WO2021132154A1 - Agent de nettoyage acide pour matériau métallique à base d'aluminium, et procédé de nettoyage de matériau métallique à base d'aluminium - Google Patents

Agent de nettoyage acide pour matériau métallique à base d'aluminium, et procédé de nettoyage de matériau métallique à base d'aluminium Download PDF

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Publication number
WO2021132154A1
WO2021132154A1 PCT/JP2020/047674 JP2020047674W WO2021132154A1 WO 2021132154 A1 WO2021132154 A1 WO 2021132154A1 JP 2020047674 W JP2020047674 W JP 2020047674W WO 2021132154 A1 WO2021132154 A1 WO 2021132154A1
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WO
WIPO (PCT)
Prior art keywords
aluminum
based metal
concentration
ion
metal materials
Prior art date
Application number
PCT/JP2020/047674
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English (en)
Japanese (ja)
Inventor
佐藤　新
雅之 神村
Original Assignee
日本ペイント・サーフケミカルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ペイント・サーフケミカルズ株式会社 filed Critical 日本ペイント・サーフケミカルズ株式会社
Publication of WO2021132154A1 publication Critical patent/WO2021132154A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • 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
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • 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
    • C11D7/10—Salts
    • C11D7/16—Phosphates including polyphosphates
    • 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
    • C11D7/34—Organic compounds containing sulfur
    • 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
    • C23G1/12—Light metals

