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WO2012008269A1 - Agent anticorrosif pour le lavage d'un métal à l'acide, composition de solution de détergent, et procédé de lavage de métal - Google Patents

Agent anticorrosif pour le lavage d'un métal à l'acide, composition de solution de détergent, et procédé de lavage de métal Download PDF

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Publication number
WO2012008269A1
WO2012008269A1 PCT/JP2011/064025 JP2011064025W WO2012008269A1 WO 2012008269 A1 WO2012008269 A1 WO 2012008269A1 JP 2011064025 W JP2011064025 W JP 2011064025W WO 2012008269 A1 WO2012008269 A1 WO 2012008269A1
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WIPO (PCT)
Prior art keywords
acid
metal
structural unit
cleaning
corrosion inhibitor
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PCT/JP2011/064025
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English (en)
Japanese (ja)
Inventor
宏之 高山
中田　泰仁
Original Assignee
日東紡績株式会社
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Publication date
Application filed by 日東紡績株式会社 filed Critical 日東紡績株式会社
Priority to JP2012524505A priority Critical patent/JP5630672B2/ja
Priority to US13/808,670 priority patent/US20130109607A1/en
Publication of WO2012008269A1 publication Critical patent/WO2012008269A1/fr

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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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3796—Amphoteric polymers or zwitterionic polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • 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
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals

Definitions

  • the present invention relates to a corrosion inhibitor for metal acid cleaning, which is excellent in a corrosion inhibiting effect and its stability, and its use.
  • a black oxide film such as a mill scale adheres to a metal surface such as a metal steel plate. Therefore, when processing rust prevention, plating, etc. on a metal steel sheet for the purpose of improving the performance of the final product, etc., the oxide film is removed before that to prevent rust on the steel sheet surface. It is widely practiced to impart a uniform thickness or to improve the adhesion between the steel sheet surface and the plating film.
  • the metal acid cleaning liquid include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, phosphoric acid, sulfamic acid, hydrofluoric acid, oxalic acid, citric acid, glycolic acid, organic acids such as formic acid, chelating agents such as ethylenediaminetetraacetic acid, And aqueous solutions of these and the like.
  • inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid
  • phosphoric acid phosphoric acid
  • sulfamic acid hydrofluoric acid
  • oxalic acid citric acid
  • glycolic acid organic acids
  • organic acids such as formic acid
  • chelating agents such as ethylenediaminetetraacetic acid
  • a corrosion inhibitor added to an acid has been used.
  • a corrosion inhibitor for example, a nitrogen-containing organic compound is representative.
  • a quaternary ammonium salt is known as a nitrogen-containing organic compound used as a corrosion inhibitor (see, for example, Patent Document 1).
  • a quaternary ammonium salt 1-vinyl-3-ethylimidazolinium bromide, 3-ethylbenzothiazolium bromide, ethyltriethanolammonium bromide and the like are used.
  • a nitrogen-containing organic compound other than the quaternary ammonium salts For example, hexamethylenetetramine is used (Patent Document 1).
  • Such nitrogen-containing organic compounds have the disadvantage of slowing the pickling rate.
  • thiourea and its derivative are proposed as a nitrogen-containing organic compound which is a corrosion inhibitor (for example, refer patent document 2).
  • thiourea and its derivatives have the same drawbacks as quaternary ammonium salts.
  • a nitrogen-containing organic compound that is a corrosion inhibitor a cationic polymer such as a homopolymer of a quaternary ammonium salt-substituted vinyl compound, a polyamine compound having a cationic constituent unit and a sulfur dioxide unit (see, for example, Patent Document 3) ) Etc.
  • polyamine compounds have a higher corrosion-inhibiting effect than conventional nitrogen-containing organic compounds, and are useful as additives for metal acid cleaning solutions.
  • the pickling time has been shortened to improve the efficiency of pickling, and as a result, the acid content in the metal pickling solution has been increased. Therefore, development of a corrosion inhibitor having a stronger corrosion inhibition effect is demanded.
