WO2023067903A1 - 水系の金属防食処理方法 - Google Patents
水系の金属防食処理方法 Download PDFInfo
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- WO2023067903A1 WO2023067903A1 PCT/JP2022/032714 JP2022032714W WO2023067903A1 WO 2023067903 A1 WO2023067903 A1 WO 2023067903A1 JP 2022032714 W JP2022032714 W JP 2022032714W WO 2023067903 A1 WO2023067903 A1 WO 2023067903A1
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- WIPO (PCT)
- Prior art keywords
- component
- maleic acid
- water
- metal
- agent
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 148
- 239000002184 metal Substances 0.000 title claims abstract description 148
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 238000005260 corrosion Methods 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 64
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 173
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 172
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 172
- 239000011976 maleic acid Substances 0.000 claims abstract description 172
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 124
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 62
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- 239000011575 calcium Substances 0.000 claims description 22
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 11
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- 239000003814 drug Substances 0.000 description 20
- 238000001879 gelation Methods 0.000 description 18
- 229940079593 drug Drugs 0.000 description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 16
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- 125000001174 sulfone group Chemical group 0.000 description 13
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- 239000008233 hard water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
Definitions
- the present invention relates to a water-based metal anticorrosion method and the like.
- metal members are often used for devices and flow paths. Parts of metal members provided in a water system that come into contact with water are susceptible to corrosion. Reactors, pipes, etc. are corroded by contact with cooling water. In order to prevent this corrosion, in general, metal members provided in the water system, particularly the parts that come into contact with water, are subjected to anti-corrosion treatment, for example, by adding chemicals to the water system during operation.
- reaction vessels and piping in order to suppress corrosion of carbon steel heat exchangers, reaction vessels and piping, conventionally, it is selected from orthophosphate, hexametaphosphate, hydroxyethylidene diphosphonate, phosphonobutanetricarboxylate, etc.
- At least one anticorrosion phosphorus compound is added to a water system, such as a cooling water system.
- a water system such as a cooling water system.
- Patent Document 1 a method for effectively suppressing corrosion of metals without causing such environmental problems, for example, (A) a copolymer of acrylic acid and sulfonic acid, (B) maleic acid is added to a cooling water system for non-phosphorus and zinc treatment. and isobutylene, and (C) a method in which a zinc compound is present (Patent Document 1).
- the present inventors have found that a good anticorrosion effect can be exhibited not only in high-hardness water quality but also in low-hardness water quality, and the anticorrosion effect is further enhanced even in low-hardness water quality, and furthermore, the use of a phosphorus compound for anticorrosion.
- the present invention can exhibit a good anticorrosion effect without using a phosphorus compound that causes eutrophication as a metal anticorrosive agent, and can exhibit a good anticorrosion effect not only in high-hardness water but also in low-hardness water.
- a main object of the present invention is to provide a technology for water-based metal anticorrosion treatment that can exhibit
- the present inventors initially focused on the carboxyl group content in the maleic acid polymer.
- the carboxyl group content in the polymer contained in the drug added to the water system is high, it is likely to bind with calcium ions in water to form an insolubilized substance.
- a maleic acid-based polymer having a high carboxyl group content in the polymer is used alone, insolubilized substances tend to form even in low-hardness water, and a good anticorrosion effect cannot be obtained.
- the present inventors have been earnestly studying the anticorrosion effect of using a copolymer. The effect was not very good.
- the present invention is as follows.
- the present invention can provide a water-based metal anticorrosion treatment method in which the following component (A) and component (B) are present in the water-based system at a weight ratio of 1:9 to 7:3.
- component (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer
- component (B) A maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more in the maleic acid-based polymer
- the present invention uses the following (i) metal anticorrosion agent or (ii) metal anticorrosion agent kit, or the following (i) metal anticorrosion agent or (ii) metal anticorrosion agent kit, water-based metal
- An anti-corrosion treatment method can be provided.
- Component (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer, and component (B) a maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g. containing a maleic acid-based polymer that is above, A metal anticorrosion treatment agent, wherein the mass content ratio of component (A):component (B) is 1:9 to 7:3.
- component (ii) component (A) metal anti-corrosion primary agent containing copolymer of (meth)acrylic acid monomer and sulfonic acid monomer, and component (B) carboxyl group in maleic acid polymer
- the sulfonic acid monomer in component (A) may be a monoethylenically unsaturated sulfonic acid monomer.
- the weight average molecular weight of the copolymer in component (A) may be from 1,000 to 1,000,000.
- the molar ratio of the (meth)acrylic acid monomer and the sulfonic acid monomer in the component (A) may be 97:3 to 30:70.
- the maleic acid polymer in component (B) may have a weight average molecular weight of 500 to 5,000.
- the maleic acid-based polymer in component (B) may be a copolymer of a maleic acid monomer and an isobutylene monomer and/or polymaleic acid.
- An anti-corrosion agent may also be present in the aqueous system. Calcium hardness of the aqueous system may be 300 mg/L as CaCO 3 or less.
- a good anticorrosion effect can be exhibited without using a phosphorus compound, which is a causative agent of eutrophication, as a metal anticorrosive agent, and good anticorrosion effects can be obtained not only in high hardness water but also in low hardness water. It is possible to provide a water-based metal anticorrosion treatment technique capable of exhibiting an anticorrosion effect. Note that the effects of the present invention are not necessarily limited to the effects described herein, and may be any of the effects described in this specification.
- the present invention provides a water-based system in which the component (A) is a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer, and the component (B) is a maleic acid-based polymer having a carboxyl group content of 11. It is possible to provide a water-based metal anticorrosion treatment method in which a maleic acid-based polymer of 0.5 mmol/g or more is present at a mass usage ratio of 1:9 to 7:3.
- metal anti-corrosion agent or (ii) metal anti-corrosion agent kit is provided, and (i) metal anti-corrosion agent or (ii) metal anti-corrosion agent kit is used, water-based metal anti-corrosion A processing method can be provided.
- Component (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer, and component (B) a maleic acid-based polymer having a carboxyl group content of a predetermined amount or more.
- component (ii) component (A) metal anti-corrosion primary agent containing copolymer of (meth)acrylic acid monomer and sulfonic acid monomer, and component (B) carboxyl group in maleic acid polymer
- a metal anticorrosion second agent containing a maleic acid-based polymer having a content of not less than a predetermined content is included as a constituent agent, and the mass content ratio of the component (A):the component (B) is within a predetermined range.
- a good anticorrosion effect can be exhibited without using a phosphorus compound, which is a causative agent of eutrophication, as a metal anticorrosive agent, and good anticorrosion effects can be obtained not only in high hardness water but also in low hardness water. It is possible to provide a water-based metal anticorrosion treatment technique capable of exhibiting an anticorrosion effect.
- the target of corrosion protection is not particularly limited, but is a metal material.
- the metal material include carbon steel, copper, galvanized steel, zinc, aluminum, aluminum alloy, stainless steel, etc. One or two or more selected from these alloys and the like can be used.
- iron-based materials are preferable, and examples of the iron-based materials include iron materials in general (e.g., pure iron, carbon steel, cast iron, etc.), and more preferably, for example, It is a carbon steel material that is often used for carbon steel pipes (for example, STB steel pipes) for boilers and heat exchangers.
- the carbon steel material has a carbon content of 0.02 mass% to about 2 mass% (more specifically, 0.02 to 2.14 mass%).
- low carbon steel has a carbon content of 0.25 mass% or less
- medium carbon steel has a carbon content of 0.25 to 0.6 mass%
- 0.6 mass% or more is called high-carbon steel
- steel with carbon content of 0.6% by mass or less is also called ordinary steel.
- cast iron is said to have a carbon content of more than 2% by mass.
- ordinary steel, low carbon steel, medium carbon steel, and more preferably low carbon steel can exhibit a better anticorrosion effect.
- the object of anticorrosion treatment to which the present embodiment is preferably applied is preferably a metallic material that comes into contact with water or a metallic member that uses a metallic material that comes into contact with water.
- an excellent anti-corrosion effect is obtained especially for carbon steel materials that are in contact with water.
- places or devices using metal materials or metal members in water systems include various pipes such as water supply pipes, pipes, pumps, flow paths, heat exchangers, refrigerators, etc. 1 selected from these It may be one kind or two or more kinds. More specifically, these or their metal parts or portions are subject to the anti-corrosion treatment to which the present embodiment is preferably applied.
- component (A) copolymer of (meth)acrylic acid monomer and sulfonic acid monomer The copolymer (hereinafter also referred to as “component (A) copolymer”) is not particularly limited, and is not limited to these monomers, and includes “other monomers” within a range that does not impair the effects of the present invention. You can stay. Also, the component (A) copolymer may be a water-soluble salt.
- the salt used in the present embodiment is not particularly limited, but is preferably a salt that can convert a monomer or polymer into a water-soluble salt.
- examples of such salts include alkali metal salts such as sodium and potassium; Ammonium salts such as ammonium are included, and one or more selected from these groups can be used.
- (meth)acrylic acid monomer (meth)acrylic acid monomer
- the (meth)acrylic acid monomer is not particularly limited, but includes (meth)acrylic acid and salts thereof, and one or more selected from these groups can be used.
- “(meth)acrylic acid” means at least one selected from the group consisting of "acrylic acid” and "methacrylic acid”. Among these, acrylic acid or a salt thereof is preferable.
- the sulfonic acid monomer is not particularly limited, but a monomer containing a sulfone group is preferable from the viewpoint of exhibiting a better anticorrosion effect due to the combined effect of the component (A) and the component (B). and the monomer is more preferably an unsaturated monomer.
- the sulfonic acid monomer include, but are not limited to, monoethylenically unsaturated sulfonic acid monomers and salts thereof. Of these, monoethylenically unsaturated sulfonic acid monomers are preferred. be.
- the sulfonic acid monomer examples include monomers having an amide group and a sulfone group (preferably those having 6 to 9 carbon atoms), monomers containing a hydroxyl group and a sulfone group (preferably having 6 to 9), sulfonated products of aliphatic conjugated dienes (preferably those having 4 to 15 carbon atoms) and salts thereof, etc., and one or more selected from these groups can be used. can.
- a monomer having an amide group and a sulfone group preferably those having 6 to 9 carbon atoms
- a monomer containing a hydroxyl group and a sulfone group preferably those having 6 to 9 carbon atoms
- the "sulfone group" of the monomer may be a sulfone group that may have a substituent, such as an alkylsulfone group, and the number of carbon atoms in the "alkyl” of the alkylsulfone group is 1 to 8 are preferred, and a methylpropanesulfone group (also referred to as a tert-butylsulfone group) is more preferred.
- a better anti-corrosion effect can be exhibited due to the combined effect of the component (A) and the component (B).
- Examples of the monomer having an amide group and a sulfone group include (meth)acrylamidoalkylpropanesulfonic acid, crotonamidoalkylpropanesulfonic acid, etc. More specifically, for example, 2-acrylamido-2-methyl propanesulfonic acid, 3-acrylamido-3,3-dimethylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-3,3-dimethylpropanesulfonic acid and the like, from these groups 1 type or 2 or more types selected can be used.
- Examples of monomers containing a hydroxy group and a sulfone group include 3-allyloxy-2-hydroxypropanesulfonic acid, 3-methacryloxy-2-hydroxypropanesulfonic acid, and 3-allyloxy-1-hydroxypropane-2-sulfone. acid, 3-methacroxy-1-hydroxypropane-2-sulfonic acid, etc., and one or more selected from these groups can be used.
- sulfonated aliphatic conjugated diene examples include sulfonated 1,3-butadiene and sulfonated 2,3-dimethyl-1,3-butadiene, and one or two selected from these groups. The above can be used.
