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WO2021132154A1 - Acidic cleaning agent for aluminum-based metal materials, and method for cleaning aluminum-based metal material - Google Patents

Acidic cleaning agent for aluminum-based metal materials, and method for cleaning aluminum-based metal material 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
Other languages
French (fr)
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
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Publication of WO2021132154A1 publication Critical patent/WO2021132154A1/en

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (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

Provided are: a coating composition which makes it possible to form a lower-gloss high-strength matte coating film; and a coating film produced from the coating composition.　An acidic cleaning agent containing a phosphoric acid ion, a sulfuric acid ion and a ferric ion, wherein the phosphoric acid ion is a main component and the ratio of the concentration of the phosphoric acid ion to the concentration of the ferric ion falls within a specified range. More specifically, the concentration of the phosphoric acid ion is 15 to 26 g/L, the concentration of the phosphoric acid ion is adjusted to a value larger than the concentration of the sulfuric acid ion, and the ratio of the concentration of the phosphoric acid ion to the concentration of the ferric ion is 35:1 to 180:1.

Description

アルミニウム系金属材料用酸性洗浄剤およびアルミニウム系金属材料の洗浄方法Acid cleaning agent for aluminum-based metal materials and cleaning method for aluminum-based metal materials
　本発明は、アルミニウム系金属材料用酸性洗浄剤およびアルミニウム系金属材料の洗浄方法に関する。さらに詳細には、低温で洗浄した場合であっても、脱スマット性が良好であり、化成処理を省略してもブラウンスポット発生を抑制することのできる、アルミニウム系金属材料用酸性洗浄剤、および当該洗浄剤を用いたアルミニウム系金属材料の洗浄方法に関する。 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.
　アルミニウムまたはアルミニウム合金から製造されるアルミニウム系金属材料には、その表面に、アルミニウム酸化物や油分等が存在しているのが一般的である。さらに、ドローイング・アンド・アイアニング加工（以下、ＤＩ加工という）と呼ばれる引き抜き加工によって製造される飲料缶等のアルミニウム缶は、その表面に、引き抜き時に削られて発生するアルミニウム粉末（以下、スマットという）や潤滑油が付着している。 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.
　ここで、通常、飲料缶等のアルミニウム缶には、化成処理により化成処理皮膜が形成され、その後、塗装処理により塗装塗膜が形成されて実用される。そして、強固な化成処理皮膜および塗装塗膜を形成するためには、表面に存在しているアルミニウム酸化物や、油分、およびスマット等を、十分に除去して清浄化する必要がある。 Here, usually, in an aluminum can such as a beverage can, 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.
　一般的に、アルミニウム系金属材料の表面を清浄化する方法としては、表面を適度にエッチングして洗浄するタイプの酸性洗浄剤を用いた処理が挙げられる。酸性洗浄剤としては、従来、フッ化水素酸系の洗浄剤が用いられていたが、近年では環境保護の観点から、フッ素フリーの洗浄剤が用いられつつある。 Generally, as a method of cleaning the surface of an aluminum-based metal material, there is a treatment using an acidic detergent of a type that appropriately etches and cleans the surface. Conventionally, 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.
　このようなフッ素フリーの洗浄剤として、無機酸から選ばれる少なくとも一種と、臭素イオンと、酸化型金属イオンとを、各所定量ずつ含有するアルミニウム系金属材料用酸性洗浄水溶液が提案されている（特許文献１参照）。 As such a fluorine-free cleaning agent, an acidic cleaning aqueous solution for aluminum-based metal materials containing at least one selected from inorganic acids, bromine ions, and oxidized metal ions in predetermined amounts has been proposed (Patented). Reference 1).
特開平７－１１３１８９号公報Japanese Unexamined Patent Publication No. 7-113189
　しかしながら、第２鉄イオン（Ｆｅ３＋）やメタバナジン酸イオン（ＶＯ３－）等の酸化型金属イオンを含む酸性洗浄剤は、エッチング能力を確保するために、処理温度を７０～８０℃という高温に設定する必要があり、経済性に劣るという問題があった。 However, 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.
　また、上記の通り、飲料缶等のアルミニウム缶は、酸性洗浄剤によって表面を清浄化した後に、化成処理を実施して化成処理皮膜を形成する工程が実施されている。化成処理皮膜が未形成の場合には、水洗水が乾燥する際に、水洗水とアルミニウムとが反応して水酸化アルミニウムとなり、当該部分が褐色に見える、いわゆるブラウンスポットが発生するためである。 Further, as described above, 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.