Definitions

  • the present invention relates to an acidic detergent for aluminum-based metal materials and a method for cleaning aluminum-based metal materials. More specifically, an acidic detergent for aluminum-based metal materials, which has good de-smutability even when washed at a low temperature and can suppress the occurrence of brown spots even if chemical conversion treatment is omitted, and The present invention relates to a method for cleaning an aluminum-based metal material using the cleaning agent.
  • Aluminum oxides, oils, etc. are generally present on the surface of aluminum-based metal materials manufactured from aluminum or aluminum alloys. Furthermore, aluminum cans such as beverage cans manufactured by drawing processing called drawing and ironing processing (hereinafter referred to as DI processing) have aluminum powder (hereinafter referred to as smut) generated on the surface of the aluminum cans that are scraped during drawing. And lubricating oil are attached.
  • DI processing drawing processing
  • smut aluminum powder
  • a chemical conversion treatment film is formed by a chemical conversion treatment, and then a coating coating film is formed by a painting treatment for practical use. Then, in order to form a strong chemical conversion treatment film and a coating film, it is necessary to sufficiently remove and clean the aluminum oxide, oil, smut and the like existing on the surface.
  • an acidic detergent of a type that appropriately etches and cleans the surface.
  • a hydrofluoric acid-based cleaning agent has been used as the acidic cleaning agent, but in recent years, a fluorine-free cleaning agent has been used from the viewpoint of environmental protection.
  • acidic detergents containing oxidized metal ions such as ferric ion (Fe 3+ ) and metavanadate ion (VO 3- ) have a high treatment temperature of 70 to 80 ° C. in order to secure the etching ability. There was a problem that it was necessary to set it and it was inferior in economic efficiency.
  • aluminum cans such as beverage cans are subjected to a step of forming a chemical conversion treatment film by performing a chemical conversion treatment after cleaning the surface with an acidic detergent. This is because when the chemical conversion treatment film is not formed, when the washing water is dried, the washing water reacts with aluminum to form aluminum hydroxide, and a so-called brown spot is generated in which the portion looks brown.
  • the chemical conversion treatment step for forming the chemical conversion treatment film can be omitted. If the chemical conversion treatment step can be omitted, it is possible to shift to the painting step as it is after cleaning, so that the economic effect of omitting the step is very large. However, at present, no such cleaning agent has been proposed.
  • the present invention has been made to solve the above problems, and an object of the present invention is to have good desmutability even when washed at a low temperature, and to omit a chemical conversion treatment as a brown spot. It is an object of the present invention to provide an acidic cleaning agent for an aluminum-based metal material and a method for cleaning an aluminum-based metal material, which can suppress the generation.
  • the present inventors have conducted diligent studies to solve the above problems. Then, in an acidic detergent containing a phosphate ion, a sulfate ion, and a ferric ion, if the phosphate ion is the main component and the concentration ratio of the phosphate ion and the ferric ion is within a specific range.
  • the present invention is completed by finding that the surface of an aluminum-based metal material can be sufficiently cleaned and a phosphorus-based film can be formed even if the treatment temperature is low, and as a result, the above-mentioned problems can be solved. It came to.
  • the present invention is an acidic detergent for aluminum-based metal materials containing phosphate ion, sulfate ion, and ferric ion, and the concentration of the phosphate ion is 13 to 26 g / L.
  • the concentration of the phosphate ion is larger than the concentration of the sulfate ion, and the concentration ratio of the phosphate ion to the ferric ion is 35: 1 to 180: 1.
  • Acidic cleaning for aluminum-based metal materials Agent containing phosphate ion, sulfate ion, and ferric ion, and the concentration of the phosphate ion is 13 to 26 g / L.
  • the concentration of the phosphate ion is larger than the concentration of the sulfate ion, and the concentration ratio of the phosphate ion to the ferric ion is 35: 1 to 180: 1.
  • the concentration of the sulfate ion may be 0.25 to 1.25 g / L.
  • the concentration of the ferric ion may be 0.1 to 0.5 g / L.
  • the concentration ratio of the phosphate ion to the sulfate ion may be 10: 1 to 75: 1.
  • the concentration of the surfactant may be 0.5 to 3.0 g / L.
  • It may further contain organic sulfonic acid.
  • Another invention of the present invention comprises a cleaning step of cleaning the above-mentioned acidic cleaning agent for an aluminum-based metal material at a liquid temperature of 40 to 70 ° C. by bringing it into contact with the surface of the aluminum-based metal material. It is a cleaning method of.
  • the contact time may be 15 to 60 seconds.
  • the acidic detergent for aluminum-based metal materials of the present invention has good de-smutability even when the aluminum-based metal material is washed at a low temperature, and brown spots are generated even if the chemical conversion treatment is omitted after cleaning. Can be suppressed. Therefore, its economic value is great.
  • the acidic detergent for aluminum-based metal materials of the present invention contains phosphate ions, sulfate ions, and ferric ions as essential components. Then, the phosphate ion is the main component, and the concentration ratio of the phosphate ion and the ferric ion is in a specific range.
  • Phosphate ion Phosphate ions contained in the aluminum-based metal material for the acidic cleaning agent of the present invention (PO 4 3-), among components constituting the aluminum-based metal material for acid cleaner, and serves as a main component.
  • the acidic detergent for aluminum-based metal materials of the present invention contains phosphate ion, sulfate ion, and ferrous ion as essential components, but the concentration of phosphate ion is larger than the concentration of sulfate ion. ..
  • the main component is phosphate ions
  • the exposure of aluminum can be suppressed, and the brown spots generated by reacting with water washing can be suppressed.
  • the acidic cleaning agent for aluminum-based metal materials of the present invention it is possible to omit the conventional step of forming a chemical conversion treatment film by chemical conversion treatment, and after cleaning, the process proceeds to the coating treatment as it is.
  • a coating film can be formed. Therefore, in the field of beverage cans and the like, it is possible to greatly contribute to the economic effect of omitting the process.
  • the concentration of phosphate ions is 13 to 26 g / L, preferably 18 to 23 g / L, and particularly preferably 18 to 20 g / L.
  • the phosphate ion concentration is less than 15 g / L, the effects of removing smut and suppressing brown spots will be insufficient.
  • the concentration of phosphate ions exceeds 26 g / L, the mat is excessively removed, and the formation of a phosphorus-based film having a brown spot suppressing effect is inhibited.
  • the concentration ratio of phosphate ion to ferric ion is 35: 1 to 180: 1, preferably 90: 1 to 115: 1, and preferably 90: 1 to 100: 1. Especially preferable.
  • the concentration ratio of phosphate ion to sulfate ion is preferably 10: 1 to 75: 1, more preferably 30: 1 to 52: 1, and preferably 36: 1 to 40: 1. Especially preferable.
  • the source of phosphate ions contained in the acidic cleaning agent for aluminum-based metal materials of the present invention is not particularly limited as long as the cleaning agent can generate phosphate ions by ionization.
  • the cleaning agent can generate phosphate ions by ionization.
  • phosphoric acid, phosphoric acid, pyrophosphoric acid, metaphosphoric acid and the like can be mentioned.