  • an object of the present invention is to provide a corrosion inhibitor for pickling metals that has a strong corrosion inhibiting effect when pickling a metal surface and has a small change in corrosion inhibition rate even if the inhibitor concentration changes. is there.
  • the present invention relates to any one of (1) to (7) below.
  • R 2 and R 3 is each independently a hydrogen atom, a methyl group, an ethyl group, or a benzyl group, and X ⁇ is a counter ion).
  • At least one anionic structural unit (B) represented by the following structural formula (III), (IV), or (V) (In the above formula (III), R 4 is hydrogen or a methyl group, and in (III), (IV), and (V), Y is independently hydrogen, Na, K, NH 4 , 1 / 2Ca, 1 / 2Mg, 1 / 2Fe, 1 / 3Al, or 1 / 3Fe.), And an amphoteric compound having a structural unit (C) represented by the following structural formula (VI) A metal acid cleaning corrosion inhibitor comprising the molecular compound (P). (2) The corrosion inhibitor according to (1), wherein the counter ion X ⁇ is an anion derived from an organic acid or an inorganic acid.
  • the cationic structural unit (A) is at least partly derived from a cationic monomer selected from diallylamines, inorganic acid salts, and organic acid salts thereof. Corrosion inhibitor. (4) At least a part of the cationic structural unit (A) is derived from diallyldimethylammonium chloride, and at least a part of the anionic structural unit (B) is derived from maleic acid.
  • R 5 is a hydrogen atom, a methyl group, an ethyl group, or a benzyl group.
  • R 6 and R 7 are independently a hydrogen atom, a methyl group, , An ethyl group, or a benzyl group, and Z ⁇ is a counter ion).
  • Itaconic acid, citraconic acid, mesaconic acid, maleic acid, fumaric acid, and methylenemalonic acid, and all or part of hydrogen in these carboxyl groups are Na, K, NH 4 , 1 / 2Ca, 1 / 2Mg, Amphoteric obtained by copolymerizing at least one monomer ( ⁇ ) selected from the group consisting of compounds substituted with at least one compound selected from 1 / 2Fe, 1 / 3Al, and 1 / 3Fe, and sulfur dioxide
  • a metal acid cleaning corrosion inhibitor comprising a polymer compound (P ′).
  • a cleaning liquid composition comprising an acid solution and the corrosion inhibitor according to any one of (1) to (5), wherein the amphoteric polymer compound (P) or the amphoteric polymer compound (P The cleaning liquid composition as described above, wherein the content of ') is 0.1 to 50000 mg with respect to 1 L of the acid liquid.
  • a method for cleaning a metal wherein the cleaning is performed by spraying the cleaning liquid composition according to (6) on a metal surface or immersing the metal surface in the cleaning liquid composition.
  • the corrosion inhibitor for acid cleaning of a metal of the present invention when the metal surface is acid cleaned, the corrosion of the metal can be effectively suppressed.
  • the metal acid cleaning corrosion inhibitor of the present invention has a very small change in the corrosion inhibition rate even when the inhibitor concentration changes, so that the quality of the final product is easily maintained constant.
  • the metal acid cleaning corrosion inhibitor of the present invention greatly contributes to the development of various industries such as the metal industry.
  • the corrosion inhibitor for acid cleaning of the first metal of the present invention has a structure represented by the following structural formula (Ia) or (Ib), or a structure thereof that is an inorganic acid salt or an organic acid salt, or At least one cationic structural unit (A) having the structure represented by the structural formula (IIa) or (IIb) (In the above formulas (Ia) and (Ib), R 1 is a hydrogen atom, a methyl group, an ethyl group, or a benzyl group.
  • R 2 and R 3 is each independently a hydrogen atom, a methyl group, an ethyl group, or a benzyl group, and X ⁇ is a counter ion).
  • At least one anionic structural unit (B) represented by the following structural formula (III), (IV), or (V) (In the above formula (III), R 4 is hydrogen or a methyl group, and in (III), (IV), and (V), Y is independently hydrogen, Na, K, NH 4 , 1 / 2Ca, 1 / 2Mg, 1 / 2Fe, 1 / 3Al, or 1 / 3Fe.), And an amphoteric compound having a structural unit (C) represented by the following structural formula (VI) The molecular compound (P) is included.