　ここで、酸性洗浄剤によって表面を清浄化する際に、同時に、アルミニウム系金属材料に皮膜を形成できれば、化成処理皮膜を形成するための化成処理工程を省略することが可能となる。化成処理工程を省略できれば、洗浄後にそのまま塗装工程に移行することが可能となるため、工程省略による経済的効果は非常に大きい。しかしながら現在のところ、そのような洗浄剤は提案されていなかった。 Here, when the surface is cleaned with an acidic detergent, if a film can be formed on the aluminum-based metal material at the same time, 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.
　本発明は、上記の課題を解決するためになされたものであり、その目的は、低温で洗浄した場合であっても、脱スマット性が良好であるとともに、化成処理を省略してもブラウンスポット発生を抑制することのできる、アルミニウム系金属材料用酸性洗浄剤およびアルミニウム系金属材料の洗浄方法を提供することにある。 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.
　本発明者らは、上記課題を解決するため鋭意検討を行った。そして、リン酸イオンと、硫酸イオンと、第２鉄イオンと、を含む酸性洗浄剤において、リン酸イオンを主成分とし、リン酸イオンと第２鉄イオンとの濃度比を特定範囲とすれば、処理温度が低くても、アルミニウム系金属材料の表面を十分に清浄化できるとともに、リン系の皮膜を形成することが可能となり、その結果、上記課題を解決できることを見出し、本発明を完成するに至った。 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.
　すなわち本発明は、リン酸イオンと、硫酸イオンと、第２鉄イオンと、を含むアルミニウム系金属材料用酸性洗浄剤であって、前記リン酸イオンの濃度は、１３～２６ｇ／Ｌであり、前記リン酸イオンの濃度は、前記硫酸イオンの濃度よりも大きく、前記リン酸イオンと前記第２鉄イオンとの濃度比は、３５：１～１８０：１である、アルミニウム系金属材料用酸性洗浄剤。 That is, 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.
　前記硫酸イオンの濃度は、０．２５～１．２５ｇ／Ｌであってもよい。 The concentration of the sulfate ion may be 0.25 to 1.25 g / L.
　前記第２鉄イオンの濃度は、０．１～０．５ｇ／Ｌであってもよい。 The concentration of the ferric ion may be 0.1 to 0.5 g / L.
　前記リン酸イオンと前記硫酸イオンとの濃度比は、１０：１～７５：１であってもよい。 The concentration ratio of the phosphate ion to the sulfate ion may be 10: 1 to 75: 1.
　さらに界面活性剤を含んでいてもよい。 Further may contain a surfactant.
　前記界面活性剤の濃度は、０．５～３．０ｇ／Ｌであってもよい。 The concentration of the surfactant may be 0.5 to 3.0 g / L.
　さらに有機スルホン酸を含んでいてもよい。 It may further contain organic sulfonic acid.
　また別の本発明は、上記のアルミニウム系金属材料用酸性洗浄剤を、液温４０～７０℃とし、これをアルミニウム系金属材料の表面に接触させて洗浄する洗浄工程を含む、アルミニウム系金属材料の洗浄方法である。 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.
　前記接触の時間は、１５～６０秒であってもよい。 The contact time may be 15 to 60 seconds.
　本発明のアルミニウム系金属材料用酸性洗浄剤は、アルミニウム系金属材料を低温で洗浄した場合であっても、脱スマット性が良好であるとともに、洗浄後に化成処理を省略してもブラウンスポットの発生を抑制することができる。したがって、その経済的価値は大きい。 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.
　以下、本発明の実施形態について説明する。なお、本発明は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.
　＜アルミニウム系金属材料用酸性洗浄剤＞
　本発明のアルミニウム系金属材料用酸性洗浄剤は、リン酸イオンと、硫酸イオンと、第２鉄イオンとを、必須の成分として含む。そして、リン酸イオンを主成分とし、リン酸イオンと第２鉄イオンとの濃度比が特定範囲となっている。 <Acid cleaning agent for aluminum-based metal materials>
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.
　［リン酸イオン］
　本発明のアルミニウム系金属材料用酸性洗浄剤に含まれるリン酸イオン（ＰＯ４ ３－）は、アルミニウム系金属材料用酸性洗浄剤を構成する成分の中で、主成分となるものである。 [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.