- More preferred sulfonic acid monomers include (meth)acrylamidomethylpropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, (meth)allylsulfonic acid, vinylsulfonic acid, styrenesulfonic acid, and 2-sulfoethyl Examples include sulfone group-containing unsaturated monomers such as methacrylates, salts thereof, and the like, and one or more selected from these groups can be used. Among these, at least one monomer selected from 2-acrylamido-2-methylpropanesulfonic acid and 3-allyloxy-2-hydroxypropanesulfonic acid is preferred. As a result, a better anticorrosion effect can be exhibited due to the combined effect of the component (A) and the component (B).
- component (A) copolymer Other Monomers>
- “other monomers” in the component (A) copolymer include, but are not limited to, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl monomers such as N-vinyl-methylacetamide and N-vinyloxazolidone; nitrogen-containing nonionic unsaturated monomers such as (meth)acrylamide, t-butylacrylamide, N,N-dimethylacrylamide and N-isopropylacrylamide; hydroxyl group-containing unsaturated monomers such as monomers, 3-(meth)-allyloxy-1,2-dihydroxypropane, (meth)allyl alcohol and isoprenol; adding about 1 to 200 moles of ethylene oxide to (meth)allyl alcohol; Polyoxyethylene group-containing unsaturated monomers such as polyoxyethylene group-containing compounds; (meth) acrylics
- the molar ratio (mol%) of the (meth)acrylic acid monomer and the sulfonic acid monomer in the copolymer of component (A) (meth)acrylic acid monomer and sulfonic acid monomer is particularly limited.
- component (A) copolymer used in this embodiment can be produced by a known production method.
- Preferred component (A) copolymers include (i) a (meth)acrylic acid monomer and (ii) a monomer having an amide group and a sulfone group, a monomer containing a hydroxy group and a sulfone group, and the like. It is a polymer obtained by copolymerizing a sulfonic acid monomer selected from and a predetermined mass ratio.
- More preferred component (A) copolymers are selected from (i) acrylic acid monomers and (ii) 2-acrylamido-2-methylpropanesulfonic acid and 3-allyloxy-2-hydroxypropanesulfonic acid It is a polymer obtained by copolymerizing at least one sulfonic acid monomer at a predetermined mass ratio. Still more preferred component (A) copolymers are copolymers of acrylic acid monomers and 2-acrylamido-2-methylpropanesulfonic acid monomers, acrylic acid monomers and 3-allyloxy-2- One or two or more selected from the group consisting of copolymers with hydroxypropanesulfonic acid monomers, etc.
- the predetermined molar ratio is 97:3 to 70:30, and the molar ratio (mol%) in the above-described component (A) copolymer can be appropriately adopted.
- the phosphorus compound is not used as a metal anticorrosive agent, it is possible to exhibit a better anticorrosion effect and better anti-gelling ability even in water with a low hardness concentration.
- the weight-average molecular weight of the copolymer of the (meth)acrylic acid monomer and the sulfonic acid monomer by GPC method is not particularly limited, but is preferably 1,000 to 1,000,000, more preferably 3,000. 000 to 1,000,000, more preferably 3,000 to 80,000, more preferably 5,000 to 50,000 (preferably 30,000).
- the weight average molecular weight of the polymer can be measured by ⁇ GPC analysis of weight average molecular weight of polymer> (converted to polyacrylic acid). By adjusting the weight-average molecular weight, it is possible to exhibit a better anticorrosion effect due to the effect of the combined use of the component (A) and the component (B).
- Component (B) maleic acid-based polymer used in the present invention is such that the carboxyl group content in the polymer is at least a predetermined amount. From the viewpoint of exhibiting a better anticorrosion effect due to the combined effect of B), the predetermined content is preferably a predetermined amount or more, for example, 11.5 mmol/g or more.
- the component (B) maleic acid-based polymer used in the present embodiment is preferably a polymer containing maleic acid as a main structural unit, and the component (B) maleic acid-based polymer is a homopolymer or Any copolymer may be used.
- homopolymers include polymaleic acid polymerized from maleic acid-based monomers, for example, maleic acid.
- the copolymer is not particularly limited, but includes a copolymer of a maleic acid-based monomer and another monomer copolymerizable therewith.
- the component (B) maleic acid-based polymer may be a water-soluble salt, and the salt described in "1-1.” above can be appropriately employed as the salt.
- the component (B) maleic acid-based polymer is not particularly limited, and may be either a polymer obtained by an organic solvent-based polymerization method or an aqueous polymerization method, and the polymerization method may be appropriately carried out by adopting known techniques.
- a commercially available product may be used.
- a method capable of polymerizing such that the carboxyl group content in the polymer becomes a predetermined level or higher, for example, 11.5 mmol/g or more, can be appropriately adopted.
- monomers copolymerizable with the maleic acid-based monomers preferably maleic acid monomers
- maleic polymer maleic monomer>
- the maleic acid-based monomer is not particularly limited. A species or two or more species can be used. Among the maleic acid-based monomers, maleic acid monomers are preferred, maleic anhydride-based monomers are preferred, and maleic anhydride is more preferred.
- a hydrolyzate of maleic anhydride (maleic acid) may also be used as a monomer, and the maleic anhydride-based monomer includes maleic anhydride and a hydrolyzate of maleic anhydride. included. Thereby, a better anticorrosion effect can be exhibited due to the combined effect of the component (A) and the component (B).
- maleate examples include mono- or dialkali metal salts such as lithium salts, sodium salts and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; and ammonium salts such as ammonium salts and diammonium salts.
- the maleic acid ester examples include saturated hydrocarbon alcohols such as methanol and ethanol, unsaturated hydrocarbon alcohols such as allyl alcohol and methallyl alcohol, polyalkylene glycols, polyoxyalkylene monomethyl ethers, and polyoxyalkylene monoallyl ethers. and the like, and one or more selected from the group consisting of these can be used.
- component (B) maleic acid polymer copolymerizable monomer
- the copolymerizable monomer (hereinafter also referred to as “component (B) copolymerizable monomer”) in the component (B) maleic acid polymer is not particularly limited, but for example, N-vinyl N-vinyl monomers such as pyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-methylacetamide, N-vinyloxazolidone; (meth)acrylamide, t-butylacrylamide , N,N-dimethylacrylamide, nitrogen-containing nonionic unsaturated monomers such as N-isopropylacrylamide; 3-(meth)-allyloxy-1,2-dihydroxypropane, (meth)allyl alcohol, hydroxyl group-containing such as isoprenol Unsaturated monomers; polyoxyethylene group-containing unsaturated monomers such as
- the copolymerizable monomers of component (B) unsaturated hydrocarbon monomers (preferably ethylenically unsaturated hydrocarbon monomers) are preferred, and the unsaturated hydrocarbon monomers are chain Monoethylenically unsaturated hydrocarbon monomers are preferred, and those having 4 to 6 carbon atoms are preferred.
- the copolymerizable monomers of component (B) chain monoethylenically unsaturated hydrocarbon monomers are preferred, and among chain monoethylenically unsaturated hydrocarbon monomers, isobutylene Monomers are more preferred. Thereby, a better anticorrosion effect can be exhibited due to the combined effect of the component (A) and the component (B).
- Examples of monoethylenically unsaturated hydrocarbons having 4 to 6 carbon atoms among the copolymerizable monomers of component (B) include isobutene, 1-butene, 2-butene, 1-pentene, 2- chain monoethylenically unsaturated hydrocarbons such as pentene, methylbutene, methylpentene, and hexene; cyclic monoethylenically unsaturated hydrocarbons such as cyclopentene, methylcyclopentene, and cyclohexene; One or two or more selected from can be used. Thereby, a better anticorrosion effect can be exhibited due to the combined effect of the component (A) and the component (B).
- component (B) maleic acid polymer is a copolymer of maleic acid monomer and monoethylenically unsaturated hydrocarbon monomer (preferably isobutylene monomer) and/or polymaleic acid (preferably homopolymers of maleic acid monomers) are preferred. Thereby, a better anticorrosion effect can be exhibited due to the combined effect of the component (A) and the component (B).
- the carboxyl group content in the component (B) maleic acid-based polymer is the total content of carboxyl groups in the polymer, regardless of whether it is a homopolymer or a copolymer, and regardless of whether it is derived from a monomer.
- the carboxyl group content in the polymer is preferably 11.5 mmol/g or more, more preferably 11.7 mmol/g or more, still more preferably 12 mmol/g or more, and more preferably 12.5 mmol as a suitable lower limit.
- the carboxyl group content in the component (B) maleic acid-based polymer is determined according to ⁇ Test 1: Titration analysis of carboxyl group content in maleic acid-based polymer (samples 1 to 5)> in [Examples] described later. , can be asked.
- the component (A) copolymer by using the component (A) copolymer together, even if the carboxyl group content in the component (B) maleic acid polymer is set to a predetermined height or more, the above-mentioned Since the gelation of the component (B) can be better suppressed and dispersed better, the anticorrosion effect improved by increasing the carboxyl group content in the polymer of the component (B) can be better exhibited. can be made
- the weight-average molecular weight of the component (B) maleic acid-based polymer as determined by GPC is not particularly limited, but the preferred lower limit is preferably 250 or more, more preferably 500 or more, and the preferred upper limit is Preferably 10,000 or less, more preferably 8,000 or less, still more preferably 5,000 or less, more preferably 3,000 or less, the preferred numerical range is preferably 500 to 5,000, more preferably 500 ⁇ 3,000.
- the weight average molecular weight of the polymer can be measured by ⁇ GPC analysis of weight average molecular weight of polymer> (converted to polyacrylic acid). By adjusting the weight-average molecular weight, it is possible to exhibit a better anticorrosion effect due to the effect of the combined use of the component (A) and the component (B).
- component (A) copolymer and the component (B) maleic acid-based polymer are -1.” and the component (B) maleic acid-based polymer described in “1-2.” can be appropriately employed and combined.
- the weight ratio of the component (A) copolymer and the component (B) maleic acid-based polymer used in the present invention is not particularly limited, but it is preferable that they are present in an aqueous system at a ratio of 1:9 to 7:3, respectively. , more preferably 2:8 to 7:3, more preferably 3:7 to 7:3, more preferably 3:7 to 6:4, more preferably 3:7 to 5.5:4.5 is.
- mass usage ratio mass usage ratio
- gelation that occurs in the aqueous system due to the component (B) maleic acid polymer can be suppressed more satisfactorily, and due to the combined effect of these components (A) and (B) A better anticorrosion effect can be exhibited.
- mass ratio used is said component (A) copolymer (mg soil/L): said component (B) maleic acid polymer (mg soil/L).
- the amount of the component (A) copolymer added to the aqueous system is not particularly limited, but a suitable lower limit is preferably 0.1 mg/L or more, and more It is preferably 0.5 mg/L or more, more preferably 1 mg/L or more, more preferably 2 mg/L or more, still more preferably 3 mg/L or more, more preferably 4 mg/L or more.
- the component (A) copolymer is preferably 100 mg / L or less, more preferably 50 mg / L or less, still more preferably 30 mg / L or less, still more preferably 20 Or 15 mg/L or less, more preferably 7 or 6 mg/L or less, and the preferred numerical range is preferably 3 to 15 mg/L.
- the amount (mg soil/L, hereinafter referred to as "mg/L") of the component (B) maleic acid-based polymer added to the aqueous system is not particularly limited, but a suitable lower limit is preferably 0.1 mg/L or more.
- the value is not particularly limited, it is preferably 100 mg/L or less, more preferably 50 mg/L or less, still more preferably 30 mg/L or less, and even more preferably from the viewpoint of the balance between reducing the amount of chemical used and exhibiting anticorrosion effects. is 20 or 15 mg/L or less, more preferably 7 or 6 mg/L or less, and the preferred numerical range is preferably 3 to 15 mg/L.