  • the first metal acid cleaning corrosion inhibitor of the present invention is composed of the amphoteric polymer compound (P) and a part thereof is highly amphoteric. When it is composed of the molecular compound (P), it is used to include both.
  • the amphoteric polymer compound (P) used for this invention is the said cationic structural unit (A), anionic structural unit (B), and a structure as a 4th structural unit.
  • a structural unit not corresponding to any of the units (C) for example, a structural unit derived from a monomer such as monoallylamine or acrylamide may be included.
  • a structural unit derived from a monomer such as monoallylamine or acrylamide may be contained in an amount of, for example, 15 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, based on the total structural units.
  • the copolymerization molar ratio of the cationic structural unit (A) / anionic structural unit (B) is preferably 10/1 to 1/3, more preferably 8/1 to 1/2. 6/1 to 1/1 is particularly preferable.
  • the copolymerization molar ratio of the cationic structural unit (A) / the structural unit derived from sulfur dioxide (C) is preferably 1/1 to 1 / 0.01, and 1.1 / 1 to 1 / 0.025 is more preferable, and 1.3 / 1 to 1 / 0.05 is particularly preferable.
  • the copolymerization ratio of the anionic structural unit (B) / the structural unit derived from sulfur dioxide (C) is preferably 20/1 to 1/20, and 15/1 to 1 / 15 is more preferable, and 10/1 to 1/10 is particularly preferable.
  • the molecular weight of the amphoteric polymer compound (P) is usually 1,000 to 10,000,000, preferably 3,000 to 1,000,000, more preferably 5,000 to 100. 5,000, more preferably 10,000 to 50,000, and particularly preferably 15,000 to 30,000.
  • Cationic structural unit (A) The cationic structural unit (A) constituting the amphoteric polymer compound (P) used in the present invention has a structure represented by the following structural formula (Ia) or (Ib), or an inorganic acid salt or an organic acid salt thereof. Or a structure represented by the following structural formula (IIa) or (IIb).
  • R 1 represents a hydrogen atom, a methyl group, an ethyl group, or a benzyl group
  • R 2 and R 3 Are each independently a hydrogen atom, a methyl group, an ethyl group, or a benzyl group
  • X ⁇ is a counter ion.
  • X ⁇ is preferably an anion derived from an organic acid or an inorganic acid, particularly preferably a halogen ion (more preferably, Cl ⁇ , Br ⁇ , or I ⁇ ), methyl sulfate ion, ethyl sulfate ion, or acetic acid. Ion.
  • At least a part of the cationic structural unit (A) is preferably derived from a cationic monomer selected from diallylamines and their inorganic acid salts and organic acid salts. Moreover, it is particularly preferable that at least a part of the cationic structural unit (A) is a structural unit derived from diallyldimethylammonium chloride.
  • each cationic structural unit is a range represented by the same general structural formula (Ia), (Ib), (IIa), or (IIb). They may have different structures or may have different structures represented by different general structural formulas. In the former case, for example, a plurality of types of cationic structural units (A) represented by the general structural formula (Ia), which have different structures due to different structures of R 1 , may be used.
  • one cationic structural unit (A) having a structure represented by Structural Formula (Ia) and another cationic structural unit (A) having a structure represented by Structural Formula (IIa) And may be used.
  • a cationic structural unit (A) having a structure represented by Structural Formula (Ia) and another cationic structural unit (A) having a structure represented by Structural Formula (IIa) And may be used.
  • Anionic structural unit (B) The anionic structural unit (B) constituting the amphoteric polymer compound (P) used in the present invention has a structure represented by the following structural formula (III), (IV), or (V). However, in said formula (III), R ⁇ 4 > is hydrogen or a methyl group, In (III), (IV), and (V), Y is hydrogen, Na, K each independently for every carboxy group to couple
  • amphoteric polymer compound (P) only one type of anionic structural unit (B) may be used alone, or a plurality of types of anionic structural units (B) having different structures may be used in combination. Good.
  • the respective anionic structural units are different from each other within the range represented by the same general structural formula (III), (IV), or (V).