　本発明のアルミニウム系金属材料用酸性洗浄剤は、リン酸イオンと、硫酸イオンと、第２鉄イオンと、を必須の成分として含むが、リン酸イオンの濃度は、硫酸イオンの濃度よりも大きい。 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. ..
　リン酸イオンが主成分であることで、本発明の酸性洗浄剤によって洗浄したアルミニウム系金属材料の表面には、リン系の皮膜を形成することが可能となる。アルミニウム系金属材料の表面をリン系の皮膜が被覆することで、アルミニウムの露出を抑制することができ、水洗水と反応して生じるブラウンスポットを抑制することができる。 Since the main component is phosphate ions, it is possible to form a phosphorus-based film on the surface of the aluminum-based metal material cleaned with the acidic detergent of the present invention. By coating the surface of the aluminum-based metal material with a phosphorus-based film, the exposure of aluminum can be suppressed, and the brown spots generated by reacting with water washing can be suppressed.
　このため、本発明のアルミニウム系金属材料用酸性洗浄剤によれば、従来実施されてきた化成処理による化成処理皮膜の形成工程を省略することが可能となり、洗浄後、そのまま塗装処理に移行して塗装塗膜を形成することができる。したがって、飲料缶等の分野においては、工程省略による経済的効果に大きく貢献することができる。 Therefore, according to 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.
　リン酸イオンの濃度は、１３～２６ｇ／Ｌであり、１８～２３ｇ／Ｌであることが好ましく、１８～２０ｇ／Ｌであることが特に好ましい。 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.
　リン酸イオンの濃度が１５ｇ／Ｌ未満である場合には、スマット除去およびブラウンスポット抑制の効果が十分でなくなる。一方で、リン酸イオンの濃度が２６ｇ／Ｌを超える場合には、過剰にマットが除去されて、ブラウンスポット抑制効果をもつリン系皮膜の形成が阻害される。 If the phosphate ion concentration is less than 15 g / L, the effects of removing smut and suppressing brown spots will be insufficient. On the other hand, when 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.
　また、リン酸イオンと第２鉄イオンとの濃度比は、３５：１～１８０：１であり、９０：１～１１５：１であることが好ましく、９０：１～１００：１であることが特に好ましい。 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.
　リン酸イオンと第２鉄イオンとの濃度比が３５：１～１８０：１の範囲から外れる場合には、スマット除去およびブラウンスポット抑制の効果が十分でなくなる。 When the concentration ratio of phosphate ion and ferric ion is out of the range of 35: 1 to 180: 1, the effect of removing smut and suppressing brown spots becomes insufficient.
　リン酸イオンと硫酸イオンとの濃度比は、１０：１～７５：１であることが好ましく、３０：１～５２：１であることがより好ましく、３６：１～４０：１であることが特に好ましい。 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.
　リン酸イオンと硫酸イオンとの濃度比が１０：１～７５：１の範囲から外れる場合には、スマット除去およびブラウンスポット抑制の効果が十分でなくなる。 When the concentration ratio of phosphate ion and sulfate ion is out of the range of 10: 1 to 75: 1, the effects of removing smut and suppressing brown spots become insufficient.
　本発明のアルミニウム系金属材料用酸性洗浄剤に含まれるリン酸イオンの発生源は、洗浄剤において電離してリン酸イオンを発生することができるものであれば、特に限定されるものではない。例えば、リン酸、ホスホン酸、ピロリン酸、メタリン酸等が挙げられる。本発明において、リン酸イオンの発生源となる物質は、１種のみならず、２種類以上を組み合わせて用いてもよい。 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. For example, phosphoric acid, phosphoric acid, pyrophosphoric acid, metaphosphoric acid and the like can be mentioned. In the present invention, 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.
　これらの中では、工業的に広く適用され食品添加物としても用いられることから、リン酸が好ましい。リン酸は、エッチング促進剤としての機能も発現する。 Among these, 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.
　［硫酸イオン］
　本発明のアルミニウム系金属材料用酸性洗浄剤に、必須の成分として含まれる硫酸イオンは、エッチング促進剤としての機能を有する。 [Sulfate ion]
Sulfate ions 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.