  • the substance that is the source of phosphate ions may be used not only of one type but also in combination of two or more types.
  • phosphoric acid is preferable because it is widely applied industrially and is also used as a food additive.
  • Phosphoric acid also exhibits a function as an etching accelerator.
  • Sulfate ion contained as an essential component in the acidic detergent for aluminum-based metal materials of the present invention have a function as an etching accelerator.
  • the concentration of sulfate ion is preferably 0.25 to 1.25 g / L, more preferably 0.5 to 1.25 g / L.
  • the concentration of sulfate ions is less than 0.25 g / L, the etching rate will decrease and the effect of removing smut will not be sufficient.
  • the concentration of sulfate ions exceeds 1.25 g / L, no further effect is observed on etching, which is economically disadvantageous.
  • the source of sulfate ions contained in the acidic cleaning agent for aluminum-based metal materials of the present invention is not particularly limited as long as the cleaning agent can generate sulfate ions by ionization.
  • sulfuric acid or a salt thereof iron sulfate, aluminum sulfate, calcium sulfate, sodium sulfate, etc.
  • the substance that is the source of sulfate ions may be used not only of one type but also in combination of two or more types.
  • ferric sulfate when ferric sulfate is supplied as a source of ferric ions, which is an essential component of the acidic detergent for aluminum-based metal materials of the present invention, the sulfate ions are ionized together with the ferric ions. It becomes.
  • the concentration of sulfate ion contained in the acidic detergent can be adjusted by combining ferric sulfate and another sulfate ion source.
  • Sulfuric acid is particularly preferable as a source of sulfate ions because it is widely applied industrially and has excellent economic efficiency.
  • the ferric ion contained as an essential component in the acidic detergent for aluminum-based metal materials of the present invention has a function as an etching accelerator.
  • the etching reaction of an aluminum-based metal in an acidic detergent consists of an anodic reaction in which aluminum becomes aluminum ions (Al 3+ ) and a cathode reaction in which H + in the acidic detergent is reduced to 1 / 2H 2 . Therefore, when ferrous ion (Fe 3+ ), which is an oxidized metal ion, is present in the acidic cleaning agent, the anode reaction in which Fe 3+ is reduced to Fe 2+ is the reduction of H + . It occurs at the same time and the etching reaction of iron is promoted.
  • the concentration of ferric ion is preferably 0.1 to 0.5 g / L, more preferably 0.2 to 0.5 g / L.
  • the concentration of ferric ion is less than 0.1 g / L, the etching rate will decrease and the effect of removing smut will not be sufficient. On the other hand, when the concentration of ferric ion exceeds 0.5 g / L, no further effect is observed on the etching, which is economically disadvantageous.
  • the source of ferric ions contained in the acidic cleaning agent for aluminum-based metal materials of the present invention is not particularly limited as long as the cleaning agent can generate ferric ions by ionization. Absent.
  • the ferric ion is supplied as a ferric sulfate or ferric nitrate because it is preferably supplied as a water-soluble salt such as a sulfate or a nitrate.
  • the sulfate ion is ionized together with the ferric ion, and when supplied as ferric nitrate, the nitrate ion is ionized together with the ferric ion.
  • ORP oxidation-reduction potential
  • the acidic detergent for aluminum-based metal materials of the present invention may optionally contain other components in addition to the essential components of phosphate ion, sulfate ion, and ferric ion.
  • surfactants, organic sulfonic acids and the like can be mentioned.
  • the surfactant is mainly added to remove the oil and fat component adhering to the surface of the aluminum-based metal material.
  • the surfactant plays a role of removing the lubricant.
  • the surfactant prevents the removed oil and fat components and lubricant components from floating in the cleaning agent.
  • the oil / fat component or the lubricant component is suspended in the cleaning agent, it may be re-adsorbed on the surface of the aluminum-based metal material, but this can be avoided by adding a surfactant.
  • the type of surfactant is not particularly limited, and any of nonionic, cationic, anionic, and zwitterionic surfactants can be used.
  • nonionic type is preferable, and for example, ethoxylated alkylphenol type, hydrogen carbonate derivative, abietic acid derivative, primary ethoxylated alcohol, modified polyethoxylated alcohol and the like are preferably used.
  • the concentration of the surfactant is preferably 0.5 to 3.0 g / L, more preferably 1.0 to 2.5 g / L, and more preferably 1.5 to 2.0 g / L. Is particularly preferable.
  • the concentration of the surfactant is less than 0.5 g / L, the detergency, especially the degreasing property, is lowered.
  • the concentration of the surfactant exceeds 3.0 g / L, it foams in the detergent, which makes the cleaning treatment difficult and puts a load on the wastewater treatment.
  • Organic sulfonic acid (Organic sulfonic acid)
  • the organic sulfonic acid is mainly blended in order to exert a sufficient etching effect even under low temperature conditions.
  • the organic sulfonic acid has a structure represented by the following formula (1).
  • [Chemical 1] R-SO 3 H ⁇ ⁇ ⁇ (1) (In the formula, R represents a methyl group or a substituted alkyl group having 1 to 9 carbon atoms and having at least 1 or more hydroxyl groups.)
  • the substituted alkyl group in the above formula (1) is not limited to a straight chain and may be a branched chain.
  • Specific examples of the organic sulfonic acids other HSO 3 -CH 3, HSO 3 -CH 2 OH, HSO 3 -CH 2 CH 2 OH, HSO 3 -CH 2 CH 2 CH 2 OH, HSO 3 -CH 2 CH (OH) CH 2 OH and the like can be mentioned.
  • the organic sulfonic acid may be used alone or in combination of two or more.
  • the content of organic sulfonic acid is preferably 0.01 g / L to 0.2 g / L. If the content is less than 0.01 g / L, the effect is insufficient, and if it exceeds 0.2 g / L, no further effect is observed, which is economically disadvantageous.
  • the above-mentioned acidic detergent for an aluminum-based metal material of the present invention is cleaned at a liquid temperature of 50 to 60 ° C. and brought into contact with the surface of the aluminum-based metal material for cleaning. It includes a process. As long as the cleaning step is included, other steps may be optionally included.
  • the method of bringing the acidic detergent into contact with the aluminum-based metal material is not particularly limited, and a method known in the art can be appropriately selected. For example, a spray method or a dipping method can be mentioned.
  • the method for cleaning aluminum-based metal materials of the present invention is used with a liquid temperature of 40 to 70 ° C. for an acidic detergent. That is, it is possible to wash at a low temperature as compared with the conventional washing method.
  • a more preferable treatment temperature is 40 to 60 ° C., most preferably 40 to 50 ° C.
  • the time for contacting the acidic cleaning agent with the aluminum-based metal material is particularly limited as long as it can be sufficiently etched and a uniform phosphorus-based film can be formed on the surface of the aluminum-based metal material. is not it. It can be set appropriately according to the processing temperature.
  • the contact time is preferably 15 to 60 seconds. More preferably, it is 25 to 45 seconds, and most preferably 25 to 45 seconds.
  • each material was mixed and stirred with industrial water so as to have the concentrations shown in Tables 1 and 2. At this time, only the activator was added last after mixing each material. After preparing the acidic detergent for aluminum-based metal materials, the temperature was raised until the predetermined treatment conditions were met.
  • the prepared container without a lid was spray-treated with the acidic detergents for aluminum-based metal materials obtained in Examples and Comparative Examples under the treatment conditions shown in Tables 1 and 2.