  • a plurality of types of anionic structural units (B) represented by the general structural formula (III) and having different structures due to different Y elements may be used.
  • one anionic structural unit (B) having a structure represented by Structural Formula (III) and another anionic structural unit (B) having a structure represented by Structural Formula (IV) And may be used.
  • At least a part of the anionic structural unit (B) is preferably derived from maleic acid, and at this time, the anionic structural unit (B) has a structure represented by the above formula (IV). And Y is all hydrogen.
  • limiting in particular in content of the anionic structural unit (B) in an amphoteric polymer compound (P) It is preferable that it is the quantity corresponded to the above-mentioned copolymerization molar ratio.
  • the structural unit (C) constituting the amphoteric polymer compound (P) used in the present invention has a structure represented by the following structural formula (VI).
  • the structural unit (C) can usually be introduced into the polymer by using sulfur dioxide as a monomer.
  • sulfur dioxide as a monomer.
  • the amphoteric polymer compound (P) can be usually produced by copolymerizing a cationic monomer ( ⁇ ), an anionic monomer ( ⁇ ) and sulfur dioxide described later.
  • a cationic monomer ( ⁇ ) an anionic monomer ( ⁇ ) and sulfur dioxide described later.
  • the copolymerization ratios of the structural units (A), (B), and (C) are determined based on the respective monomers ( ⁇ ), ( ⁇ ), and dioxide dioxide. It is substantially the same as the charging ratio of sulfur.
  • the cationic monomer ( ⁇ ) has a structure represented by the following structural formula (VII), a structure that is an inorganic acid salt or an organic acid salt thereof, or a structure represented by the following structural formula (VIII).
  • R 5 is a hydrogen atom, a methyl group, an ethyl group, or a benzyl group.
  • R 6 and R 7 are independently a hydrogen atom, a methyl group, , An ethyl group, or a benzyl group, and Z ⁇ is a counter ion.
  • examples of the cationic monomer ( ⁇ ) include diallylamines such as diallylamine, N-hydrocarbon group-substituted diallylamines, and diallyldialkylammonium salts (that is, compounds having a diallylamine skeleton).
  • diallyldialkylammonium salt is preferred from the viewpoint that the corrosion inhibitor is easily dissolved in the liquid, and therefore, an acid cleaning liquid composition can be easily prepared.
  • N-hydrocarbon group-substituted diallylamines used in the present invention include N-methyldiallylamine, N-ethyldiallylamine, N-benzyldiallylamine and the like.
  • diallylamine or N-hydrocarbon group-substituted diallylamines as the cationic monomer ( ⁇ )
  • inorganic acids such as hydrochlorides, sulfates, nitrates and phosphates of the respective amines and organic acids such as acetates
  • a salt or the like may be used as a starting monomer for copolymerization.
  • diallyldialkylammonium salt used in the present invention includes diallyldimethylammonium chloride (diallyldimethylammonium chloride), diallyldimethylammonium bromide, diallyldimethylammonium iodide, diallyldimethylammonium sulfate, diallyldimethylammonium sulfate, diallyldiethylammonium chloride.
  • the combination of the groups R 6 and R 7 is preferably dimethyl, diethyl, ethylmethyl, dibenzyl, methylbenzyl, or ethylbenzyl, and the counter ion Z ⁇ is a halogen ion, methyl Although it is preferable that they are a sulfate ion or an ethyl sulfate ion, neither is limited to these.
  • an anionic monomer ( ⁇ ) in the production of the amphoteric polymer compound (P) used in the present invention, an anionic monomer ( ⁇ ) can be used to introduce the anionic structural unit (B).
  • the anionic monomer ( ⁇ ) contains itaconic acid, citraconic acid, mesaconic acid, maleic acid, fumaric acid, and methylenemalonic acid, and all or part of hydrogens in these carboxyl groups are Na, K, NH 4 , a monomer selected from the group consisting of compounds substituted with at least one selected from 1 / 2Ca, 1 / 2Mg, 1 / 2Fe, 1 / 3Al, and 1 / 3Fe.