　硫酸イオンの濃度は、０．２５～１．２５ｇ／Ｌであることが好ましく、０．５～１．２５ｇ／Ｌであることがより好ましい。 The concentration of sulfate ion is preferably 0.25 to 1.25 g / L, more preferably 0.5 to 1.25 g / L.
　硫酸イオンの濃度が０．２５ｇ／Ｌ未満である場合には、エッチング速度が低下し、スマット除去の効果が十分でなくなる。一方で、硫酸イオンの濃度が１．２５ｇ／Ｌを超える場合には、エッチングに対してそれ以上の効果が認められなくなり、経済的に不利となる。 If 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. On the other hand, when the concentration of sulfate ions exceeds 1.25 g / L, no further effect is observed on etching, which is economically disadvantageous.
　本発明のアルミニウム系金属材料用酸性洗浄剤に含まれる硫酸イオンの発生源は、洗浄剤において電離して硫酸イオンを発生することができるものであれば、特に限定されるものではない。例えば、硫酸、またはその塩（硫酸鉄、硫酸アルミニウム、硫酸カルシウム、硫酸ナトリウム等）が挙げられる。本発明において、硫酸イオンの発生源となる物質は、１種のみならず、２種類以上を組み合わせて用いてもよい。 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. For example, sulfuric acid or a salt thereof (iron sulfate, aluminum sulfate, calcium sulfate, sodium sulfate, etc.) can be mentioned. In the present invention, 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.
　例えば、本発明のアルミニウム系金属材料用酸性洗浄剤の必須の成分である第２鉄イオンの発生源として、硫酸第２鉄を供給する場合には、第２鉄イオンとともに硫酸イオンが電離することとなる。本発明においては、硫酸第２鉄とともに、別の硫酸イオン発生源を組み合わせて、酸性洗浄剤に含まれる硫酸イオンの濃度を調製することができる。 For example, 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. In the present invention, the concentration of sulfate ion contained in the acidic detergent can be adjusted by combining ferric sulfate and another sulfate ion source.
　硫酸イオンの発生源としては、工業的に広く適用され経済性にも優れることから、硫酸が特に好ましい。 Sulfuric acid is particularly preferable as a source of sulfate ions because it is widely applied industrially and has excellent economic efficiency.
　［第２鉄イオン］
　本発明のアルミニウム系金属材料用酸性洗浄剤に、必須の成分として含まれる第２鉄イオンは、エッチング促進剤としての機能を有する。 [Ferric ion]
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.
　通常、酸性洗浄剤におけるアルミニウム系金属のエッチング反応は、アルミニウムがアルミニウムイオン（Ａｌ３＋）となるアノード反応と、酸性洗浄剤におけるＨ＋が還元されて１／２Ｈ２となるカソード反応とからなる。このため、酸性洗浄剤中に、酸化型金属イオンである第二鉄イオン（Ｆｅ３＋）が存在していると、このＦｅ３＋がＦｅ２＋に還元されるアノード反応が、前記Ｈ＋の還元と同時に起こり、アルミニウムのエッチング反応が促進される。 Usually, 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.
　第２鉄イオンの濃度は、０．１～０．５ｇ／Ｌであることが好ましく、０．２～０．５ｇ／Ｌであることがより好ましい。 The concentration of ferric ion is preferably 0.1 to 0.5 g / L, more preferably 0.2 to 0.5 g / L.
　第２鉄イオンの濃度が０．１ｇ／Ｌ未満である場合には、エッチング速度が低下し、スマット除去の効果が十分でなくなる。一方で、第２鉄イオンの濃度が０．５ｇ／Ｌを超える場合には、エッチングに対してそれ以上の効果が認められなくなり、経済的に不利となる。 If 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.
　本発明のアルミニウム系金属材料用酸性洗浄剤に含まれる第２鉄イオンの発生源は、洗浄剤において電離して第２鉄イオンを発生することができるものであれば、特に限定されるものではない。 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.
　なかでは、硫酸塩または硝酸塩のような水溶性塩で供給されることが好ましいため、第２鉄イオンは、硫酸第２鉄または硝酸第２鉄として供給されることが好ましい。硫酸第２鉄として供給される場合には、第２鉄イオンとともに硫酸イオンが電離し、硝酸第２鉄として供給される場合には、第２鉄イオンとともに硝酸イオンが電離する。 Among them, it is preferable that 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. When supplied as ferric sulfate, 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.
