DL, manufactured by NOF Corporation)
E-6: Palm fatty acid-N, N-diethanolamide (trade name: Stahome DF, manufactured by NOF Corporation)
E-7: Oleic acid-N, N-diethanolamide (trade name: Stahome DO, manufactured by NOF Corporation)
E-8: Lauric acid-N-isopropanolamide (trade name: Stahome LIPA, manufactured by NOF Corporation)
E-9: Palm fatty acid-N-ethanolamide (trade name: Stahome MF, manufactured by NOF Corporation)
E-10: N, N-dimethyloleic acid amide (trade name: Texnol ODM, manufactured by Nippon Emulsifier Co., Ltd.)
E-11: Tall fatty acid-N, N-dimethylamide (50% or more) + aliphatic alcohol ethoxylate (10-30%) mixture (trade name: DMAD, manufactured by Bachman Laboratories)
E-12: Tall fatty acid-N, N-dimethylamide (90.1%) + ethoxylated dodecylphenol (9.9%) mixture (trade name: SPI-2400, manufactured by Bachman Laboratories)

(B) Polymer of component (F) monoethylenically unsaturated carboxylic acid and water-soluble salt thereof F-1: Acrylic acid polymer A; Copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid [Copolymerization ratio (weight) 60:40, average molecular weight 10,000]
F-2: acrylic acid polymer B; copolymer of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and N-tert-butylacrylamide [copolymerization ratio (weight) 50:40:10, weight average molecular weight 10,000]
F-3: maleic acid polymer; maleic acid homopolymer (average molecular weight 500) (trade name: BELCLENE 200LA, manufactured by BWA)
F-4: Itaconic acid polymer; Itaconic acid homopolymer (average molecular weight 1000), according to the method described on pages 137 to 175 of “Vinyl polymerization experiment method” (Kyoritsu Shuppan) (1960), written by Takayuki Otsu and Kiichi Takemoto. Manufactured. An appropriate amount of chain transfer agent was added to adjust the molecular weight.

(B) Component (G) Organic phosphonic acid and water-soluble salt thereof G-1: HEDP; 1-hydroxyethylidene-1,1-diphosphonic acid (trade name: BELCLENE 660LA, manufactured by BWA)
(B) Component (H) phosphonocarboxylic acid and water-soluble salt thereof H-1: PBTC; 2-phosphonobutane-1,2,4-tricarboxylic acid (trade name: BELCLENE 650, manufactured by BWA)
(B) Component (I) Phosphinopolycarboxylic acid and water-soluble salt thereof 1-1: Phosphinopolycarboxylic acid; acrylic acid-maleic acid-hypophosphorous acid (2: 1: 1) copolymer (average It was produced according to the method described in Japanese Patent Publication No. 6-47113.

(C) Component 1,2,3-benzotriazole (Brand name: BELCLENE 510, manufactured by BWA)
Tolyltriazole (Brand name: BELCLENE 511, manufactured by BWA)
Xylene sulfonic acid (reagent: m-xylene-4-sulfonic acid n hydrate, manufactured by Kanto Chemical Co., Inc.)
1-octanesulfonic acid (reagent: sodium 1-octanesulfonate, manufactured by Kanto Chemical Co., Inc.)
2-ethylhexanoic acid (reagent: manufactured by Kanto Chemical Co., Inc.)
Sorbic acid (reagent: manufactured by Kanto Chemical Co., Inc.)
DIACID 1550 (trade name: manufactured by Meadwestvaco); dimer acid TRITON H-66 (trade name: manufactured by Dow Chemical Co.); cresyl phosphate

(D) Component potassium hydroxide (reagent: manufactured by Kanto Chemical Co., Inc.)
Sodium hydroxide (reagent: manufactured by Kanto Chemical Co., Inc.)

Nonionic surfactant Adecatol LB-83 (trade name: manufactured by ADEKA); lauryl alcohol ethoxylate

(Compound used in Comparative Example)
PEG: Polyethylene glycol 2000 (molecular weight 2000) (reagent: manufactured by Tokyo Chemical Industry Co., Ltd.)
PAM: polyacrylamide (molecular weight 10,000) (reagent: polyacrylamide, MW10000, 50% aqueous solution, manufactured by Wako Pure Chemical Industries, Ltd.)
PEI: Polyethyleneimine (molecular weight 600) (trade name: Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd.)