- a preferred aspect is better anticorrosion due to the combined effect of the component (A) and the component (B).
- the component (A) is a copolymer of a (meth)acrylic acid monomer and a monoethylenically unsaturated sulfonic acid monomer
- the component (B) is a maleic acid polymer.
- component (A) copolymer and the component (B) maleic acid-based polymer exhibits a better anticorrosive effect.
- component (A) a copolymer of an acrylic acid monomer and a monomer having an amide group and an alkylsulfone group, or an acrylic acid monomer and a hydroxy group and an alkylsulfone group and (ii) in component (B), a polymer of a maleic acid monomer and a monoethylenically unsaturated hydrocarbon monomer, or a maleic acid monomer Homopolymers are mentioned.
- More preferred embodiments of the component (A) include copolymers of acrylic acid monomers and (meth)acrylamidoalkylpropanesulfonic acid monomers, and acrylic acid monomers and allyloxyhydroxypropanesulfonic acid monomers. and a polymer of an acrylic acid monomer and a methacryloxyhydroxypropanesulfonic acid monomer.
- a copolymer of acrylic acid monomer and 2-acrylamido-2-methylpropanesulfonic acid and/or a copolymer of acrylic acid monomer and 3-allyloxy-2-hydroxypropanesulfonic acid is more preferred. Thereby, a better anticorrosion effect can be exhibited due to the combined effect of the component (A) and the component (B).
- a maleic acid monomer preferably maleic anhydride
- a chain monoethylenically unsaturated hydrocarbon having 4 to 6 carbon atoms preferably isobutylene
- polymaleic acid preferably a polymer composed of maleic anhydride
- optional components may be used in the aqueous system or included in the drug as appropriate within a range that does not impair the effects of the present invention.
- the optional component is not particularly limited, for example, one or more selected from the group consisting of pH adjusters, antifoaming agents, anticorrosives, scale inhibitors, bactericides, algicides, etc. good.
- a scale inhibitor other than these components may be present in the aqueous system.
- the scale inhibitor include phosphonic acid and its salts, phosphotartaric acid and its salts, acrylic acid-based polymers and their salts, maleic acid-based polymers and their salts, polyaspartic acid and its salts, and the like. 1 type or 2 types or more can be used.
- a slime control agent is present as a component other than these. It is preferable to let The slime control agent is not particularly limited, but may be selected from hypochlorous acid and its salts, chlorine gas, hypobromous acid and its salts, stabilized chlorine, stabilized bromine, organic disinfectants, and the like. 1 type or 2 types or more can be used.
- ⁇ Anticorrosive agent> in the aqueous system, in addition to the combined use of the above-described component (A) copolymer and component (B) maleic acid polymer, further components other than the combination of component (A) and component (B) (C)
- an anti-corrosion agent more preferably an anti-corrosion metal compound
- the metal compound for anticorrosion is a metal compound used for anticorrosion, and the metal compound is a metal compound that can easily release heavy metal ions into water. , is not particularly limited.
- the component (C) anticorrosion agent is not particularly limited, but examples include zinc salts, tin salts, manganates, anticorrosion metal compounds such as aluminum and aluminates, organic acid compounds, acrylic acid polymers and salts thereof. , polyaspartic acid and its salts, polyitaconic acid and its salts, amine compounds, amino acid compounds, etc., and one or more selected from the group consisting of these are combined with the component (A) copolymer and the component (B) It can be used in combination with the maleic acid-based polymer.
- the anticorrosion metal compound is more preferable, and among these anticorrosion metal compounds, zinc salts and/or tin salts are preferable, and zinc salts are more preferable.
- the amount (mg soil/L, hereinafter referred to as "mg/L") of the component (C) anticorrosive added to the aqueous system is not particularly limited, but a suitable lower limit is preferably 0.1 mg/L or more, and more It is preferably 0.5 mg/L or more, and a suitable upper limit is preferably 5 mg/L or less, more preferably 4 mg/L or less, still more preferably 3 mg/L or less, and more preferably 2 mg/L or less.
- a suitable lower limit is preferably 0.1 mg/L or more, and more It is preferably 0.5 mg/L or more, and a suitable upper limit is preferably 5 mg/L or less, more preferably 4 mg/L or less, still more preferably 3 mg/L or less, and more preferably 2 mg/L or less.
- the phosphorus compound as an anticorrosive agent A good anti-corrosion effect can be exhibited without using
- the amount of the phosphorus compound added to the aqueous system is not particularly limited, but from the viewpoint of reducing eutrophication, it is preferably 0.5 mg/L as P or less, more preferably 0.3 mg/L as P or less. , More preferably, it is 0.1 mg/L as P or less, and it is more preferable that it is substantially not used or not included.
- the "substantially not used or not included” is preferably 0.05 mg/L as P or less, more preferably 0.01 mg/L as P or less, and no phosphorus compound added to the water system. It is more suitable.
- the phosphorus concentration can be measured using the molybdenum blue (ascorbic acid reduction) method (JIS K 0102 46.1.1).
- the above-described component (A) copolymer and component (B) maleic acid polymer are added at a predetermined mass usage ratio or mass content ratio. , it is preferably present in an aqueous system, more preferably at a ratio of 1:9 to 7:3.
- the component (A) copolymer and the component (B) maleic acid-based polymer can be added to the aqueous system as a one-component chemical agent or as a multi-component chemical agent.
- the component (A) copolymer and the component (B) maleic acid polymer may be added to the aqueous system so that they can be mixed at least, and they may be added at the same time or separately. , and may be continuous or intermittent.
- a water-based metal anticorrosion treatment method using the following (i) metal anticorrosion agent or (ii) metal anticorrosion agent kit can be provided.
- (i) (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer, and (B) a maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more, A metal anti-corrosion treatment agent, wherein the mass content ratio of (A):(B) is 1:9 to 7:3.
- the water system to which this embodiment is applied is not particularly limited, and examples thereof include a cooling water system, an RO water system, a paper pulp process water system, a scrubber water system, and the like.
- This embodiment has an excellent feature that it can be applied to a wide range of water quality from high hardness to low hardness.
- the anticorrosion effect is sufficiently exhibited if the water quality is that of a general cooling water system.
- the anticorrosion effect is sufficiently exhibited without using a phosphorus compound as a metal anticorrosive agent, so it can be applied to the phosphorus concentration wastewater standards of each country.
- the phosphorus concentration described in the amount can be appropriately adopted, for example, the phosphorus concentration as a water quality condition is preferably 0.5 mg/L as P or less, more preferably 0.1 mg/L as P or less. .
- the calcium hardness is not particularly limited as a water quality condition of the water system, and in the present embodiment, the anticorrosion effect can be obtained not only at high hardness but also at low hardness, and the preferable upper limit is not particularly limited, For example, it is 1000 mg/L as CaCO 3 or less, preferably 500 mg/L as CaCO 3 or less, more preferably 300 mg/L as CaCO 3 or less.
- a suitable lower limit is preferably 1 mg/L as CaCO 3 or more, more preferably 5 mg/L as CaCO 3 or more.
- Calcium hardness can be determined according to JIS K0101 industrial water test method.
- M alkalinity (acid consumption (pH 4.8)) is not particularly limited as a water quality condition of the aqueous system, preferably 10 to 1000 mg/L as CaCO 3 , more preferably 25 to 500 mg/L as CaCO 3 , and still more preferably. is 100-300 mg/L as CaCO 3 .
- the acid consumption (PH4.8) can be determined according to JIS K0101 industrial water test method.
- the magnesium hardness is not particularly limited as a water quality condition of the water system, and is preferably 500 mg/L or less, more preferably 300 mg/L or less, still more preferably 200 mg/L or less, and more preferably 100 mg/L or less.
- Magnesium hardness can be determined according to JIS K0101 industrial water test method.
- the silica concentration is not particularly limited as a water quality condition of the aqueous system, and is preferably 5 to 250 mg/L, more preferably 10 to 150 mg/L, and still more preferably 15 to 100 m/L.
- the silica concentration can be determined according to JIS K0101 industrial water test method.
- the chloride ion concentration is not particularly limited as a water quality condition of the aqueous system, and is preferably 5 to 500 mg/L, more preferably 50 to 300 mg/L, and even more preferably 50 to 200 mg/L.
- the chloride ion concentration can be determined according to JIS K0101 industrial water test method.
- the sulfate ion concentration is not particularly limited as a water quality condition of the aqueous system, and is preferably 500 mg/L or less, more preferably 300 mg/L or less, and still more preferably 200 mg/L or less.
- the sulfate ion concentration can be determined according to JIS K0101 industrial water test method.
- the pH is preferably 6 to 11, more preferably 6.5 to 10, and even more preferably 7 to 9 as a water quality condition of the aqueous system.
- the water temperature of the aqueous system is not particularly limited, but is preferably 0 to 100°C, more preferably 5 to 80°C, and still more preferably 10 to 60°C.
- the present embodiment it is suitable to apply to a water system in which metal materials that are easily corroded by water are used in various places (for example, heat exchangers, piping, etc.), more preferably cooling It is water-based and can be suitably applied to a circulating cooling water system. According to this embodiment, the anticorrosion effect of the anticorrosion treatment method of the present invention is sufficiently exhibited.
- the method of the present embodiment can also be realized by a control unit including a CPU in a device (for example, a computer, PLC, server, cloud service, etc.) for managing the metal anticorrosion treatment described above and the cooling water system described later.
- a control unit including a CPU in a device (for example, a computer, PLC, server, cloud service, etc.) for managing the metal anticorrosion treatment described above and the cooling water system described later.
- the method of the present embodiment may be stored as a program in a hardware resource including a recording medium (nonvolatile memory (USB memory, etc.), HDD, CD, DVD, Blu-ray, etc.) and implemented by the control unit. It is possible.
- the recording medium is preferably a computer-readable recording medium. It is also possible to provide an apparatus comprising the controller or the system, such as a metal anticorrosion treatment system that controls the addition of chemicals to the water system by the controller.
- the management device includes at least a CPU as a component of a computer, an input unit such as a keyboard, a communication unit such as a network, a display unit such as a display, a storage unit such as an HDD, a ROM, a RAM, and the like. , one or more of these can be selected. Among these, it is preferable to include a RAM, a storage section, a display section, and an input section, and each selected component is connected by a bus as a data transmission line, for example.
- the cooling water system in the present embodiment refers to a system through which cooling water used for operating heat exchangers and the like is passed in air-conditioning equipment such as buildings and regional facilities, plants, and the like.
- the cooling water system may be of a once-through type, an open circulation type, or a closed circulation type.
- the circulating cooling water system is not particularly limited, and is preferably a water system including cooling towers installed in air conditioners, petrochemical complexes, general factories, etc., for example.
- the circulating cooling water system is preferably configured to indirectly cool the heat sources generated in these air conditioning, general factories, etc., and is configured to include a heat exchanger, a circulating water channel, and a cooling tower. It may be a general water system with water.
- the type of the circulating cooling water system is not particularly limited, but it may be either an open circulating cooling water system or a closed circulating cooling water system. It is preferable that the closed circulation cooling water system is closed and has a configuration in which cooling water can be circulated.
- the cooling water system metal corrosion prevention treatment method (more specifically, the metal corrosion prevention treatment method for metal members in the cooling water system) of the present embodiment includes, in the cooling water system, the component (A) copolymer and the component (B) It is preferable to have at least a step of adding a maleic acid-based polymer and bringing it into contact with the metal member.