　なお、エッチング反応が進行するにつれて第１鉄イオン（Ｆｅ２＋）濃度が増大するため、酸化還元電位（以下、ＯＲＰ：ｏｘｉｄａｔｉｏｎ－ｒｅｄｕｃｔｉｏｎ　ｐｏｔｅｎｔｉａｌという）が低下し（洗浄剤の老化ともいう）、アルミニウム表面のエッチング促進効果が消失してしまう。そこで、ＯＲＰをコントロールする酸化剤を随時添加、または当初から添加して、第１鉄イオンを第２鉄イオンに酸化してもよい。 As the etching reaction progresses, the concentration of ferrous ions (Fe 2+ ) increases, so the redox potential (hereinafter referred to as ORP: oxidation-reduction potential) decreases (also referred to as aging of the cleaning agent), and the aluminum surface. The effect of promoting etching is lost. Therefore, an oxidizing agent that controls ORP may be added at any time, or may be added from the beginning to oxidize ferric ions to ferric ions.
　［その他の成分］
　本発明のアルミニウム系金属材料用酸性洗浄剤には、必須成分となる、リン酸イオンと、硫酸イオンと、第２鉄イオン以外に、任意に、他の成分が配合されていてもよい。例えば、界面活性剤、有機スルホン酸等が挙げられる。 [Other ingredients]
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. For example, surfactants, organic sulfonic acids and the like can be mentioned.
　（界面活性剤）
　界面活性剤は、主として、アルミニウム系金属材料の表面に付着していた油脂成分を除去するために配合される。特に、ＤＩ加工後のアルミニウム缶に対しては、潤滑剤を除去する役割を担う。 (Surfactant)
The surfactant is mainly added to remove the oil and fat component adhering to the surface of the aluminum-based metal material. In particular, for aluminum cans after DI processing, it plays a role of removing the lubricant.
　また、界面活性剤は、除去した油脂成分や潤滑剤成分が、洗浄剤中で浮遊することを防止する。油脂成分や潤滑剤成分が洗浄剤中に浮遊している場合には、アルミニウム系金属材料の表面に再吸着するおそれがあるが、界面活性剤を配合することにより、これを回避できる。 In addition, the surfactant prevents the removed oil and fat components and lubricant components from floating in the cleaning agent. When 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.
　界面活性剤の種類としては、特に限定されるものではなく、ノニオン系、カチオン系、アニオン系、両性イオン系のいずれも用いうる。なかでは、ノニオン系が好ましく、例えばエトキシ化アルキルフェノール系、炭酸水素誘導体、アビエチン酸誘導体、第１級エトキシ化アルコール、変性ポリエトキシ化アルコール等が好ましく用いられる。 The type of surfactant is not particularly limited, and any of nonionic, cationic, anionic, and zwitterionic surfactants can be used. Among them, 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.
　界面活性剤の濃度は、０．５～３．０ｇ／Ｌであることが好ましく、１．０～２．５ｇ／Ｌであることがより好ましく、１．５～２．０ｇ／Ｌであることが特に好ましい。 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.
　界面活性剤の濃度が０．５ｇ／Ｌ未満である場合には、洗浄性、特に脱脂性が低下する。一方で、界面活性剤の濃度が３．０ｇ／Ｌを超える場合には、洗浄剤中で発泡して洗浄処理が困難となるうえ、廃水処理に負荷がかかる。 When the concentration of the surfactant is less than 0.5 g / L, the detergency, especially the degreasing property, is lowered. On the other hand, when 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.
　（有機スルホン酸）
　有機スルホン酸は、主として、低温条件下においても十分なエッチング効果を発揮させるために配合される。 (Organic sulfonic acid)
The organic sulfonic acid is mainly blended in order to exert a sufficient etching effect even under low temperature conditions.
　有機スルホン酸は、下記の式（１）で表される構造を有する。
　［化１］
　　　Ｒ－ＳＯ３Ｈ　　　・・・（１）
（式中、のＲは、メチル基、または、炭素数が１～９であって少なくとも１以上の水酸基を有する置換アルキル基を示す。） 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.)