1. Scale suppression test (1) (Examples 1-7, Comparative Examples 1-4)
A solution containing 400 mg / L of silica prepared by dissolving sodium metasilicate pentahydrate in water is passed through a column packed with H-type strongly acidic ion exchange resin to prepare an orthosilicate solution, and calcium chloride is added thereto. The solution, magnesium sulfate solution, and sodium bicarbonate solution were added to prepare a solution containing calcium hardness 300 mg CaCO ₃ / L, magnesium hardness 50 mg CaCO ₃ / L, bicarbonate ion concentration 300 mg CaCO ₃ / L, and silica concentration 400 mg / L. To this solution, the compound (a), the compound (b), and the other component shown in Table 1 were added so as to have the addition concentrations shown in Table 1 in terms of active ingredients. Aluminum was added at 3 mg / L as Al, and the pH was adjusted to 8.7 with a sodium hydroxide solution to prepare a test solution. In addition, “no addition” in Comparative Example 4 is an example in which none of the compounds of component (a), component (b), and other components was added. After leaving the test solution at 50 ° C. for 5 days, the test solution was No. It filtered with the filter paper for 6 fixed_quantity | quantitative_assay, and the residual silica density | concentration and the residual calcium hardness were measured. The higher the value of residual silica concentration and residual calcium (Ca) hardness, the higher the scale suppression effect. Here, the residual silica concentration was measured by the following method. Residual calcium hardness was measured by a chelate titration method defined in JIS K0101: 1998, section 15.2.1. The test results are shown in Table 1.
[Method for measuring residual silica concentration]
1 mL of the test solution was placed in a fluororesin round bottom test tube, 2 mL of 1 mol / L sodium hydroxide was added, and then heated for 20 minutes with a hot block heated to 110 ° C. Subsequently, 2 mL of 1 mol / L hydrochloric acid was added, the test tube was cooled to 20 ° C., and the silica concentration was measured by the molybdenum yellow method of JIS K0101. The residual silica concentration measured here is the total concentration of soluble silica such as orthosilicic acid, orthosilicate ion, polysilicate ion and colloidal silica.

  According to the results in Table 1, the scale-inhibiting effect of the present invention when the component (ii) having the silica-based scale inhibitory effect and the component (b) having the calcium-based scale inhibitory effect is used is the conventional silica. It is clearly superior to the scale control effect of the comparative example in which PEG, PAM, PEI, which are known as system scale inhibitors, and the component (b) having a calcium system scale control effect are used in combination. Even under harsh conditions in which the presence of water is present, the excellent scale-suppressing effect of the present invention by the combined use of component (a) and component (b) was shown.

2. Scale suppression test (2) (Examples 8-30, Comparative Examples 5-29)
A solution containing 400 mg / L of silica prepared by dissolving sodium metasilicate pentahydrate in water is passed through a column packed with H-type strongly acidic ion exchange resin to prepare an orthosilicate solution, and calcium chloride is added thereto. The solution, magnesium sulfate solution, and sodium bicarbonate solution were added to prepare a solution containing calcium hardness 300 mg CaCO ₃ / L, magnesium hardness 50 mg CaCO ₃ / L, bicarbonate ion concentration 300 mg CaCO ₃ / L, and silica concentration 400 mg / L. To this solution, the compound of component (a), the compound of component (b), and the compound of other components shown in Table 2 are added so as to have the addition concentrations shown in Table 2 in terms of active ingredients, respectively, and a sodium hydroxide solution The pH was adjusted to 9.0 to prepare a test solution. Polyaluminum chloride was not added. “No addition” in Comparative Example 29 is an example in which none of the compounds of component (a), component (b), and other components was added. After leaving the test solution at 50 ° C. for 5 days, the test solution was No. It filtered with the filter paper for 6 fixed_quantity | quantitative_assay, and the residual silica density | concentration and the residual calcium hardness were measured. The higher the value of residual silica concentration and residual calcium (Ca) hardness, the higher the scale suppression effect. Here, the residual silica concentration was measured by the following method. Residual calcium hardness was measured by a chelate titration method defined in JIS K0101: 1998, section 15.2.1. The test results are shown in Table 2.
[Method for measuring residual silica concentration]
1 mL of the test solution was placed in a fluororesin round bottom test tube, 2 mL of 1 mol / L sodium hydroxide was added, and then heated for 20 minutes with a hot block heated to 110 ° C. Subsequently, 2 mL of 1 mol / L hydrochloric acid was added, the test tube was cooled to 20 ° C., and the silica concentration was measured by the molybdenum yellow method of JIS K0101. The residual silica concentration measured here is the total concentration of soluble silica such as orthosilicic acid, orthosilicate ion, polysilicate ion and colloidal silica.