- the component (A) and the component (B) may be added in a metal anticorrosion treatment agent that is a one-component chemical, or in a metal anticorrosion treatment agent kit that is a multi-component chemical. It may be added.
- the place where the chemical is added is not particularly limited, and may be any place in the cooling water system. preferably a replenishing water supply means, a drug injection means, a circulating water channel, a transfer pump, etc., and can be added at one or more locations selected from these.
- the synergistic effect of both the component (A) and the component (B) can impart an excellent anticorrosion effect to the metal member.
- a metal anti-corrosion treatment method for an open circulation cooling water system 1, which is an example of the present embodiment, will be described with reference to FIG. 1, but the present embodiment is not limited to this.
- the open circulation cooling water system 1 the water containing the component (A) copolymer and the component (B) maleic acid polymer is transferred from the pit 15 to the heat exchanger 30 through the circulation channel 20 by the transfer pump 21. , the heat exchanger 30 and the open cooling tower 10 through the circulation water line 20 .
- the water containing the component (A) and the component (B) passes through the sprinkler means 12 and the filler region 13, is stored in the pit 15, and is transferred to the circulating water channel 20 by the pump 21 again. be done.
- the coexistence of the component (A) and the component (B) allows the component (B) to maintain a well-dispersed state without gelation.
- the anti-corrosion effect can be maintained.
- the component (A) and the component (B) present in the water in the water system can come into contact with the metal member and exhibit anticorrosion effects on the metal member.
- the component (A) and the component (B) are transferred to the pit 15 at the same time or at different times by one or more drug injection means 17, and both are mixed in the piping during this transfer. Alternatively, both may be mixed within the pit 15 .
- one or more drug injection means 17 may be provided.
- a plurality of separate drug injection means may be provided for the component (A) and for the component (B), respectively.
- a single drug injection means may be provided for adding a one-component drug containing to the aqueous system.
- the component (C) anticorrosion agent preferably anticorrosion metal compound
- these agent injection means may be used, or a separate agent injection means may be provided.
- Water lacking due to transpiration or the like is supplied to the pit 15 by the make-up water supply means 16 as needed, and the passage for supplying this make-up water to the pit 15 is filled with one or more chemicals from the chemical injection means 17. It may be configured to allow Air for cooling is discharged from the looper 18 through the loopers 13 and 12 by the external air discharge by the air blowing means 11 from the looper 11 .
- Metal anti-corrosion agent and metal anti-corrosion agent kit according to the present embodiment
- Water-based metal anti-corrosion treatment method according to the present embodiment Descriptions of component (A), component (B), each addition amount, each mass usage ratio, each configuration, each method, each term, etc., which overlap with the description of , are omitted as appropriate, but the description of the above "1.”
- the mass usage ratio, etc. in the above “1.” can also be changed to a mass content ratio, etc.
- the medicament of the present embodiments can be provided as either a one-part medicament or a multi-part medicament.
- the agent of the present embodiment comprises (i) component (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer, and It is possible to provide a metal anti-corrosion agent containing component (B) a maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more in the maleic acid-based polymer.
- the mass content ratio of the component (A) to the component (B) in the anticorrosion agent is from 1:9 to 7:3.
- the agent of the present embodiment comprises, as a metal anticorrosion treatment agent kit, a metal anticorrosion first agent containing a component (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer, and a component ( B) Providing a metal anti-corrosion treatment agent kit containing, as a constituent agent, a metal anti-corrosion secondary agent containing a maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more in the maleic acid-based polymer. More preferably, the weight ratio of component (A):component (B) is 1:9 to 7:3. In the kit, the component (A) and the component (B) may be contained in separate containers.
- optional ingredients such as the component (C) anticorrosive agent and phosphorus compound may be included in the metal anticorrosion treatment kit in a separate container as constituent agents of the third agent, or the first agent and/or may be incorporated into the first drug and/or the second drug as a mixed component of the second drug.
- the sulfonic acid monomer in component (A) is preferably a monoethylenically unsaturated sulfonic acid monomer.
- the weight average molecular weight of the copolymer in component (A) is preferably from 1,000 to 1,000,000.
- the molar ratio of the (meth)acrylic acid monomer and the sulfonic acid monomer in the component (A) is preferably 97:3 to 30:70.
- the weight average molecular weight of the maleic acid-based polymer in the component (B) is 500 to 5,000. It is preferable that the maleic acid-based polymer in the component (B) is a copolymer of a maleic acid monomer and an isobutylene monomer and/or a polymaleic acid.
- the metal anti-corrosion treatment agent further contains an anti-corrosion agent (preferably an anti-corrosion metal compound), or the metal anti-corrosion treatment agent kit further contains an anti-corrosion agent (preferably an anti-corrosion metal compound). It is preferable to include a contained third agent for metal corrosion prevention.
- the metal anti-corrosion agent or the metal anti-corrosion agent kit can be used appropriately according to the water quality conditions of the water system. It is suitable to use with the said calcium hardness.
- the component (A) copolymer and the component (B) maleic acid-based polymer can exert a metal anticorrosion action. Therefore, the component (A) copolymer and the component (B) maleic acid-based polymer can be contained as active ingredients in a metal anticorrosion agent or the like, or can be used in the metal anticorrosion agent or the like. In addition, the said agent may be a composition. Further, the component (A) copolymer and the component (B) maleic acid polymer can be used for producing a metal anti-corrosion agent and the like.
- the present embodiment provides the component (A) copolymer and the component (B) maleic acid-based polymer, or uses thereof, for anticorrosion treatment of metals or for use in anticorrosion treatment of metals.
- This embodiment is a metal anticorrosion treatment method using the component (A) copolymer and the component (B) maleic acid-based polymer, or a metal anticorrosion treatment using a one-component agent or a multi-component agent containing these. It is also possible to provide a method.
- a water-based metal anticorrosion treatment method in which the following component (A) and component (B) are present in a water-based system at a mass ratio of 1:9 to 7:3.
- (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer, and
- (B) A maleic acid polymer having a carboxyl group content of 11.5 mmol/g or more
- the sulfonic acid monomer in (A) is a monoethylenically unsaturated sulfone
- component (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer, and (B) a maleic acid polymer for producing a metal anticorrosion agent A maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more, or use thereof.
- component (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer
- component (B ) A maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more, or use thereof.
- a metal anticorrosion first agent containing component (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer for producing a metal anticorrosion agent kit, and the above (B) A second agent for preventing corrosion of metals containing a maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more in the maleic acid-based polymer, or the use thereof.
- Component (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer, or use thereof, for producing the metal anticorrosion first agent of the metal anticorrosion agent kit.
- a metal containing component (A) a copolymer of a (meth)acrylic acid monomer and a sulfonic acid monomer for use in a metal anticorrosion agent kit or for a metal anticorrosion agent kit
- a first anticorrosion agent and a second anticorrosion agent for metals containing component (B) a maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more in the maleic acid-based polymer, or use thereof.
- Component (A) (meth)acrylic acid monomer and sulfonic acid monomer for use as the first metal anticorrosion agent of the metal anticorrosion treatment agent kit or for the first metal anticorrosion agent or the use thereof.
- the carboxyl group content in the component (B) maleic acid-based polymer is 11.5 mmol/g for use in the second metal anticorrosion agent of the metal anticorrosion treatment agent kit or for the second metal anticorrosion agent.
- ⁇ Test 1 Titration analysis of carboxyl group content in maleic acid polymer (samples 1 to 5)> ⁇ Method> Titrando (Metorom) was used for titration analysis. 1 g of a maleic acid-based polymer was dissolved in 20 mL of pure water, and after lowering the pH to 2 or less using hydrochloric acid, the solution was set in Titrando and titrated with 0.5 mol/L NaOH. The amount of NaOH required for neutralization of the maleic acid polymer is calculated from the difference between the amount of NaOH added to the neutralization point of the hydrochloric acid and the amount of NaOH added to the neutralization point of the maleic acid polymer.
- the carboxyl group content in the acid polymer was calculated.
- the calculation formula is as follows.
- Carboxyl group content (mmol/g) in maleic acid-based polymer (NaOH aqueous solution (0.5 mol/L) amount (mL) required for neutralization of maleic acid-based polymer/0.5 (mol/L) ) ⁇ used maleic acid polymer 1 (g)
- Samples 1 to 5 used commercially available products, Sample 1: Isovan KPS-3 (maleic anhydride: manufactured by Kuraray), Sample 2: Bellclean 288 (manufactured by Italmatch), Sample 3: Bellclean 272 (manufactured by Italmatch), Sample 4. : Crest Guard 559 (manufactured by Crestwater), Sample 5: HPMA-S Manufactured by Changzhou Dongna Chemical Co., Ltd. Samples 1 to 3 and 5 were polymerized in an organic solvent system, and sample 4 was polymerized in an aqueous system.
- Maleic anhydride is generally used as a raw material for maleic acid-based polymers.
- maleic anhydride is used as a raw material for sample 1.
- Table 1 shows the maleic acid-based polymers (Samples 1 to 5) subjected to titration analysis and their carboxyl group contents. Samples 4 and 5 have in common that they have a higher carboxyl group content than other maleic acid-based polymers. From sample 3 and sample 4, a maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more in the maleic acid-based polymer was obtained. It was set as a system polymer.
- GPC gel permeation chromatography
- each test water (Comparative Examples 2-1 to 2-4, Examples 2-1 to 2-7) was prepared so that the first drug and the second drug were added at concentrations shown in Table 2. It is prepared by adding to raw water.
- the operating conditions for evaluating the anticorrosion effect are a water temperature of 30° C., a test period of 3 days, and a rotation speed of 150 rpm.
- the water quality conditions of the raw water used were calcium hardness 100 mg/L as CaCO 3 , acid consumption (pH 4.8) 100 mg/L as CaCO 3 , magnesium hardness 50 mg/L, silica 20 mg/L, chloride ion concentration 100 mg/L. , sulfate ion concentration 100 mg/L, pH 8.2.
- the material used for the test is an SPCC test piece (30 mm x 50 mm x 1 mm).
- the SPCC steel used has a carbon content of 0.02 to 0.15% by mass and is classified as low carbon steel.
- Corrosion rate (mdd) corrosion weight loss (mg)/test piece surface area (dm 2 )/test period (day)
- Table 2 shows the measurement results of the corrosion rate.
- the calcium hardness solution was added so as to have a predetermined concentration, each polymer solution was added so that the concentration in the test water was 100 mg/L, and ultrapure water was added so that the total amount was 500 mL.
- Table 3 shows the test conditions and the absorbance measurement results. Turbidity of the test solution was confirmed at a specific calcium hardness for each of the maleic acid-based polymers of Samples 1 to 4, indicating that gelation had occurred. However, it was found that the calcium concentration at which gelation occurs (calcium hardness) differs depending on the type of polymer. Compared with the carboxyl group content in the polymer shown in Table 1, it was found that gelation occurs at a lower calcium concentration in the test solution as the carboxyl group content in the polymer increases. On the other hand, it was confirmed that AA/AMPS-1 and AA/HAPS-1 did not gel even when the calcium hardness was 1000 mg/L as CaCO 3 .
- Ultrapure water was added in a total amount of 500 mL so that each polymer solution and calcium hardness solution had a predetermined concentration.
- Table 4 shows the test conditions and the absorbance measurement results. Gelation occurred in conditions 3 and 4 in which only sample 4 was added as a maleic acid polymer having a carboxyl group content of 11.5 mmol/g or more in the polymer. In contrast, when AA/AMPS-1 and Sample 4 were used together, gelation did not occur. From this fact, by using a maleic acid-based polymer having a high carboxyl group content in the polymer and the AA/AMPS-1 polymer together, calcium ions in water and a maleic acid-based polymer having a high carboxyl group content in the polymer can be obtained.