　上記式（１）中の置換アルキル基は、直鎖に限られず、分岐鎖であってもよい。上記有機スルホン酸の具体例としては、ＨＳＯ３－ＣＨ３の他、ＨＳＯ３－ＣＨ２ＯＨ、ＨＳＯ３－ＣＨ２ＣＨ２ＯＨ、ＨＳＯ３－ＣＨ２ＣＨ２ＣＨ２ＯＨ、ＨＳＯ３－ＣＨ２ＣＨ（ＯＨ）ＣＨ２ＯＨ等が挙げられる。有機スルホン酸は、単独で使用しても、２種類以上を併用して用いてもよい。 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.
　有機スルホン酸の含有量は、０．０１ｇ／Ｌ～０．２ｇ／Ｌであることが好ましい。含有量が０．０１ｇ／Ｌ未満では、効果が不十分となり、０．２ｇ／Ｌを超える場合には、それ以上の効果が認められなくなり、経済的に不利となる。 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.
　＜アルミニウム系金属材料の洗浄方法＞
　本発明のアルミニウム系金属材料の洗浄方法は、上記した本発明のアルミニウム系金属材料用酸性洗浄剤を、液温５０～６０℃とし、これをアルミニウム系金属材料の表面に接触させて洗浄する洗浄工程を含むものである。洗浄工程を含んでいれば、他の工程を任意に含んでいてもよい。 <How to clean aluminum-based metal materials>
In the method for cleaning an aluminum-based metal material of the present invention, 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.
　アルミニウム系金属材料に酸性洗浄剤を接触させる方法としては、特に限定されるものではなく、本分野で公知の方法を適宜選択することができる。例えば、スプレー法または浸漬法が挙げられる。 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.
　本発明のアルミニウム系金属材料の洗浄方法は、酸性洗浄剤の液温４０～７０℃として用いる。すなわち、従来の洗浄方法と比較して、低温で洗浄することが可能となる。より好ましい処理温度は４０～６０℃であり、４０～５０℃が最も好ましい。 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.
　アルミニウム系金属材料に酸性洗浄剤を接触させる時間は、十分にエッチングが可能であり、また、アルミニウム系金属材料の表面に均一なリン系の皮膜が形成できる時間であれば、特に限定されるものではない。処理温度に応じて適宜設定することができる。 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.
　例えば、酸性洗浄剤の液温を５０～６０℃として用いる場合には、接触の時間は、１５～６０秒とすることが好ましい。さらに好ましくは２５～４５秒であり、２５～４５秒が最も好ましい。 For example, when the liquid temperature of the acidic detergent is set to 50 to 60 ° C., the contact time is preferably 15 to 60 seconds. More preferably, it is 25 to 45 seconds, and most preferably 25 to 45 seconds.
　以下に、実施例等に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail based on Examples and the like, but the present invention is not limited to these Examples.
　＜材料＞
　実施例および比較例で用いた材料を、以下に示す。
　［リン酸イオン発生源］
　　リン酸（コープケミカル社製、商品名：７５％リン酸）
　［硫酸イオン発生源］
　　硫酸（三菱マテリアル社製、商品名：希硫酸）
　［第２鉄イオン発生源］
　　硫酸第二鉄（十條合成化学 研究所社製、商品名：硫酸第二鉄液）
　［有機スルホン酸］
　　メタンスルホン酸（ＢＡＳＦジャパン社製、商品名：Ｌｕｔｒｏｐｕｒ　ＭＳＡ）
　［界面活性剤］
　　ポリオキシアルキレンエーテル（ADEKA社製、商品名：アデカノールＬＧ２９４） <Material>
The materials used in the examples and comparative examples are shown below.
[Phosphate ion source]
Phosphoric acid (manufactured by CO-OP CHEMICAL, Inc., trade name: 75% phosphoric acid)
[Sulfate ion source]
Sulfuric acid (manufactured by Mitsubishi Materials, trade name: dilute sulfuric acid)
[Ferric ion source]
Ferric sulfate (manufactured by Tojo Synthetic Chemistry Laboratory, trade name: ferric sulfate solution)
[Organic sulfonic acid]
Methanesulfonic acid (manufactured by BASF Japan, trade name: Lutropur MSA)
[Surfactant]
Polyoxyalkylene ether (manufactured by ADEKA, trade name: Adecanol LG294)
　＜実施例１～１６、比較例１～２０＞
　［塗料組成物の調製］
　表１および表２に示す濃度となるように各材料を混合して、実施例および比較例のアルミニウム系金属材料用酸性洗浄剤を調製した。 <Examples 1 to 16, Comparative Examples 1 to 20>
[Preparation of paint composition]
Each material was mixed so as to have the concentrations shown in Tables 1 and 2, and acidic detergents for aluminum-based metal materials of Examples and Comparative Examples were prepared.