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

Abstract

L'invention fournit une composition de matériau de revêtement qui permet de former un film de revêtement mat de faible brillance et hautement résistant, et un film de revêtement obtenu à partir de cette composition de matériau de revêtement.　En outre, l'invention concerne un agent de nettoyage acide qui contient des ions d'acide phosphorique, des ions d'acide sulfurique et des ions ferriques, et dans lequel les ions d'acide phosphorique constituent le composant principal, et le rapport de concentration des ions d'acide phosphorique et des ions ferriques, se situe dans une plage spécifique. Plus précisément, la concentration en ions d'acide phosphorique est comprise entre １５ et ２６ｇ／Ｌ, et est telle qu'elle est supérieure à la concentration en ions d'acide sulfurique, et le rapport de concentration des ions d'acide phosphorique et des ions ferriques, est compris entre ３５：１ et １８０：１.
PCT/JP2020/047674 2019-12-27 2020-12-21 Agent de nettoyage acide pour matériau métallique à base d'aluminium, et procédé de nettoyage de matériau métallique à base d'aluminium WO2021132154A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-239660 2019-12-27
JP2019239660 2019-12-27

Publications (1)

Publication Number Publication Date
WO2021132154A1 true WO2021132154A1 (fr) 2021-07-01

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PCT/JP2020/047674 WO2021132154A1 (fr) 2019-12-27 2020-12-21 Agent de nettoyage acide pour matériau métallique à base d'aluminium, et procédé de nettoyage de matériau métallique à base d'aluminium

Country Status (2)

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JP (1) JP2021107576A (fr)
WO (1) WO2021132154A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0273983A (ja) * 1988-09-07 1990-03-13 Nippon Parkerizing Co Ltd アルミニウム用酸性洗浄液
JP2007197775A (ja) * 2006-01-26 2007-08-09 Nippon Paint Co Ltd アルミニウム系金属材料用酸性洗浄剤及びその洗浄方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0273983A (ja) * 1988-09-07 1990-03-13 Nippon Parkerizing Co Ltd アルミニウム用酸性洗浄液
JP2007197775A (ja) * 2006-01-26 2007-08-09 Nippon Paint Co Ltd アルミニウム系金属材料用酸性洗浄剤及びその洗浄方法

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JP2021107576A (ja) 2021-07-29

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