- the water quality conditions of the raw water used were calcium hardness 100 mg/L as CaCO 3 , acid consumption (pH 4.8) 100 mg/L as CaCO 3 , magnesium hardness 50 mg/L, silica 20 mg/L, chloride ion concentration 150 mg/L. , sulfate ion concentration 150 mg/L, pH 8.2, AA/AMPS-1 6 mg/L, maleic acid polymer 6 mg/L.
- the material used for the test is an SPCC test piece (30 mm x 50 mm x 1 mm). One test piece was immersed in 1 L of test water and stirred with a stirrer under the operating conditions described above.
- Corrosion rate (mdd) corrosion weight loss (mg)/test piece surface area (dm 2 )/test period (day)
- Table 5 shows the concentration of chemicals used in the corrosion test and the measurement results of the corrosion rate.
- a good anticorrosion effect was confirmed when Samples 4 and 5 were used as the maleic acid-based polymer with a high carboxyl group content.
- the carboxyl group contents in the polymers of Samples 4 and 5 are the highest, indicating that the carboxyl group content in the maleic acid-based polymer is 11.5 mmol/g or more.
- the maleic acid-based polymer was considered to contribute to the good anticorrosion effect.
- the water quality conditions of the raw water used were calcium hardness 100 mg/L as CaCO 3 , acid consumption (pH 4.8) 100 mg/L as CaCO 3 , magnesium hardness 50 mg/L, silica 20 mg/L, chloride ion concentration 400 mg/L. , sulfate ion concentration 400 mg/L, pH 8.2, AA/AMPS-1 6 mg/L, maleic acid polymer 6 mg/L, zinc chloride 1.5 mg/L as Zn.
- the material used for the test is an SPCC test piece (30 mm x 50 mm x 1 mm). One test piece was immersed in 1 L of test water and stirred with a stirrer under the operating conditions described above.
- Corrosion rate (mdd) corrosion weight loss (mg)/test piece surface area (dm 2 )/test period (day)
- Table 6 shows the concentration of chemicals used in the corrosion test and the measurement results of the corrosion rate. Even when zinc was used in combination, good anticorrosion effects were confirmed when samples 4 and 5 were used as the maleic acid-based polymer. It was found that a maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more in the maleic acid-based polymer can obtain good effects even when used in combination with zinc.
- AA/AMPS-1 as a copolymer (meth)acrylic acid monomer and sulfonic acid monomer (first agent) or a copolymer of acrylic acid monomer and acrylamidomethylpropanesulfonic acid monomer (weight-average molecular weight: 6000, molar ratio: 89:11, hereinafter also referred to as AA/AMPS-2) was used as the maleic acid-based polymer (second agent), each polymer of sample 1 and sample 4 in Table 1.
- the operating conditions for evaluating the anticorrosion effect are a water temperature of 30° C., a test period of 3 days, and a rotation speed of 150 rpm.
- the water quality conditions of the raw water used were calcium hardness 500 mg/L as CaCO 3 , acid consumption (pH 4.8) 200 mg/L as CaCO 3 , magnesium hardness 250 mg/L, silica 20 mg/L, chloride ion concentration 500 mg/L. , a sulfate ion concentration of 500 mg/L and a pH of 8.6.
- the material used for the test is an SPCC test piece (30 mm x 50 mm x 1 mm). One test piece was immersed in 1 L of test water and stirred with a stirrer under the operating conditions described above.
- Corrosion rate (mdd) corrosion weight loss (mg)/test piece surface area (dm 2 )/test period (day)
- Table 7 shows the concentration of chemicals used in the corrosion test and the measurement results of the corrosion rate.
- Patent Document 1 in high hardness water quality, the combination of AA / AMPS-2, sample 1, and zinc also shows a good effect, but the polymer of sample 4 rather than the polymer of sample 1 A good effect is similarly obtained when a polymer is used. From this, it can be seen that a maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more in the maleic acid-based polymer is applicable.
- a maleic acid-based polymer having a carboxyl group content of 11.5 mmol/g or more in the maleic acid-based polymer may be used in combination with a metal anticorrosive agent other than zinc (such as tin).
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Abstract
Description
(A)(メタ)アクリル酸単量体と、スルホン酸単量体との共重合体、及び、
(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体
(i)成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、及び、成分(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体、を含有し、
前記成分(A):前記成分(B)の質量含有割合が、1:9~7:3である、金属防食処理剤。
(ii)成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体を含む金属防食用第一剤、及び、成分(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体を含む金属防食用第二剤、を含む、金属防食処理剤キット。
前記成分(A)における共重合体の重量平均分子量は、1,000~1,000,000であってもよい。
前記成分(A)における(メタ)アクリル酸単量体とスルホン酸単量体とのモル比率は、97:3~30:70であってもよい。
前記成分(B)におけるマレイン酸系重合体の重量平均分子量が、500~5,000であってもよい。
前記成分(B)におけるマレイン酸系重合体が、マレイン酸単量体とイソブチレン単量体との共重合体、及び/又は、ポリマレイン酸であってもよい。
水系に、さらに防食剤を存在させてもよい。
前記水系のカルシウム硬度が、300mg/L as CaCO3以下であってもよい。
(i)成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、及び、成分(B)マレイン酸系重合体中のカルボキシル基含有量が所定以上であるマレイン酸系重合体、を含有し、前記成分(A):前記成分(B)の質量含有割合が所定の範囲である、金属防食処理剤。
(ii)成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体を含む金属防食用第一剤、及び、成分(B)マレイン酸系重合体中のカルボキシル基含有量が所定以上であるマレイン酸系重合体を含む金属防食用第二剤を、構成薬剤として、含み、前記成分(A):前記成分(B)の質量含有割合が所定の範囲になるように使用する、金属防食処理剤キット。
水系において金属材料又は金属部材を使用している箇所又は装置として、例えば、送水配管等の各種配管やパイプ、ポンプ、流路、熱交換器、冷凍機等が挙げられ、これらから選択される1種又は2種以上でもよい。より具体的には、これら又はこれらが有する金属製部品又は部分が、本実施形態を好適に適用する防食処理の対象となる。
本実施形態において用いる成分(A)である(メタ)アクリル酸単量体とスルホン酸単量体との共重合体(以下、「成分(A)共重合体」ともいう)は、特に限定されず、これら単量体のみに限らず本発明の効果を損なわない範囲において「その他単量体」を含んでいてもよい。また、当該成分(A)共重合体は、水溶性塩であってもよい。
前記(メタ)アクリル酸単量体は、特に限定されないが、(メタ)アクリル酸及びその塩が挙げられ、これら群から選ばれる1種又は2種以上を用いることができる。本実施形態において、「(メタ)アクリル酸」とは、「アクリル酸」及び「メタクリル酸」からなる群から選ばれる少なくとも1種を意味する。このうち、アクリル酸又はその塩が好適である。
前記スルホン酸単量体としては、特に限定されないが、スルホン基を含有する単量体が、前記成分(A)及び前記成分(B)の併用効果によるより良好な防食効果発揮の観点から、好適であり、当該単量体は不飽和の単量体が、さらに好ましい。
前記スルホン酸単量体として、例えば、モノエチレン性不飽和スルホン酸単量体及びその塩等が挙げられるが、これに限定されず、このうちモノエチレン性不飽和スルホン酸単量体が好適である。
前記スルホン酸単量体として、例えば、アミド基とスルホン基を有する単量体(好適には炭素数6~9のもの)、ヒドロキシ基とスルホン基を含有する単量体(好適には炭素数6~9のもの)、脂肪族共役ジエンのスルホン化物(好適には炭素数4~15のもの)及びそれらの塩等が挙げられ、これら群から選ばれる1種又は2種以上を用いることができる。このうち、アミド基とスルホン基を有する単量体(好適には炭素数6~9のもの)、ヒドロキシ基とスルホン基を含有する単量体(好適には炭素数6~9のもの)が好適である。また、当該単量体の「スルホン基」は、置換基を有してもよいスルホン基であってもよく、例えば、アルキルスルホン基が挙げられ、当該アルキルスルホン基の「アルキル」の炭素数は1~8が好適であり、メチルプロパンスルホン基(tert-ブチルスルホン基ともいう)がより好適である。これにより、前記成分(A)及び前記成分(B)の併用効果によるより良好な防食効果を発揮できる。