　具体的には、工業用水に対し、表１および表２に示す濃度となるよう各材料を混合して撹拌した。このとき、活性剤に限っては、各材料混合後、最後に添加した。アルミニウム系金属材料用酸性洗浄剤を調製後は、所定の処理条件となるまで昇温した。 Specifically, 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.
　［アルミニウム系金属材料の処理］
　３１０４合金のアルミニウム板をＤＩ加工して得られた、潤滑油とスマットが付着した蓋なし容器を準備した。準備した蓋無し容器に対して、実施例および比較例で得られたアルミニウム系金属材料用酸性洗浄剤を用いて、表１および表２に示す処理条件にて、スプレー処理した。 [Treatment of aluminum-based metal materials]
A lidless container to which lubricating oil and smut were attached, which was obtained by DI processing an aluminum plate of 3104 alloy, was prepared. 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.
　次いで、１５秒間水道水で洗浄し、続いて５秒間脱イオン水でスプレー水洗し、１９５℃で３分間乾燥させた。 Next, it was washed with tap water for 15 seconds, then sprayed with deionized water for 5 seconds, and dried at 195 ° C. for 3 minutes.
　＜評価＞
　乾燥後、得られた各容器について、以下の評価を実施した。 <Evaluation>
After drying, the following evaluations were carried out for each of the obtained containers.
　［脱スマット性］
　乾燥後の容器内面に、透明粘着テープを密着し、これを剥離して白色台紙上に貼り付けた。同様に、剥離操作をしていないテープを、白色台紙上に貼り付けた。その後、テープ張り付け面の白さについて、剥離操作を実施したテープと、剥離操作をしていないテープとで比較した。具体的には、テープ張り付け面の汚染（付着物の有無、または黒変）の程度に応じて、以下の１０段階で評価した。
　　　５　　　汚染なし
　　　４．５　目視発見困難な汚染
　　　４　　　痕跡程度の汚染
　　　３．５　僅かな汚染
　　　３　　　軽微な汚染
　　　２．５　２点より軽度な汚染
　　　２　　　中程度の汚染
　　　１．５　１点より軽度な汚染
　　　１　　　多大な汚染
　　　０　　　全面に付着物または汚染 [De-smut property]
A transparent adhesive tape was adhered to the inner surface of the container after drying, which was peeled off and attached on a white mount. Similarly, a tape that had not been peeled off was attached onto the white mount. After that, the whiteness of the tape-attached surface was compared between the tape subjected to the peeling operation and the tape not subjected to the peeling operation. Specifically, it was evaluated in the following 10 stages according to the degree of contamination (presence or absence of deposits or blackening) on the tape-attached surface.
5 No pollution 4.5 Hard-to-find pollution 4 Trace pollution 3.5 Slight pollution 3 Minor pollution 2.5 Lighter pollution than 2 points 2 Moderate pollution 1.5 Lighter pollution than 1 point 1 Heavy pollution 0 Adhesion or contamination on the entire surface
　［ブラウンスポット発生有無］
　工業用水５．０ｍＬを、処理後の缶底部（ドーム部）中心にスポイトで滴下し、１９５℃、３分間熱風乾燥炉で乾燥させた後、ドーム部の変色発生数の割合を目視で確認した。評価基準を、以下に示す。評価数は１００缶とし、変色発生数の割合を確認した。
　　　４　　発生なし
　　　３　　処理数の１．０％未満発生
　　　２　　処理数の５．０％未満発生
　　　１　　処理数の５．０％以上発生 [Presence / absence of brown spot]
5.0 mL of industrial water was dropped onto the center of the bottom (dome) of the treated can with a dropper, dried in a hot air drying oven at 195 ° C. for 3 minutes, and then the ratio of the number of discolorations in the dome was visually confirmed. .. The evaluation criteria are shown below. The number of evaluations was 100 cans, and the ratio of the number of discolorations was confirmed.