  • the anionic monomer ( ⁇ ) fumaric acid, maleic acid, citraconic acid, itaconic acid or a sodium salt, potassium salt or ammonium salt thereof can be used.
  • the amphoteric polymer compound (P) used in the present invention is particularly preferably used as the cationic monomer ( ⁇ ) by using at least one diallyldimethylammonium salt as an anionic monomer ( ⁇ ) Of fumaric acid, maleic acid, itaconic acid and citraconic acid, and a copolymer obtained by copolymerizing sulfur dioxide.
  • amphoteric Polymer Compound (P) Next, a method for producing the amphoteric polymer compound (P) used in the present invention will be described. Although there is no restriction
  • the molar ratio of the cationic monomer ( ⁇ ) / anionic monomer ( ⁇ ) is preferably 10/1 to 1/3, more preferably 8/1 to 1/2, and 6/1. ⁇ 1 / 1 is particularly preferred.
  • the molar ratio of the cationic monomer ( ⁇ ) / sulfur dioxide monomer is preferably 1/1 to 1 / 0.01, more preferably 1.1 / 1 to 1 / 0.025. 1.3 / 1 to 1 / 0.05 is particularly preferable.
  • the molar ratio of the anionic monomer ( ⁇ ) / sulfur dioxide monomer is preferably 20/1 to 1/20, more preferably 15/1 to 1/15, and 10/1 to 1 / 10 is particularly preferred.
  • the polar solvent include water, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, and mixed solvents thereof. Among these, water is preferable from the viewpoints of polymerization reactivity and safety.
  • a cationic monomer ( ⁇ ), an anionic monomer ( ⁇ ) And sulfur dioxide for example, monomers such as monoallylamine and acrylamide are, for example, not more than 15 mol%, preferably not more than 10 mol%, more preferably, all monomers. May be used in an amount of 5 mol% or less.
  • the monomer concentration in the reaction solution during the polymerization of the amphoteric polymer compound (P) varies depending on the type of the monomer, but is usually 10 to 75% by mass, preferably 30 to 70% by mass, and more Preferably, it is 50 to 65% by mass.
  • This copolymerization reaction is usually a radical polymerization reaction and is performed in the presence of a radical polymerization catalyst.
  • the type of radical polymerization catalyst is not particularly limited, and preferred examples thereof include peroxides such as t-butyl hydroperoxide, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, azobis-based, Examples thereof include water-soluble azo compounds such as diazo compounds.
  • the addition amount of the radical polymerization catalyst is generally 0.1 to 20 mol%, preferably 1.0 to 10 mol%, based on the total monomers.
  • the polymerization temperature is generally 0 to 100 ° C., preferably 5 to 80 ° C.
  • the polymerization time is generally 20 to 150 hours, preferably 30 to 100 hours.
  • the polymerization atmosphere does not cause a significant problem in the polymerizability even in the air, but can also be performed in an atmosphere of an inert gas such as nitrogen.
  • Amphoteric polymer compound (P ') The corrosion inhibitor for acid cleaning of the second metal of the present invention is obtained by copolymerizing at least one cationic monomer ( ⁇ ), at least one anionic monomer ( ⁇ ), and sulfur dioxide. The resulting amphoteric polymer compound (P ′) is included.
  • the cationic monomer ( ⁇ ), the anionic monomer ( ⁇ ), and sulfur dioxide are the same as those described in detail above. Further, the meaning of “comprising” is the same as that described for the corrosion inhibitor for acid cleaning of the first metal of the present invention.
  • the amphoteric polymer compound (P ′) may correspond to the amphoteric polymer compound (P) described above.
  • the metal acid cleaning corrosion inhibitor of the present invention may be entirely composed of an amphoteric polymer compound (P) or an amphoteric polymer compound (P ′). A part thereof may be composed of an amphoteric polymer compound (P) or an amphoteric polymer compound (P ′). Therefore, after the completion of the polymerization, the amphoteric polymer compound (P) or the amphoteric polymer compound (P ′) may be used as it is as a corrosion inhibitor for acid cleaning of the metal of the present invention.
  • An organic solvent such as acetone may be added to the liquid after completion to cause reprecipitation and solidification, and then used as a corrosion inhibitor.