前記成分(A)共重合体における「その他の単量体」としては、特に限定されないが、例えば、N-ビニルピロリドン、N-ビニルホルムアミド、N-ビニルアセトアミド、N-ビニル-N-メチルホルムアミド、N-ビニル-メチルアセトアミド、N-ビニルオキサゾリドン等のN-ビニル単量体;(メタ)アクリルアミド、t-ブチルアクリルアミド、N,N-ジメチルアクリルアミド、N-イソプロピルアクリルアミド等の窒素含有ノニオン性不飽和単量体、3-(メタ)-アリルオキシ-1,2-ジヒドロキシプロパン、(メタ)アリルアルコール、イソプレノール等の水酸基含有不飽和単量体;(メタ)アリルアルコールにエチレンオキサイドを1~200モル程度付加させた化合物等のポリオキシエチレン基含有不飽和単量体;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ヒドロキシエチル等の(メタ)アクリル酸エステル;マレイン酸、イタコン酸等の不飽和カルボン酸単量体;スチレン等の芳香族不飽和単量体等が挙げられ、これらからなる群から選ばれる1種又は2種以上を用いることができる。
成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体における(メタ)アクリル酸単量体とスルホン酸単量体とのモル比率(モル%)は、特に限定されないが、好ましくは99:1~20:80、より好ましくは97:3~30:70、さらに好ましくは95:5~30:70、さらに好ましくは90:10~30:70(好適には40:60)、より好ましくは90:10~50:50、より好ましくは90:10~60:40、より好ましくは90:10~70:30、より好ましくは90:10~75:25である。前記成分(A)共重合体を当該モル比率にすることにより、水系に存在する前記成分(B)マレイン酸系重合体に対して、高硬度水質であっても低硬度水質であってもより良好に分散能力を発揮できる。
本実施形態に用いる成分(A)共重合体は、公知の製造方法により製造することができる。好適な成分(A)共重合体は、(i)(メタ)アクリル酸単量体と、(ii)アミド基とスルホン基を有する単量体、ヒドロキシ基とスルホン基を含有する単量体等から選択されるスルホン酸単量体とを、所定の質量使用割合で、共重合させてなる重合体である。
より好適な成分(A)共重合体は、(i)アクリル酸単量体と、(ii)2-アクリルアミド-2-メチルプロパンスルホン酸及び3-アリロキシ-2-ヒドロキシプロパンスルホン酸から選択される少なくとも1種のスルホン酸単量体とを所定の質量使用割合で、共重合させてなる重合体である。
さらにより好適な成分(A)共重合体は、アクリル酸単量体と2-アクリルアミド-2-メチルプロパンスルホン酸単量体との共重合体、アクリル酸単量体と3-アリロキシ-2-ヒドロキシプロパンスルホン酸単量体との共重合体等からなる群から選ばれる1種又は2種以上であり、このとき、より好適な(メタ)アクリル酸単量体とスルホン酸単量体との所定モル比率は、97:3~70:30であり、当該モル比率は上述した成分(A)共重合体における前記モル比率(モル%)を適宜採用することができる。これにより、リン化合物を金属防食剤として利用しなくとも、低硬質濃度の水に対してもより良好な防食効果及びより良好な耐ゲル化能を発揮することができる。
(メタ)アクリル酸単量体とスルホン酸単量体との共重合体のGPC法による重量平均分子量は、特に限定されないが、好ましくは1,000~1,000,000、より好ましくは3,000~1,000,000、さらに好ましくは3,000~80,000、さらに好ましくは5,000以上50,000(好適には30,000)以下である。ポリマーの重量平均分子量は、<ポリマーの重量平均分子量のGPC分析>により測定することができる(ポリアクリル酸換算)。当該重量平均分子量に調整することにより、前記成分(A)及び前記成分(B)の併用効果によるより良好な防食効果を発揮させることができる。
本発明に用いる成分(B)マレイン酸系重合体は、当該重合体中のカルボキシル基含有量が所定以上であることが、前記成分(A)及び前記成分(B)の併用効果によるより良好な防食効果発揮の観点から、好適であり、当該所定の含有量は、所定以上、例えば11.5mmol/g以上が好適である。
前記マレイン酸系単量体は、特に限定されないが、例えば、無水マレイン酸、マレイン酸、マレイン酸塩等のマレイン酸単量体、マレイン酸エステル等が挙げられ、これらから群から選択される1種又は2種以上を用いることができる。
前記マレイン酸系単量体のうち、マレイン酸単量体が好ましく、さらにこのうち、無水マレイン酸系単量体が好ましく、より好ましくは無水マレイン酸である。水系重合の場合には無水マレイン酸の加水分解物(マレイン酸)も単量体として用いる場合があり、当該無水マレイン酸系単量体には、無水マレイン酸及び無水マレイン酸の加水分解物が含まれる。これにより、前記成分(A)及び前記成分(B)の併用効果によるより良好な防食効果を発揮することができる。
前記マレイン酸塩として、例えば、リチウム塩、ナトリウム塩、カリウム塩等のモノ又はジアルカリ金属塩、カルシウム塩、マグネシウム塩等のアルカリ土類金属塩、アンモニウム塩、ジアンモニウム塩等のアンモニウム塩等が挙げられ、これらからなる群から選択される1種又は2種以上を用いることができる。
前記マレイン酸エステルとして、例えば、メタノール、エタノール等の飽和炭化水素のアルコール、アリルアルコール、メタリルアルコール等の不飽和炭化水素のアルコール、ポリアルキレングリコール、ポリオキシアルキレンモノメチルエーテル、ポリオキシアルキレンモノアリルエーテル等のポリアルキレングリコール誘導体とのエステル化物等が挙げられ、これらからなる群から選択される1種又は2種以上を用いることができる。
成分(B)マレイン酸系重合体における前記共重合可能な単量体(以下、「成分(B)の共重合可能な単量体」ともいう)として、特に限定されないが、例えば、N-ビニルピロリドン、N-ビニルホルムアミド、N-ビニルアセトアミド、N-ビニル-N-メチルホルムアミド、N-ビニル-メチルアセトアミド、N-ビニルオキサゾリドン等のN-ビニル単量体;(メタ)アクリルアミド、t-ブチルアクリルアミド、N,N-ジメチルアクリルアミド、N-イソプロピルアクリルアミド等の窒素含有ノニオン性不飽和単量体;3-(メタ)-アリルオキシ-1,2-ジヒドロキシプロパン、(メタ)アリルアルコール、イソプレノール等の水酸基含有不飽和単量体;(メタ)アリルアルコールにエチレンオキサイドを1~200モル程度付加させた化合物等のポリオキシエチレン基含有不飽和単量体;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ヒドロキシエチル等の(メタ)アクリル酸エステル;(メタ)アクリル酸、イタコン酸等の不飽和カルボン酸単量体;スチレン等の芳香族不飽和単量体;イソブチレン等の不飽和炭化水素等が挙げられ、これらからなる群から選ばれる1種又は1種以上を用いることができる。
好適な成分(B)マレイン酸系重合体は、マレイン酸単量体とモノエチレン性不飽和炭化水素単量体(好適にはイソブチレン単量体)との共重合体、及び/又は、ポリマレイン酸(好適にはマレイン酸単量体のホモポリマー)が好適である。これにより、前記成分(A)及び前記成分(B)の併用効果によるより良好な防食効果を発揮することができる。
成分(B)マレイン酸系重合体中のカルボキシル基含有量は、ホモポリマー又はコポリマーに関わらず、また、単量体由来に関わらず、当該重合体中のカルボキシル基の合計の含有量である。当該重合体中のカルボキシル基含有量は、好適な下限値として、好ましくは11.5mmol/g以上、より好ましくは11.7mmol/g以上、さらに好ましくは12mmol/g以上、より好ましくは12.5mmol/g以上、より好ましくは13mmol/g以上であり、また、好適な上限値として、特に限定されず、理論上17.2mmol/gとなり、製造可能な範囲内で設定することができ、例えば、17、16、又は15mmol/g以下等にすることができる。前記成分(B)マレイン酸系重合体中のカルボキシル基含有量は、後記〔実施例〕における<試験1:マレイン酸系重合体(サンプル1~5)中のカルボキシル基含有量の滴定分析>に従って、求めることができる。
本実施形態であれば、前記成分(A)共重合体と併用することで、前記成分(B)マレイン酸系重合体中のカルボキシル基含有量を所定以上の高さにしても水系での前記成分(B)のゲル化をより良好に抑制できるとともにより良好に分散できるので、前記成分(B)における重合体中のカルボキシル基含有量の高含有化によって向上した防食効果を、より良好に発揮させることができる。
成分(B)マレイン酸系重合体のGPC法による重量平均分子量は、特に限定されないが、その好適な下限値として、好ましくは250以上、より好ましくは500以上、また、その好適な上限値として、好ましくは10,000以下、より好ましくは8,000以下、さらに好ましくは5,000以下、より好ましくは3,000以下、当該好適な数値範囲として、好ましくは500~5,000、より好ましくは500~3,000である。ポリマーの重量平均分子量は、<ポリマーの重量平均分子量のGPC分析>により測定することができる(ポリアクリル酸換算)。当該重量平均分子量に調整することにより、前記成分(A)及び前記成分(B)の併用効果によるより良好な防食効果を発揮させることができる。
本実施形態に用いる、前記成分(A)共重合体と前記成分(B)マレイン酸系重合体は、前記「1-1.」に記載の前記成分(A)共重合体、及び、前記「1-2.」に記載の前記成分(B)マレイン酸系重合体を適宜採用して組み合わせることができる。
本発明に用いる成分(A)共重合体及び成分(B)マレイン酸系重合体との質量使用割合は、特に限定されないが、水系において、それぞれ1:9~7:3で存在させることが好適であり、より好ましくは2:8~7:3、さらに好ましくは3:7~7:3、より好ましくは3:7~6:4、より好ましくは3:7~5.5:4.5である。当該質量使用割合(質量含有割合)により、前記成分(B)マレイン酸系重合体による水系で発生するゲル化をより良好に抑制でき、かつこれら成分(A)及び成分(B)の併用効果によりより良好な防食効果を発揮させることができる。なお、質量使用割合は、前記成分(A)共重合体(mg soild/L):前記成分(B)マレイン酸系重合体(mg soild/L)である。
水系に対する前記成分(A)共重合体の添加量(mg soild/L、以下「mg/L」とする)は特に限定されないが、好適な下限値として、好ましくは0.1mg/L以上、より好ましくは0.5mg/L以上、さらに好ましくは1mg/L以上、より好ましくは2mg/L以上、さらに好ましくは3mg/L以上、より好ましくは4mg/L以上であり、また、好適な上限値として、特に限定されないが、薬剤の使用量低減及び防食効果発揮とのバランスの観点から、好ましくは100mg/L以下、より好ましくは50mg/L以下、さらに好ましくは30mg/L以下、さらにより好ましくは20又は15mg/L以下、より好ましくは7又は6mg/L以下であり、当該好適な数値範囲として、好ましくは3~15mg/Lである。前記成分(A)共重合体を上記好適な量にて水系に存在させることで、前記成分(B)マレイン酸系重合体との併用効果をより良好に発揮させることができる。
水系に対する前記成分(B)マレイン酸系重合体の添加量(mg soild/L、以下「mg/L」とする)は特に限定されないが、好適な下限値として、好ましくは0.1mg/L以上、より好ましくは0.5mg/L以上、さらに好ましくは1mg/L以上、より好ましくは2mg/L以上、さらに好ましくは3mg/L以上、より好ましくは4mg/L以上であり、また、好適な上限値として、特に限定されないが、薬剤の使用量低減及び防食効果発揮とのバランスの観点から、好ましくは100mg/L以下、より好ましくは50mg/L以下、さらに好ましくは30mg/L以下、さらにより好ましくは20又は15mg/L以下、より好ましくは7又は6mg/L以下であり、当該好適な数値範囲として、好ましくは3~15mg/Lである。前記成分(B)マレイン酸系重合体を上記好適な量にて水系に存在させることで、前記成分(A)共重合体との併用効果をより良好に発揮させることができる。
本実施形態の前記成分(A)共重合体及び成分(B)マレイン酸系重合体の併用において、好適な態様は、前記成分(A)及び前記成分(B)の併用効果によるより良好な防食効果発揮の観点から、成分(A)(メタ)アクリル酸単量体とモノエチレン性不飽和スルホン酸単量体との共重合体、及び、成分(B)マレイン酸系重合体である。
本実施形態では、上記成分(A)及び成分(B)以外に、本発明の効果を損なわない範囲内で、適宜、任意成分を、水系に使用したり、薬剤中に含ませてもよい。当該任意成分として、特に限定されないが、例えば、pH調整剤、消泡剤、防食剤、スケール防止剤、殺菌剤、殺藻剤等からなる群から選ばれる1種又は2種以上を用いてもよい。
本実施形態では、水系において、上述した成分(A)共重合体及び成分(B)マレイン酸系重合体との併用に加えて、さらに当該成分(A)及び成分(B)の組み合わせ以外の成分(C)防食剤(より好適には防食用金属化合物)を存在させることが好適である。なお、防食用金属化合物とは、防食のために用いる金属化合物であって、当該金属化合物は重金属イオンを水中に容易に放出させうる金属化合物をいい、この効果を発揮させうる金属化合物であれば、特に限定されない。