  According to the result of Table 2, the scale inhibitory effect of the Example which used (a) component and (b) component of this invention together is the scale inhibitory effect of the comparative example which uses (a) component or (b) component independently. It is clearly superior to the above, and it is superior to the additive effect of the component (b) and component (b) assumed from the result of single use. ) The synergistic effect of specific scale suppression by the combined use of components was shown.

3. (A) Composition stability test for water treatment using (E) fatty acid monoamide as component (compositions 1-14)
As an example of the present invention, a water treatment composition having the composition shown in Table 3 was prepared. The final product pH of these water treatment compositions was adjusted to 12.5 or higher. On the other hand, as a comparative example, in the compositions for water treatment 1 to 6 in Table 3, the composition containing no component (c), and in the compositions for water treatment 1 to 6, the amount of sodium hydroxide or potassium hydroxide was reduced to the final. A composition in which the product pH is adjusted to 11.5, a composition in which 2-ethylhexanoic acid having 8 carbon atoms is replaced with capric acid having 10 carbon atoms in water-treating composition 3, and carbon number in water-treating composition 3 A composition in which 8-ethylhexanoic acid of 8 is replaced with lauric acid having 12 carbons, and in composition 5 for water treatment, 1-octanesulfonic acid having 8 carbons is replaced with 1-decanesulfonic acid having 10 carbons. A composition in which 1-octanesulfonic acid having 8 carbon atoms was replaced with 1-dodecanesulfonic acid having 12 carbon atoms in composition 5 for water treatment was prepared. A 100 mL sample of each prepared water treatment composition was placed in a plastic bottle, sealed and allowed to stand at room temperature for 30 days, and then visually checked for the presence of turbidity, precipitation, separation, and the like.

  In the water treatment compositions 1 to 14 which are examples of the present invention, the sample was turbid after standing at room temperature for 30 days, and no precipitation or separation was observed. On the other hand, phase separation was confirmed in all samples of the water treatment composition prepared as a comparative example. From this result, when (E) a fatty acid monoamide is used as the component (a) of the water treatment composition of the present invention, the solubilizer of the fatty acid monoamide as the component (d) and the alkali metal water as the component (d) It was shown that a stable one-part aqueous solution can be prepared by adding the oxide.

4). Water treatment composition performance test The test apparatus and test method conformed to the on-site test method of JIS G0593-2002 "Testing method for corrosion and scale prevention of water treatment agents".
(Test equipment)
The test apparatus shown in FIG. 1 was used. The cooling water is held in the water tank 2 and is sent to the heat exchanger 7 as circulating water by the circulation pump 3. The amount of circulating water is measured by the flow meter 6 and appropriately adjusted by the flow rate adjusting valve 5. The circulating water heated and raised in the heat exchanger 7 is cooled by the cooling tower 1 after passing through the test piece holder 8 and returned to the water tank 2. The return water temperature of the circulating water is appropriately maintained by adjusting the fan operation of the cooling tower 1 by the water temperature control device 9. On the other hand, the electric conductivity signal of the cooling water measured by the electric conductivity measuring cell 4 is input to the electric conductivity control device 11 so as to be within a predetermined electric conductivity range of the cooling water based on the signal. The blow-down pump 10 is operated. The makeup water 12 is supplied to the water tank 2 in response to a drop in the water level of the water tank 2 as the blow starts, and as a result, the concentration of the cooling water is maintained within a predetermined range. Further, simultaneously with the start of blowing, the water treatment agent injection device 13 is operated to maintain the water treatment agent concentration in the cooling water system appropriately.

(Test conditions)
(1) Test heat transfer tube mounted on the heat exchanger 7 (outer diameter 12.7 mm, length 510 mm)
Carbon steel tube STKM11A (JIS G3445) and aluminum brass C6871 (JIS H3300) were used.
(2) Heat flux of the heat exchanger 7: 70 kW / m ²
(3) Retained water volume of the entire system including the water tank 2 and piping: 62L
(4) Circulating water volume: 210 L / h (corresponding to a linear flow rate of 0.3 m / s in the test heat transfer tube evaluation section)
(5) Cooling capacity of cooling tower 1: 1.8 cooling tons (inductive draft counterflow contact type)
(6) Temperature difference of circulating water at cooling tower inlet / outlet: 15 ° C
(7) Evaporated water amount: 4.4 L / h
(8) Makeup water volume: 5.5L / h
(9) Blowdown water volume: 1.1 L / h
(10) Concentration: 5 times (11) Test period: 1 month