  • the cleaning liquid composition of the present invention is prepared by using a metal acid cleaning corrosion inhibitor of the present invention as an amphoteric polymer compound (P) or an amphoteric polymer compound (P ′) solid or In terms of pure form, it usually contains 0.1 to 50000 mg, preferably 1 to 10000 mg, more preferably 1 to 5000 mg. Since the content is 0.1 mg or more with respect to 1 L of the acid solution, the necessary corrosion inhibiting effect can be obtained, and since it is 50000 mg or less, the corrosion inhibiting effect can be improved according to the added amount.
  • a metal acid cleaning corrosion inhibitor of the present invention as an amphoteric polymer compound (P) or an amphoteric polymer compound (P ′) solid or In terms of pure form, it usually contains 0.1 to 50000 mg, preferably 1 to 10000 mg, more preferably 1 to 5000 mg. Since the content is 0.1 mg or more with respect to 1 L of the acid solution, the necessary corrosion inhibiting effect can be obtained, and since it is 50000 mg or less, the corrosion inhibiting
  • the acid used for the acid solution is not particularly limited, but inorganic acids such as hydrochloric acid, sulfuric acid, sulfamic acid, and hydrofluoric acid, organic acids such as formic acid, succinic acid, citric acid, malic acid, hydroxyacetic acid, and gluconic acid, ethylenediaminetetraacetic acid, and the like These chelating agents are preferred.
  • the corrosion inhibitor of the present invention may be added to the acid solution at the time of use, or may be added to the acid solution in advance to obtain the cleaning solution composition of the present invention, which may be used as it is or after being diluted with water.
  • surfactants and solvents may be used to improve the mixing with the cleaning liquid, and the surfactants and solvents used for this purpose may be previously mixed with the corrosion inhibitor of the present invention, separately. You may add to the cleaning composition of this invention.
  • the corrosion inhibitor of the present invention may be used in combination with other corrosion inhibitors, and these other corrosion inhibitors may be previously mixed with the corrosion inhibitor of the present invention, and separately washed according to the present invention. It may be added to the agent composition.
  • Specific examples of other corrosion inhibitors to be used in combination include 1-vinyl-3-ethylimidazolinium bromide, 3-ethylbenzothiazolium bromide, ethyltriethanolammonium bromide and the like, but are not limited to these specific examples. Is not to be done.
  • pickling accelerators such as sulfites for improving the pickling rate can be used in combination.
  • the metal cleaning method of the present invention is characterized in that the metal surface is cleaned by spraying the cleaning liquid composition of the present invention on the metal surface or immersing the metal surface in the cleaning liquid composition.
  • the cleaning liquid composition containing the corrosion inhibitor of the present invention is cleaned by spraying the metal surface to be cleaned or immersing the metal piece to be cleaned in the cleaning liquid composition.
  • the metal to be cleaned is not particularly limited, but it is particularly effective when used for steel.
  • DADMAC abbreviation for diallyldimethylammonium chloride
  • MA abbreviation for maleic acid
  • SO 2 abbreviation for sulfur dioxide
  • AMPS abbreviation for 2-acrylamido-2-methylpropanesulfonic acid
  • DA • HCl abbreviation for diallylamine hydrochloride
  • GPC gel permeation chromatography
  • the eluent flow pump is Hitachi L-6000
  • the detector is a Shodex RI SE-61 differential refractive index detector
  • the column is Asahi Pack's water-based gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS- 620HQ (exclusion limit molecular weight 2 million) and a double connection were used.
  • the sample was adjusted to a concentration of 0.5 g / 100 mL with an eluent, and 20 ⁇ L was used.
  • a 0.4 mol / L sodium chloride aqueous solution was used as an eluent.
  • the column temperature was 30 ° C. and the flow rate was 1.0 mL / min.
  • a calibration curve is obtained using polyethylene glycols having molecular weights of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000, etc. as a standard sample, and the weight average molecular weight of the copolymer is obtained based on the calibration curve. It was.
  • Example 1 After the solution after completion of the polymerization was measured by the GPC method, the weight average molecular weight was 23,000, and the polymerization rate was 100%.