本実施形態では、水系に対して、上述した成分(A)共重合体及び成分(B)マレイン酸系重合体とを少なくとも併用することで、低硬度水質であっても、防食剤としてリン化合物を使用しなくとも、良好な防食効果を発揮することができる。水系に対して添加するリン化合物の添加量は、特に限定されないが、富栄養化の低減の観点から、好ましくは0.5mg/L as P以下、より好ましくは、0.3mg/L as P以下、さらに好ましくは、0.1mg/L as P以下であり、実質的に使用しない又は含ませないようにすることがより好適である。当該「実質的に使用しない又は含ませない」とは、0.05mg/L as P以下が好適であり、0.01mg/L as P以下がさらに好適であり、水系に対するリン化合物の無添加がより好適である。
なお、リン濃度の求め方は、モリブデン青(アスコルビン酸還元)法を用いて測定することができる(JIS K 0102 46.1.1)。
本実施形態の水系の金属防食処理方法は、上述した前記成分(A)共重合体及び前記成分(B)マレイン酸系重合体を、所定の質量使用割合又は質量含有割合にて、水系に存在させることが好適であり、より好適には1:9~7:3で存在させることである。
また、水系に対して、前記成分(A)共重合体及び前記成分(B)マレイン酸系重合体は、両者が少なくとも混合できるように水系に添加すればよく、それぞれの添加は同時期又は別々の時期の何れであってもよく、連続的又は断続的の何れであってもよい。
(i)(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、及び、
(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体、を含有し、
前記(A):前記(B)の質量含有割合が、1:9~7:3である、金属防食処理剤。
(ii)(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体を含む金属防食用第一剤、及び、(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体を含む金属防食用第二剤、を含む、金属防食処理剤キット。
また、本実施形態では、リン化合物を金属防食剤として使用しなくとも防食効果が十分に発揮されるため、各国のリン濃度の排水基準にも適用することができ、例えば、上記リン化合物の添加量で説明したリン濃度を適宜採用することができ、例えば、水系の水質の条件としてリン濃度が、好ましくは0.5mg/L as P以下、より好ましくは0.1mg/L as P以下でもよい。
本実施形態における冷却水系とは、ビルや地域施設等の空調設備、及びプラント等において、熱交換器等の運転のために用いられる冷却水が通水される系をいう。
前記冷却水系は、一過式、開放循環式又は密閉循環式の何れでもよい。
循環冷却水系は、特に限定されず、例えば、空調、石油化学コンビナート、一般工場等に設置されている冷却塔を系内に備える水系であることが好適である。当該循環冷却水系は、これら空調、一般工場等で発生する熱源を間接的に冷却するように構成されていることが好適であり、熱交換器、循環水路、冷却塔を含むように構成されている一般的な水系であってもよい。
また、薬剤の添加の場所は、特に限定されず、冷却水系の何れの場所でもよく、例えば、送風手段、散水手段、ピット、補給水供給手段、薬剤注入手段、循環水路、移送ポンプ、熱交換器等が挙げられ、好適には、補給水供給手段、薬剤注入手段、循環水路、移送ポンプ等であり、これらから選択される1種又は2種以上の場所で添加することができる。
開放循環冷却水系1において、前記成分(A)共重合体及び前記成分(B)マレイン酸系重合体を含む水は、ピット15から移送ポンプ21にて循環水路20で熱交換器30に移送され、熱交換器30を経て循環水路20で開放式冷却塔10に戻る。当該冷却塔10内で、前記成分(A)及び前記成分(B)を含む水は、散水手段12、充填材領域13を経て、ピット15に貯留され、再びポンプ21にて循環水路20に移送される。この循環中においても、前記成分(A)及び前記成分(B)が併存することで、前記成分(B)はゲル化せずに良好に分散状態を維持することができ、これにより冷却水系に対して防食効果を維持し続けることができる。この循環によって、水系中の水に存在する前記成分(A)及び前記成分(B)が、金属部材と接触することができ、当該金属部材に対して防食効果を発揮することができる。
本実施形態に係る金属防食処理剤及び金属防食処理剤キットにおける説明において、上記「1.本実施形態に係る水系の金属防食処理方法」の説明と重複する、成分(A)、成分(B)、各添加量、各質量使用割合、各構成、各方法、各用語等の説明については適宜省略するが、上記「1.」の説明が、本実施形態に係る金属防食処理剤及び金属防食処理剤キットにも当てはまり、適宜採用することができる。上記「1.」の質量使用割合等を、質量含有割合等にすることもできる。
本実施形態の薬剤は、金属防食処理剤として、(i)成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、及び、
成分(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体、を含有する金属防食処理剤を提供することができ、より好適には、金属防食処理剤中前記成分(A):前記成分(B)の質量含有割合が、1:9から7:3である。
前記金属防食処理剤又は前記金属防食処理剤キットは、水系の水質条件に対応して適宜使用することができ、例えば、水系のカルシウム硬度が300mg/L as CaCO3以下で使用するための薬剤又は当該カルシウム硬度にて使用することが好適である。
また、前記成分(A)共重合体と前記成分(B)マレイン酸系重合体とは、金属防食処理剤等を製造するために使用することができる。
また、本実施形態は、金属防食処理をするための又は金属防食処理に使用するための、前記成分(A)共重合体及び前記成分(B)マレイン酸系重合体、又はその使用を提供することもできる。
本実施形態は、前記成分(A)共重合体と前記成分(B)マレイン酸系重合体とを用いる金属防食処理方法、又はこれらを含む一液型薬剤若しくは多液型薬剤を用いる金属防食処理方法を提供することも可能である。
・〔1〕 水系に、下記の成分(A)及び成分(B)を質量使用割合1:9~7:3で存在させる、水系の金属防食処理方法。
(A)(メタ)アクリル酸単量体と、スルホン酸単量体との共重合体、及び、
(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体
・〔2〕 前記(A)におけるスルホン酸単量体が、モノエチレン性不飽和スルホン酸単量体である、前記〔1〕に記載の水系の金属防食処理方法。
・〔3〕 前記(A)における共重合体の重量平均分子量は、1,000~1,000,000である、前記〔1〕又は〔2〕に記載の水系の金属防食処理方法。
・〔4〕 前記(A)における(メタ)アクリル酸単量体とスルホン酸単量体とのモル比率は、97:3~30:70である、前記〔1〕~〔3〕の何れか1つに記載の水系の金属防食処理方法。
・〔5〕 前記(B)におけるマレイン酸系重合体の重量平均分子量が、500~5,000である、前記〔1〕~〔4〕の何れか1つに記載の水系の金属防食処理方法。
・〔6〕 前記(B)におけるマレイン酸系重合体が、マレイン酸単量体とイソブチレン単量体との共重合体、及び/又は、ポリマレイン酸である、前記〔1〕~〔5〕の何れか1つに記載の水系の金属防食処理方法。
・〔7〕 水系に、さらに防食剤(好適には防食用金属化合物)を存在させる、前記〔1〕~〔6〕の何れか1つに記載の水系の金属防食処理方法。
・〔8〕 前記水系のカルシウム硬度が、300mg/L as CaCO3以下である、前記〔1〕~〔7〕の何れか1つに記載の水系の金属防食処理方法。
・〔9〕 下記の(i)金属防食処理剤又は(ii)金属防食処理剤キット。又は、下記の(i)金属防食処理剤又は(ii)金属防食処理剤キットを使用する、水系の金属防食処理方法、或いは前記〔1〕~〔8〕の何れか1つに記載の水系の金属防食処理方法。
(i)(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、及び、
(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体、を含有し、
前記(A):前記(B)の質量含有割合が、1:9から7:3である、金属防食処理剤。
(ii)(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体を含む金属防食用第一剤、及び、(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体を含む金属防食用第二剤、を含む、金属防食処理剤キット。
・〔10〕 金属防食処理剤を製造するための、成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、及び、(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体、又はこの使用。
・〔11〕 金属防食処理剤に使用するための又は金属防食処理剤のための、成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、及び、(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体、又はその使用。
・〔12〕 金属防食処理剤キットを製造するための、成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体を含む金属防食用第一剤、及び、前記(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体を含む金属防食用第二剤、又はこの使用。
・〔13〕 金属防食処理剤キットの金属防食用第一剤を製造するための、成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、又はその使用。金属防食処理剤キットの金属防食用第二剤を製造するための、成分(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体、又はこの使用。
・〔14〕 金属防食処理剤キットに使用するための又は金属防食処理剤キットのための、成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体を含む金属防食用第一剤、及び、成分(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体を含む金属防食用第二剤、又はこの使用。
・〔15〕 金属防食処理剤キットの金属防食用第一剤に使用するための又は当該金属防食用第一剤のための、成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、又はその使用。金属防食処理剤キットの金属防食用第二剤に使用するための又は当該金属防食用第二剤のための、成分(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体、又はこの使用。
<手法>
滴定分析にはTitrando (Metorom)を用いた。マレイン酸系重合体1gを20mLの純水に溶解し、塩酸を用いてpHを2以下まで下げたのち、Titrandoにセットし、0.5mol/LのNaOHを用いて滴定した。塩酸の中和点までに滴下したNaOH量とマレイン酸系ポリマーの中和点までに滴下したNaOH量との差から、マレイン酸系ポリマーの中和に要したNaOH量を算出し、そこからマレイン酸系重合体中のカルボキシル基含有量を算出した。算出式は以下のとおりである。
マレイン酸系重合体中のカルボキシル基含有量(mmol/g)=(マレイン酸系ポリマーの中和に要したNaOH水溶液(0.5mol/L)量(mL)÷0.5(mol/L))÷使用したマレイン酸系重合体1(g)
滴定分析を実施したマレイン酸系重合体(サンプル1~5)とそのカルボキシル基含有量について表1に示す。サンプル4~5は他のマレイン酸系ポリマーよりカルボキシル基含有量が多いことが共通している。サンプル3とサンプル4から、マレイン酸系重合体中のカルボキシル基含有量11.5mmol/g以上のマレイン酸系重合体を、マレイン酸系重合体中のカルボキシル基含有量が所定以上に高いマレイン酸系重合体と設定した。
<ポリマーの重量平均分子量のGPC分析>
各ポリマーの重量平均分子量は、GPC(ゲルパーミエイションクロマトグラフィー)法により測定することができ、GPC法による標準ポリアクリル酸換算の値である。
<手法>
(メタ)アクリル酸とスルホン酸からなる共重合体とマレイン酸系重合体の併用効果を確認するために、腐食試験を実施した。(メタ)アクリル酸単量体とスルホン酸単量体とから得られる共重合体(第一薬剤)として、アクリル酸とアクリルアミドメチルプロパンスルホン酸(2-アクリルアミド-2-メチルプロパンスルホン酸)との共重合体(重量平均分子量19000、モル比率80(AA): 20(AMPS-1)、以後「AA/AMPS-1」ともいう)を、マレイン酸系重合体(第二薬剤)として、表1中のサンプル4のポリマーを用いた。AA/AMPS-1及びサンプル4の2種類の重合体の質量配合割合を変化させた場合の防食効果を評価した。表2に示すように、各試験水(比較例2-1~2-4、実施例2-1~2-7)は、第一薬剤及び第二薬剤を表2の添加濃度になるように原水に添加して調製されたものである。防食効果評価のための運転条件は、水温30℃、試験期間3日間、回転数150rpmである。使用した原水の水質条件は、カルシウム硬度 100mg/L as CaCO3、酸消費量(pH4.8) 100mg/L as CaCO3、マグネシウム硬度 50mg/L、シリカ 20mg/L、塩化物イオン濃度 100mg/L、硫酸イオン濃度 100mg/L、pH8.2である。試験に使用した材料は、SPCC製のテストピース(30mm×50mm×1mm)である。なお、使用したSPCC製は、炭素含有量0.02~0.15質量%で、低炭素鋼に分類される。
腐食速度(mdd)=腐食減量(mg)/テストピースの表面積(dm2)/試験期間(day)