(Test method)
As makeup water 12, sodium metasilicate was added to Yokkaichi city water to adjust the silica concentration, and sulfuric acid was added to adjust the pH. The water quality of the makeup water is pH: 8, electrical conductivity: 260 μS / cm, Ca hardness: 33 mg-CaCO ₃ / L, Mg hardness: 8 mg-CaCO ₃ / L, M alkalinity: 46 mg-CaCO ₃ / L, chloride Ion: 8 mg / L, sulfate ion: 50 mg / L, silica: 48 mg / L.
As an initial treatment, the makeup water is filled in the water tank 2, and 200 mg / L of the following composition to be tested and 12.5 mg / L of hexametaphosphate sodium (average degree of condensation) are added to the amount of retained water. Circulated at room temperature for 48 hours. Thereafter, the heat load was started, and the concentration reached 5 times 3 days after the start of the heat load. Therefore, blowdown was immediately started to maintain the concentration 5 times. Simultaneously with the start of the blowdown, the following composition to be tested was added to the blowdown amount by the water treatment agent injection device 13 so that the composition concentration was 60 mg / L. Moreover, the polyaluminum chloride solution was continuously added to the water tank 2 using a metering pump not shown in FIG. 1 so that the aluminum concentration in the circulating water was 2 mg / L.
The degree of concentration (N) was calculated from the concentration ratio of the calcium hardness of the circulating water and the makeup water. In addition, the quality of the circulating water was maintained so that the calculated silica concentration of the circulating water was 240 mg / L. Here calculation silica concentration _(S C: mg / L) and the silica concentration of the replenishing water enrichment (N) and the circulating water: as defined in (S mg / L) of the product (N × S), substantially Is the concentration of silica contained in the circulating water system.

(Composition for test)
(1) Examples: Compositions 5, 7 to 9, 14 shown in Table 3, and Composition 15 shown in Table 4 below
(2) Comparative Example: Compositions 16 to 21 shown in Table 4 below

  After completion of the test, the test heat transfer tube was removed from the heat exchanger 7, and the corrosion rate (average value) of the carbon steel tube and the scale deposition rate of the aluminum brass tube were measured. Moreover, the slime adhesion state of the cold water tower 1 was visually observed. As the corrosion rate and scale adhesion rate are smaller, the corrosion inhibition effect and scale inhibition effect are higher. The results are shown in Table 5. In addition, “no addition” in Comparative Example 36 is an example in which no composition was added.

  According to the results in Table 5, the composition for water treatment of the present invention has a scale inhibitory effect, a corrosion inhibitory effect, and a slime inhibitory effect as compared with the composition of the comparative example that does not contain component (b) or component (b). The water treatment composition of the present invention comprising both the component (a) and the component (b) as active ingredients suppresses the formation of scale by the addition of one composition, and is in contact with water. It has been revealed that the composition is a multifunctional composition that can suppress the corrosion of the metal to be produced and can further suppress the generation of slime.

The water treatment composition and water treatment method of the present invention are used in the process water, cooling water, boiler water, washing water, air conditioning and district heating and cooling systems of various manufacturing industries such as the pulp and paper manufacturing industry, automobile factory, and electronic factory. Used to control the accumulation of all kinds of deposits such as inorganic deposits such as scale, earth and sand, and organic deposits such as slime mainly composed of microorganisms, which are generated in water systems such as various effluents such as cold and hot water for conditioning. It can be used to suppress corrosion that comes into contact with water.

DESCRIPTION OF SYMBOLS 1 Cooling tower 2 Water tank 3 Circulation pump 4 Electrical conductivity measurement cell 5 Flow rate adjustment valve 6 Flowmeter 7 Heat exchanger 8 Test piece holder 9 Water temperature control device 10 Blow down pump 11 Electrical conductivity control device 12 Supply water 13 Water treatment Agent injection device

（式中、Ｒ１およびＲ２は、それぞれ独立に水素、炭素数１〜２２のアルキル基又はアルケニル基、炭素数１〜２２のヒドロキシアルケニル基から選択されるか、あるいはＲ１とＲ２が一緒になって環状アミドの構成単位となり、Ｒ３は炭素数８〜２２の飽和又は不飽和の脂肪酸残基である。）
That is, the invention according to claim 1 is a water treatment composition characterized by comprising the following component (a) and component (b) as active ingredients, wherein component (a) comprises ( B) A polyglycidyl ether of a polyhydric alcohol and / or polyhydric phenol, which does not have an amino group , (C) a hydrolyzate of a polyglycidyl ether of a polyhydric alcohol and / or polyhydric phenol, (D) a polyhydric acid Addition reaction product of alcohol and / or polyhydric phenol and polyglycidyl ether , wherein the polyglycidyl ether is ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentylglyce Coal diglycidyl ether, hexanediol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, hydroquinone diglycidyl ether, bisphenol A diglycidyl ether A compound selected from the group consisting of: (E) a fatty acid monoamide , which is one or more compounds selected from the compounds represented by the general formula (1) , and the component (b) is (F) ) A polymer of monoethylenically unsaturated carboxylic acid and water-soluble salt thereof, (G) organic phosphonic acid and water-soluble salt thereof, (H) phosphonocarboxylic acid and water-soluble salt thereof, and (I) phosphinopolycarboxylic acid. Acidity It is one or the water treatment composition is 2 or more compounds selected from water-soluble salts thereof.