4 No occurrence 3 Less than 1.0% of the number of treatments 2 Less than 5.0% of the number of treatments 1 More than 5.0% of the number of treatments
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (9)

  1. 　リン酸イオンと、硫酸イオンと、第２鉄イオンと、を含むアルミニウム系金属材料用酸性洗浄剤であって、
    　前記リン酸イオンの濃度は、１３～２６ｇ／Ｌであり、
    　前記リン酸イオンの濃度は、前記硫酸イオンの濃度よりも大きく、
    　前記リン酸イオンと前記第２鉄イオンとの濃度比は、３５：１～１８０：１である、
    アルミニウム系金属材料用酸性洗浄剤。     An acidic detergent for aluminum-based metal materials containing phosphate ions, sulfate ions, and ferric ions.
    The concentration of the phosphate ion is 13 to 26 g / L, and the concentration is 13 to 26 g / L.
    The concentration of the phosphate ion is higher than the concentration of the sulfate ion,
    The concentration ratio of the phosphate ion to the ferric ion is 35: 1 to 180: 1.
    Acidic cleaning agent for aluminum-based metal materials.
  2. 　前記硫酸イオンの濃度は、０．２５～１．２５ｇ／Ｌである、請求項１に記載のアルミニウム系金属材料用酸性洗浄剤。 The acidic detergent for aluminum-based metal materials according to claim 1, wherein the concentration of the sulfate ion is 0.25 to 1.25 g / L.
  3. 　前記第２鉄イオンの濃度は、０．１～０．５ｇ／Ｌである、請求項１または２に記載のアルミニウム系金属材料用酸性洗浄剤。 The acidic detergent for aluminum-based metal materials according to claim 1 or 2, wherein the concentration of the ferric ion is 0.1 to 0.5 g / L.
  4. 　前記リン酸イオンと前記硫酸イオンとの濃度比は、１０：１～７５：１である、請求項１から３いずれかに記載のアルミニウム系金属材料用酸性洗浄剤。 The acidic detergent for aluminum-based metal materials according to any one of claims 1 to 3, wherein the concentration ratio of the phosphate ion to the sulfate ion is 10: 1 to 75: 1.
  5. 　さらに界面活性剤を含む、請求項１から４いずれかに記載のアルミニウム系金属材料用酸性洗浄剤。 The acidic detergent for aluminum-based metal materials according to any one of claims 1 to 4, further comprising a surfactant.
  6. 　前記界面活性剤の濃度は、０．５～３．０ｇ／Ｌである、請求項５に記載のアルミニウム系金属材料用酸性洗浄剤。 The acidic detergent for aluminum-based metal materials according to claim 5, wherein the concentration of the surfactant is 0.5 to 3.0 g / L.
  7. 　さらに有機スルホン酸を含む、請求項１から６いずれかに記載のアルミニウム系金属材料用酸性洗浄剤。 The acidic detergent for aluminum-based metal materials according to any one of claims 1 to 6, further containing an organic sulfonic acid.
  8. 　請求項１～７いずれかに記載のアルミニウム系金属材料用酸性洗浄剤を、液温４０～７０℃とし、これをアルミニウム系金属材料の表面に接触させて洗浄する洗浄工程を含む、アルミニウム系金属材料の洗浄方法。 The aluminum-based metal according to any one of claims 1 to 7, which comprises a cleaning step in which the acidic cleaning agent for an aluminum-based metal material has a liquid temperature of 40 to 70 ° C. and is brought into contact with the surface of the aluminum-based metal material for cleaning. How to clean the material.
  9. 　前記接触の時間は、１５～６０秒である、請求項８に記載のアルミニウム系金属材料の洗浄方法。 The method for cleaning an aluminum-based metal material according to claim 8, wherein the contact time is 15 to 60 seconds.
PCT/JP2020/047674 2019-12-27 2020-12-21 Acidic cleaning agent for aluminum-based metal materials, and method for cleaning aluminum-based metal material WO2021132154A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0273983A (en) * 1988-09-07 1990-03-13 Nippon Parkerizing Co Ltd Acidic washing solution for aluminum
JP2007197775A (en) * 2006-01-26 2007-08-09 Nippon Paint Co Ltd Acidic cleaning agent for aluminum based metallic material and cleaning method therefor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0273983A (en) * 1988-09-07 1990-03-13 Nippon Parkerizing Co Ltd Acidic washing solution for aluminum
JP2007197775A (en) * 2006-01-26 2007-08-09 Nippon Paint Co Ltd Acidic cleaning agent for aluminum based metallic material and cleaning method therefor

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