腐食速度の測定結果を表2に示す。AA/AMPS-1とマレイン酸系重合体でカルボキシル基含有量が11.5mmol/g以上のものであるサンプル4の配合割合(質量比)が7:3~1:9の範囲で優れた防食効果が得られ、7:3~3:7の範囲で特に優れた防食効果を示した。AA/AMPS-1の添加比率が高くサンプル4の添加比率が低い条件では、AA/AMPS-1の防食効果が乏しいため腐食したと考えられる。また、AA/AMPS-1の添加比率が低くサンプル4の添加比率が高い条件では、サンプル4がゲル化による失活したため防食効果が低下したと考えられる。
<手法>
マレイン酸系重合体のゲル化のしやすさを評価するために、表1のサンプル1~4について、また比較としてAA/AMPS-1、及びアクリル酸と3-アリロキシ-2-ヒドロキシプロパンスルホン酸の共重合体(モル比率82(AA):18(HAPS-1)、重量平均分子量11000、以後AA/HAPS-1ともいう)について、耐ゲル化能評価試験を実施した。
500mL容のネジ口瓶に、超純水、各ポリマー溶液、カルシウム硬度溶液を都度攪拌しながら添加した。カルシウム硬度溶液は所定の濃度となるように、各ポリマー溶液は試験水中の濃度が100mg/Lになるように、超純水は総量が500mLとなるように添加した。NaOHやH2SO4等でpH8.5となるように試験液の調整を行い、ねじ口瓶のふたを閉め、90℃で1時間静置した。1時間経過後、分光光度計にて、λ=380nm、50mmセルで濁度を測定した。ポリマーの着色が吸光度に影響する場合があるため、カルシウム硬度無添加の条件の吸光度も同時に測定し、それぞれの値からこれを差し引いた。吸光度の補正値が小さいほど、ゲル化が生じておらず、良好であることを示す。
試験条件及び吸光度の測定結果を表3に示した。サンプル1~4の各マレイン酸系重合体はそれぞれ特定のカルシウム硬度において試験液の濁りが確認され、ゲル化が発生していることがわかった。しかし、ゲル化が発生するカルシウム濃度(カルシウム硬度)は、重合体の種類により異なることが分かった。表1に記載の重合体中のカルボキシル基含有量と比較する、重合体中のカルボキシル基含有量が多いほど試験液中の低濃度のカルシウム濃度でゲル化することが分かった。一方、AA/AMPS-1、AA/HAPS-1はカルシウム硬度が1000mg/L as CaCO3であってもゲル化しないことが確認された。
<手法>
(メタ)アクリル酸とスルホン酸からなる共重合体の分散能力により、マレイン酸系重合体のゲル化の抑制効果ができないか確認するため耐ゲル化能評価試験を行った。(メタ)アクリル酸とスルホン酸からなる共重合体としてAA/AMPS-1(モル比率80:20)を、マレイン酸系重合体としてサンプル4を用いた。
500mL容ネジ口瓶に、超純水、各ポリマー溶液、カルシウム硬度溶液を都度攪拌しながら添加し、総量500mLとした。各ポリマー溶液、カルシウム硬度溶液が所定の濃度となるように、超純水は総量500mLとなるように添加した。NaOHやH2SO4等でpH8.5となるように調整を行い、ネジ口瓶のふたを締め、90℃で1時間静置した。1時間経過後、分光光度計にて、λ=380nm、50mmセルで濁度を測定した。ポリマーの着色が吸光度に影響する場合があるため、カルシウム硬度無添加の条件の吸光度も同時に測定し、それぞれの値からこれを差し引いた。吸光度の補正値が小さいほど、ゲル化が生じておらず、良好であることを示す。
試験条件及び吸光度の測定結果を表4に示した。重合体中のカルボキシル基含有量が11.5mmol/g以上のマレイン酸系重合体としてサンプル4のみを添加した条件3及び4の場合にはゲル化が生じた。これに対し、AA/AMPS-1とサンプル4を併用すると、ゲル化は起こらなかった。このことから、重合体中のカルボキシル基含有量が高いマレイン酸系ポリマーとAA/AMPS-1ポリマーとの併用により、水中のカルシウムイオンと重合体中のカルボキシル基含有量が高いマレイン酸系ポリマーとのゲル化を抑制可能であることが示された。
また、カルシウム硬度0mg/L as CaCO3のときの実施例4-1及び実施例4-2を、数日間放置しても濁りがなく透明であったので、(メタ)アクリル酸とスルホン酸からなる共重合体と、重合体中のカルボキシル基含有量が高いマレイン酸系重合体とは、一液型薬剤及び多液型薬剤(薬剤キット)の何れにも適用できることが示された。
<手法>
(メタ)アクリル酸とスルホン酸との共重合体及びマレイン酸系重合体の併用効果において、最適マレイン酸系重合体の特徴を確認するために、腐食試験を実施した。(メタ)アクリル酸単量体とスルホン酸単量体との共重合体(第一薬剤)として試験2のAA/AMPS-1を、マレイン酸系重合体(第二薬剤)として表1中のサンプル1~5の各ポリマーを用いた。防食効果評価のための運転条件は、水温30℃、試験期間3日間、回転数150rpmである。使用した原水の水質条件は、カルシウム硬度 100mg/L as CaCO3、酸消費量(pH4.8) 100mg/L as CaCO3、マグネシウム硬度 50mg/L、シリカ 20mg/L、塩化物イオン濃度 150mg/L、硫酸イオン濃度 150mg/L、pH 8.2、AA/AMPS-1 6mg/L、マレイン酸系重合体 6mg/Lである。試験に使用した材料は、SPCC製のテストピース(30mm×50mm×1mm)である。1Lの試験水に対し、1枚のテストピースを浸漬し、上記運転条件にて、スターラーで撹拌した。試験結果の評価は、テストピースの試験前後における重量差から腐食減量を求め、以下の式に基づき腐食速度(mdd)を算出して行った。
腐食速度(mdd)=腐食減量(mg)/テストピースの表面積(dm2)/試験期間(day)
腐食試験に用いた薬剤の添加濃度及び腐食速度の測定結果を表5に示す。カルボキシル基高含有のマレイン酸系重合体としてサンプル4及びサンプル5を用いた場合に、良好な防食効果が確認できた。表1のカルボキシル基含有量と比較すると、サンプル4とサンプル5の重合体中のカルボキシル基含有量が最も高いことから、マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上のマレイン酸系重合体は、良好な防食効果に寄与していると考えられた。
<手法>
(メタ)アクリル酸とスルホン酸との共重合体とマレイン酸系重合体の併用効果において、亜鉛を併用した条件下における最適マレイン酸系重合体の特徴を確認するために、腐食試験を実施した。(メタ)アクリル酸単量体とスルホン酸単量体との共重合体(第一薬剤)として試験2のAA/AMPS-1を、マレイン酸系重合体(第二薬剤)として表1中のサンプル1~5の各ポリマーを用いた。防食効果評価のための運転条件は、水温30℃、試験期間3日間、回転数150rpmである。使用した原水の水質条件は、カルシウム硬度 100mg/L as CaCO3、酸消費量(pH4.8) 100mg/L as CaCO3、マグネシウム硬度 50mg/L、シリカ 20mg/L、塩化物イオン濃度 400mg/L、硫酸イオン濃度 400mg/L、pH 8.2、AA/AMPS-1 6mg/L、マレイン酸系重合体 6mg/L、塩化亜鉛 1.5mg/L as Znである。試験に使用した材料は、SPCC製のテストピース(30mm×50mm×1mm)である。1Lの試験水に対し、1枚のテストピースを浸漬し、上記運転条件にて、スターラーで撹拌した。試験結果の評価は、テストピースの試験前後における重量差から腐食減量を求め、以下の式に基づき腐食速度(mdd)を算出して行った。
腐食速度(mdd)=腐食減量(mg)/テストピースの表面積(dm2)/試験期間(day)
腐食試験に用いた薬剤の添加濃度及び腐食速度の測定結果を表6に示す。亜鉛を併用した条件においても、マレイン酸系重合体としてサンプル4及びサンプル5を用いた場合に、良好な防食効果が確認できた。マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上のマレイン酸系重合体は、亜鉛と併用しても良好な効果が得られることがわかった。
<手法>
高硬度水質における(メタ)アクリル酸とスルホン酸との共重合体、及びマレイン酸系重合体の併用効果について確認するために腐食試験を実施した。上記2種類の共重合体に加え、防食用金属化合物として塩化亜鉛又は塩化スズ(II)を併用し、試験を実施した。(メタ)アクリル酸単量体とスルホン酸単量体との共重合体(第一薬剤)としてAA/AMPS-1又はアクリル酸単量体とアクリルアミドメチルプロパンスルホン酸単量体との共重合体(重量平均分子量6000、モル比率89:11、以後AA/AMPS-2ともいう)を、マレイン酸系重合体(第二薬剤)として表1中のサンプル1とサンプル4の各ポリマーを用いた。防食効果評価のための運転条件は、水温30℃、試験期間3日間、回転数150rpmである。使用した原水の水質条件は、カルシウム硬度 500mg/L as CaCO3、酸消費量(pH4.8) 200mg/L as CaCO3、マグネシウム硬度 250mg/L、シリカ 20mg/L、塩化物イオン濃度 500mg/L、硫酸イオン濃度 500mg/L、pH 8.6である。試験に使用した材料は、SPCC製のテストピース(30mm×50mm×1mm)である。1Lの試験水に対し、1枚のテストピースを浸漬し、上記運転条件にて、スターラーで撹拌した。試験結果の評価は、テストピースの試験前後における重量差から腐食減量を求め、以下の式に基づき腐食速度(mdd)を算出して行った。
腐食速度(mdd)=腐食減量(mg)/テストピースの表面積(dm2)/試験期間(day)
腐食試験に用いた薬剤の添加濃度及び腐食速度の測定結果を表7に示す。特開2012-207279号公報(特許文献1)に示すように、高硬度水質ではAA/AMPS-2、サンプル1、亜鉛の組み合わせでも良好な効果を示すが、サンプル1のポリマーではなくサンプル4のポリマーを用いた場合も同様に良好な効果を示す。このことから、マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上のマレイン酸系重合体は適用可能であることがわかる。また、防食用金属化合物としてスズを併用した条件においては、サンプル4のポリマーを用いた場合においてのみ良好な防食効果が得られた。このことから、マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上のマレイン酸系重合体は、亜鉛以外の金属の防食剤(スズ等)と併用しても良いことがわかる。
Claims (10)
- 水系に、下記の成分(A)及び成分(B)を質量使用割合1:9~7:3で存在させる、水系の金属防食処理方法。
(A)(メタ)アクリル酸単量体と、スルホン酸単量体との共重合体、及び、
(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体 - 前記成分(A)におけるスルホン酸単量体が、モノエチレン性不飽和スルホン酸単量体である、請求項1に記載の水系の金属防食処理方法。
- 前記成分(A)における共重合体の重量平均分子量は、1,000~1,000,000である、請求項1又は2に記載の水系の金属防食処理方法。
- 前記成分(A)における(メタ)アクリル酸単量体とスルホン酸単量体とのモル比率は、97:3~30:70である、請求項1~3の何れか1項に記載の水系の金属防食処理方法。
- 前記成分(B)におけるマレイン酸系重合体の重量平均分子量が、500~5,000である、請求項1~4の何れか1項に記載の水系の金属防食処理方法。
- 前記成分(B)におけるマレイン酸系重合体が、マレイン酸単量体とイソブチレン単量体との共重合体、及び/又は、ポリマレイン酸である、請求項1~5の何れか1項に記載の水系の金属防食処理方法。
- 水系に、さらに防食剤を存在させる、請求項1~6の何れか1項に記載の水系の金属防食処理方法。
- 前記水系のカルシウム硬度が、300mg/L as CaCO3以下である、請求項1~7の何れか1項に記載の水系の金属防食処理方法。
- 下記の(i)金属防食処理剤又は(ii)金属防食処理剤キットを使用する、請求項1~8の何れか1項に記載の水系の金属防食処理方法。
(i)成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、及び、成分(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体、を含有し、
前記成分(A):前記成分(B)の質量含有割合が、1:9~7:3である、金属防食処理剤。
(ii)成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体を含む金属防食用第一剤、及び、成分(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体を含む金属防食用第二剤、を含む、金属防食処理剤キット。 - 下記の(i)金属防食処理剤又は(ii)金属防食処理剤キット。
(i)成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体、及び、成分(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体、を含有し、
前記成分(A):前記成分(B)の質量含有割合が、1:9~7:3である、金属防食処理剤。
(ii)成分(A)(メタ)アクリル酸単量体とスルホン酸単量体との共重合体を含む金属防食用第一剤、及び、成分(B)マレイン酸系重合体中のカルボキシル基含有量が11.5mmol/g以上であるマレイン酸系重合体を含む金属防食用第二剤を含む、金属防食処理剤キット。
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JP2012207279A (ja) | 2011-03-30 | 2012-10-25 | Kurita Water Ind Ltd | 冷却水系の金属防食処理方法 |
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