Wherein R1 and R2 are each independently selected from hydrogen, an alkyl or alkenyl group having 1 to 22 carbon atoms, a hydroxyalkenyl group having 1 to 22 carbon atoms, or R1 and R2 are combined together (It becomes a structural unit of cyclic amide, and R3 is a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms.)

The invention according to claim 2 is that the component (a) is a fatty acid monoamide represented by the general formula (1), and (c) a fatty acid monoamide solubilizer and (d) an alkali metal hydroxide. and a water treatment composition according to claim 1 containing as product pH of the aqueous treatment composition is 12 or higher.

（式中、Ｒ４およびＲ５は、それぞれ独立に水素、炭素数１〜２２のアルキル基又はアルケニル基、炭素数１〜２２のヒドロキシアルケニル基から選択されるか、あるいはＲ４とＲ５が一緒になって環状アミドの構成単位となり、Ｒ６は炭素数８〜２２の飽和又は不飽和の脂肪酸残基である。）である。
The invention according to claim 3 is characterized by adding the following component (a) and the following component (b) to the water system to be treated, and having the effects of inhibiting scale, corrosion of metal in contact with water, and slime. A water treatment method, wherein ( B) component is a polyglycidyl ether of ( B) polyhydric alcohol and / or polyhydric phenol, and has no amino group , (C) polyhydric alcohol and / or Polyglycidyl ether hydrolyzate of polyhydric phenol, (D) polyhydric alcohol and / or addition reaction product of polyhydric phenol and polyglycidyl ether , wherein polyglycidyl ether is ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, poly Ripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, hydroquinone A compound selected from the group consisting of diglycidyl ether, bisphenol A diglycidyl ether, and (E) a fatty acid monoamide that is one or more compounds selected from the compounds represented by formula (2) The component (B) includes (F) a polymer of monoethylenically unsaturated carboxylic acid and its water-soluble salt, (G) organic phosphonic acid and its water-soluble salt, (H) phosphonocar Phosphate and water-soluble salts thereof, and (I) phosphino polycarboxylic acids and one or water treatment process is two or more compounds selected from water-soluble salts thereof.

(Wherein R4 and R5 are each independently selected from hydrogen, an alkyl or alkenyl group having 1 to 22 carbon atoms, a hydroxyalkenyl group having 1 to 22 carbon atoms, or R4 and R5 are combined together) It is a structural unit of a cyclic amide, and R6 is a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms .

（式中、Ｒ１およびＲ２は、それぞれ独立に水素、炭素数１〜２２のアルキル基又はアルケニル基、炭素数１〜２２のヒドロキシアルケニル基から選択されるか、あるいはＲ１とＲ２が一緒になって環状アミドの構成単位となり、Ｒ３は炭素数８〜２２の飽和又は不飽和の脂肪酸残基である。）
The component (a) used in the present invention is ( B) a polyglycidyl ether of a polyhydric alcohol and / or polyhydric phenol, which has no amino group , (C) a polyhydric alcohol and / or a polyhydric alcohol. Polyglycidyl ether hydrolyzate of polyhydric phenol, (D) polyhydric alcohol and / or addition reaction product of polyhydric phenol and polyglycidyl ether , wherein polyglycidyl ether is ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, glycerol polyglycidyl ether, di A compound selected from the group consisting of glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, hydroquinone diglycidyl ether, bisphenol A diglycidyl ether, and (E) a fatty acid monoamide . And selected from the compounds represented by the general formula (1) .

Wherein R1 and R2 are each independently selected from hydrogen, an alkyl or alkenyl group having 1 to 22 carbon atoms, a hydroxyalkenyl group having 1 to 22 carbon atoms, or R1 and R2 are combined together (It becomes a structural unit of cyclic amide, and R3 is a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms.)

（ここでＲ１およびＲ２は、それぞれ独立に水素、炭素数１〜２２のアルキル基又はアルケニル基、炭素数１〜２２のヒドロキシアルケニル基から選択されるか、あるいはＲ１とＲ２が一緒になって環状アミドの構成単位となり、Ｒ３は炭素数８〜２２の飽和又は不飽和の脂肪酸残基である。）
A more preferred example of the component (A) (E) fatty acid monoamide used in the present invention is a compound represented by the following general formula (1).