  • Comparative Synthesis Example 2 Synthesis Example of 2: 1 Binary Copolymer of Diallyldimethylammonium Chloride and Maleic Acid Comparative Example was carried out in the same manner as Comparative Synthesis Example 1 except that the copolymerization ratio of diallyldimethylammonium chloride and maleic acid was changed. The title copolymer used in 2 was prepared. The weight average molecular weight was 24,000, and the polymerization rate was 100%.
  • Corrosion amount [weight of test piece before immersion (mg) ⁇ weight of test piece after immersion (mg)] / surface area of test piece (cm 2 ) ⁇ (1)
  • Corrosion inhibition rate [corrosion amount of comparative example 6 (mg / cm 2 ) ⁇ corrosion amount of each example or comparative example (mg / cm 2 )] ⁇ 100 / corrosion amount of comparative example 6 (mg / cm 2 )-(2)
  • Performance degradation rate 100 ⁇ A ⁇ (3)
  • A corrosion inhibition rate at 1000 mg addition amount (%) ⁇ 100) / corrosion inhibition rate at 50 mg addition amount (%)
  • the corrosion inhibitor for metal acid cleaning according to the present invention, and the cleaning liquid composition and the cleaning method using the same have a strong corrosion inhibitory effect in acid cleaning of various metal surfaces, and the concentration of the inhibitor changes. Since the change of the corrosion inhibition effect is small, it has high utility value and high applicability in various industries such as metal industry.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

La présente invention concerne un agent anticorrosif destiné à être utilisé pour le lavage d'un métal avec un acide, comprenant un composé polymère amphotère (P) présentant au moins une unité constitutive cationique (A) présentant une structure spécifique, au moins une unité constitutive anionique (B) présentant une structure spécifique, et une unité constitutive spécifique contenant du soufre (C) présentant une structure spécifique.
PCT/JP2011/064025 2010-07-15 2011-06-20 Agent anticorrosif pour le lavage d'un métal à l'acide, composition de solution de détergent, et procédé de lavage de métal WO2012008269A1 (fr)

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JP2012524505A JP5630672B2 (ja) 2010-07-15 2011-06-20 金属の酸洗浄用腐食抑制剤、洗浄液組成物及び金属の洗浄方法
US13/808,670 US20130109607A1 (en) 2010-07-15 2011-06-20 Anti-corrosive agent for washing of metal with acid, detergent solution composition, and method for washing of metal

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JP2019048284A (ja) * 2017-09-12 2019-03-28 オルガノ株式会社 シリカ系スケール抑制剤およびシリカ系スケールの抑制方法
WO2020175121A1 (fr) * 2019-02-28 2020-09-03 藤倉コンポジット株式会社 Agent de traitement de surface, son procédé de production et procédé de traitement de surface
KR102457605B1 (ko) * 2022-01-28 2022-10-20 김영량 산세척 과정에서 구조물의 부식을 억제하기 위한 부식억제제 조성물
JP7530847B2 (ja) 2021-02-25 2024-08-08 日本ペイント・オートモーティブコーティングス株式会社 カチオン電着塗料組成物

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KR101732657B1 (ko) 2016-03-17 2017-05-04 주식회사 성창 금속재료의 산세정 조성물
WO2019133816A1 (fr) * 2017-12-28 2019-07-04 Guardian Glass, LLC Revêtement anti-corrosion pour substrat en verre
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JP2019048284A (ja) * 2017-09-12 2019-03-28 オルガノ株式会社 シリカ系スケール抑制剤およびシリカ系スケールの抑制方法
WO2020175121A1 (fr) * 2019-02-28 2020-09-03 藤倉コンポジット株式会社 Agent de traitement de surface, son procédé de production et procédé de traitement de surface
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JP7530847B2 (ja) 2021-02-25 2024-08-08 日本ペイント・オートモーティブコーティングス株式会社 カチオン電着塗料組成物
KR102457605B1 (ko) * 2022-01-28 2022-10-20 김영량 산세척 과정에서 구조물의 부식을 억제하기 위한 부식억제제 조성물

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