(Wherein R1 and R2 are each independently hydrogen, alkyl or alkenyl group having 1 to 22 carbon atoms, or is selected from hydroxycarboxylic alkenyl group having 1 to 22 carbon atoms, or R1 and R2 together with (This is a structural unit of a cyclic amide, and R3 is a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms.)

（式中、Ｒ７は炭素数８〜２２、好ましくは１０〜１８の炭化水素基であり、直鎖であっても分岐鎖であってもよく、炭化水素基としては１級又は２級の高級アルコール、高級脂肪酸、高級脂肪酸アミドを原料とするものが挙げられる。−Ｘ−は−Ｏ−、−ＣＯＯ−、−ＣＯＮＨ−等の官能基を表し、ＥＯはエチレンオキシド、ＰＯはプロピレンオキサイド、ｎ及びｍは平均付加モル数を表し、ｎは３〜２０、好ましくは５〜１８、ｍは０〜６、好ましくは０〜３である。Ｒ８は水素原子、又は炭素数１〜６のアルキル基又はアルケニル基から選択され、好ましくは水素原子、又は炭素数１〜３のアルキル基又はアルケニル基である。また、一般式（３）において、−Ｘ−が−Ｏ−かつｍが０かつＲ８が水素のとき、ノニオン界面活性剤はアルコールエトキシレートであり、この場合において、Ｒ７の直鎖又は分岐鎖状のアルキル基又はアルケニル基の炭素数は１０〜２２、好ましくは１０〜２０、より好ましくは１０〜１８である。また、一般式（３）において−Ｘ−が−ＣＯＯ−のとき、ノニオン界面活性剤は脂肪酸エステル型ノニオン界面活性剤である。この場合において、Ｒ７の直鎖又は分岐鎖状のアルキル基又はアルケニル基の炭素数は９〜２１、好ましくは１１〜２１である。Ｒ７は不飽和結合を有していてもよい。また、この場合において、Ｒ８は、好ましくは炭素数１〜３のアルキル基である。）一般式（３）で表されるノニオン界面活性剤は、随意に１種単独で用いても２種以上を併用してもよい。
As said nonionic surfactant, the nonionic surfactant represented by the following general formula ( 3 ) is preferable.

(In the formula, R 7 is a hydrocarbon group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, which may be linear or branched, and the hydrocarbon group may be primary or secondary. Examples include higher alcohols, higher fatty acids, and higher fatty acid amides as raw materials -X- represents a functional group such as -O-, -COO-, -CONH-, EO represents ethylene oxide, PO represents propylene oxide, n And m represents an average added mole number, n is 3 to 20, preferably 5 to 18, m is 0 to 6, preferably 0 to 3. R 8 is a hydrogen atom or an alkyl having 1 to 6 carbon atoms. Selected from a group or an alkenyl group, preferably a hydrogen atom, an alkyl group or an alkenyl group having 1 to 3 carbon atoms, and, in the general formula ( 3 ), -X- is -O-, m is 0 and R 8 when hydrogen, a nonionic surfactant An alcohol ethoxylate, in this case, the number of carbon atoms of straight-chain or branched alkyl or alkenyl group R 7 is 10 to 22, preferably 10 to 20, more preferably 10 to 18. Further, In the general formula ( 3 ), when —X— is —COO—, the nonionic surfactant is a fatty acid ester type nonionic surfactant, and in this case, a linear or branched alkyl group or alkenyl group of R 7 The carbon number of is 9 to 21, preferably 11 to 21. R 7 may have an unsaturated bond, and in this case, R 8 is preferably an alkyl group having 1 to 3 carbon atoms. The nonionic surfactant represented by the general formula ( 3 ) may optionally be used alone or in combination of two or more.

(Compounds used in Examples and Reference Examples )
(A) Component (A) Polyethylene alcohol other than ethylene glycol and / or polyhydric phenol ethylene oxide adduct A-1: polyoxyethylene glyceryl ether (molecular weight 450, EO addition mole number 8.1) (trade name: UNIOX G-450, manufactured by NOF Corporation)
A-2: Pentaerythritol polyoxyethylene ether (molecular weight 330, EO addition mole number 4.4) (trade name: PNT-40, manufactured by Nippon Emulsifier Co., Ltd.)
A-3: Trimethylolpropane tripolyoxyethylene ether (molecular weight 270, EO addition mole number 3.1) (trade name: TMP-30, manufactured by Nippon Emulsifier Co., Ltd.)

1. Scale suppression test (1) (Examples 3 to 6, Reference Examples 1 , 2 , and 7 , Comparative Examples 1 to 4)
A solution containing 400 mg / L of silica prepared by dissolving sodium metasilicate pentahydrate in water is passed through a column packed with H-type strongly acidic ion exchange resin to prepare an orthosilicate solution, and calcium chloride is added thereto. The solution, magnesium sulfate solution, and sodium bicarbonate solution were added to prepare a solution containing calcium hardness 300 mg CaCO ₃ / L, magnesium hardness 50 mg CaCO ₃ / L, bicarbonate ion concentration 300 mg CaCO ₃ / L, and silica concentration 400 mg / L. To this solution, the compound (a), the compound (b), and the other component shown in Table 1 were added so as to have the addition concentrations shown in Table 1 in terms of active ingredients. 3 mg / L of aluminum was added as Al, and the pH was adjusted to 8.7 with a sodium hydroxide solution to prepare a test solution. In addition, “no addition” in Comparative Example 4 is an example in which none of the compounds of component (a), component (b), and other components was added. After leaving the test solution at 50 ° C. for 5 days, the test solution was No. It filtered with the filter paper for 6 fixed_quantity | quantitative_assay, and the residual silica density | concentration and the residual calcium hardness were measured. The higher the value of residual silica concentration and residual calcium (Ca) hardness, the higher the scale suppression effect. Here, the residual silica concentration was measured by the following method. Residual calcium hardness was measured by a chelate titration method defined in JIS K0101: 1998, section 15.2.1. The test results are shown in Table 1.
[Method for measuring residual silica concentration]
1 mL of the test solution was placed in a fluororesin round bottom test tube, 2 mL of 1 mol / L sodium hydroxide was added, and then heated for 20 minutes with a hot block heated to 110 ° C. Subsequently, 2 mL of 1 mol / L hydrochloric acid was added, the test tube was cooled to 20 ° C., and the silica concentration was measured by the molybdenum yellow method of JIS K0101. The residual silica concentration measured here is the total concentration of soluble silica such as orthosilicic acid, orthosilicate ion, polysilicate ion and colloidal silica.

2. Scale suppression test (2) (Examples 12 to 20, 24 to 26, Reference Examples 8 to 11 , 21 to 23 , 27 to 30 , Comparative Examples 5 to 29)
A solution containing 400 mg / L of silica prepared by dissolving sodium metasilicate pentahydrate in water is passed through a column packed with H-type strongly acidic ion exchange resin to prepare an orthosilicate solution, and calcium chloride is added thereto. The solution, magnesium sulfate solution, and sodium bicarbonate solution were added to prepare a solution containing calcium hardness 300 mg CaCO ₃ / L, magnesium hardness 50 mg CaCO ₃ / L, bicarbonate ion concentration 300 mg CaCO ₃ / L, and silica concentration 400 mg / L. To this solution, the compound of component (a), the compound of component (b), and the compound of other components shown in Table 2 are added so as to have the addition concentrations shown in Table 2 in terms of active ingredients, respectively, and a sodium hydroxide solution The pH was adjusted to 9.0 to prepare a test solution. Polyaluminum chloride was not added. “No addition” in Comparative Example 29 is an example in which none of the compounds of component (a), component (b), and other components was added. After leaving the test solution at 50 ° C. for 5 days, the test solution was No. It filtered with the filter paper for 6 fixed_quantity | quantitative_assay, and the residual silica density | concentration and the residual calcium hardness were measured. The higher the value of residual silica concentration and residual calcium (Ca) hardness, the higher the scale suppression effect. Here, the residual silica concentration was measured by the following method. Residual calcium hardness was measured by a chelate titration method defined in JIS K0101: 1998, section 15.2.1. The test results are shown in Table 2.
[Method for measuring residual silica concentration]
1 mL of the test solution was placed in a fluororesin round bottom test tube, 2 mL of 1 mol / L sodium hydroxide was added, and then heated for 20 minutes with a hot block heated to 110 ° C. Subsequently, 2 mL of 1 mol / L hydrochloric acid was added, the test tube was cooled to 20 ° C., and the silica concentration was measured by the molybdenum yellow method of JIS K0101. The residual silica concentration measured here is the total concentration of soluble silica such as orthosilicic acid, orthosilicate ion, polysilicate ion and colloidal silica.

3. (A) Composition stability test for water treatment using (E) fatty acid monoamide as component (compositions 1-14)
As examples and reference examples of the present invention, water treatment compositions having the compositions shown in Table 3 were prepared. The final product pH of these water treatment compositions was adjusted to 12.5 or higher. On the other hand, as a comparative example, in the compositions for water treatment 1 to 6 in Table 3, the composition containing no component (c), and in the compositions for water treatment 1 to 6, the amount of sodium hydroxide or potassium hydroxide was reduced to the final. A composition in which the product pH is adjusted to 11.5, a composition in which 2-ethylhexanoic acid having 8 carbon atoms is replaced with capric acid having 10 carbon atoms in water-treating composition 3, and carbon number in water-treating composition 3 A composition in which 8-ethylhexanoic acid of 8 is replaced with lauric acid having 12 carbons, and in composition 5 for water treatment, 1-octanesulfonic acid having 8 carbons is replaced with 1-decanesulfonic acid having 10 carbons. A composition in which 1-octanesulfonic acid having 8 carbon atoms was replaced with 1-dodecanesulfonic acid having 12 carbon atoms in composition 5 for water treatment was prepared. A 100 mL sample of each prepared water treatment composition was placed in a plastic bottle, sealed and allowed to stand at room temperature for 30 days, and then visually checked for the presence of turbidity, precipitation, separation, and the like.

In the water treatment compositions 8, 9 , 11 to 13 which are examples of the present invention and the water treatment compositions 1 to 7, 10, and 14 which are reference examples, the sample becomes cloudy and precipitates even after standing at room temperature for 30 days. No separation was observed. On the other hand, phase separation was confirmed in all samples of the composition for water treatment prepared as a comparative example. From this result, when (E) a fatty acid monoamide is used as the component (a) of the water treatment composition of the present invention, the solubilizer of the fatty acid monoamide as the component (d) and the alkali metal water as the component (d) It was shown that a stable one-part aqueous solution can be prepared by adding the oxide.

(Composition for test)
(1) Examples and Reference Examples : Compositions 5 and 7 to 9 and 14 shown in Table 3 and Composition 15 shown in Table 4 below
(2) Comparative Example: Compositions 16 to 21 shown in Table 4 below

Claims (4)

  A water treatment composition comprising the following component (a) and the following component (b) as active components, wherein the component (a) comprises (A) a polyhydric alcohol other than ethylene glycol and / or (B) polyhydridyl ether of polyhydric alcohol and / or polyhydric phenol, (C) hydrolyzate of polyglycidyl ether of polyhydric alcohol and / or polyhydric phenol, (D) polyhydric acid One or more compounds selected from addition products of alcohol and / or polyhydric phenol and polyglycidyl ether, and (E) fatty acid monoamide, (B) component is (F) monoethylenic non-reactive compound Polymers of saturated carboxylic acids and water-soluble salts thereof, (G) organic phosphonic acids and water-soluble salts thereof, (H) phosphonocarboxylic acids and water-soluble salts thereof, and ( ) Phosphino polycarboxylic acids and one or water treatment composition is 2 or more compounds selected from water-soluble salts thereof. The composition for water treatment according to claim 1, wherein the (E) fatty acid monoamide of the component (a) is a compound represented by the general formula (1).

(Wherein R1 and R2 are each independently selected from hydrogen, an alkyl group or alkenyl group having 1 to 22 carbon atoms, a hydroxyalkyl group or hydroxyalkenyl group having 1 to 22 carbon atoms, or R1 and R2 are Together, they form a structural unit of a cyclic amide, and R3 is a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms.)   The component (a) is a fatty acid monoamide represented by the general formula (1), and further comprises (c) a fatty acid monoamide solubilizer and (d) an alkali metal hydroxide. Composition for water treatment. A water treatment method having the effects of scale suppression, corrosion inhibition of metal in contact with water, and slime suppression, characterized by adding the following component (a) and component (b) below to the water system to be treated: The component (B) is a polyhydric alcohol other than ethylene glycol and / or an ethylene oxide adduct of a polyhydric phenol, (B) a polyglycidyl ether of a polyhydric alcohol and / or polyhydric phenol, (C) a polyhydric alcohol, and One or more compounds selected from hydrolyzate of polyglycidyl ether of polyhydric phenol, (D) polyhydric alcohol and / or addition reaction product of polyhydric phenol and polyglycidyl ether, and (E) fatty acid monoamide 2) or more, and the component (b) includes (F) a polymer of a monoethylenically unsaturated carboxylic acid and a water-soluble salt thereof, and (G) an organic phosphate. Water that is one or more compounds selected from acid and water-soluble salts thereof, (H) phosphonocarboxylic acid and water-soluble salts thereof, and (I) phosphinopolycarboxylic acid and water-soluble salts thereof Processing method.

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