CN1170443A - Aqueous acid cleaning solution for aluminum metal and method for cleaning the metal - Google Patents
Aqueous acid cleaning solution for aluminum metal and method for cleaning the metal Download PDFInfo
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- CN1170443A CN1170443A CN95196828A CN95196828A CN1170443A CN 1170443 A CN1170443 A CN 1170443A CN 95196828 A CN95196828 A CN 95196828A CN 95196828 A CN95196828 A CN 95196828A CN 1170443 A CN1170443 A CN 1170443A
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- 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
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- 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
- C23G1/125—Light metals aluminium
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- 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
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Detergent Compositions (AREA)
Abstract
An aqueous acid cleaning solution for aluminum metals and a washing method thereof are provided. The acid cleaning solution contains oxidized metal ions as an etching accelerator and does not contain hazardous fluorine and chromium ions. The solution contains an inorganic acid, oxidized metal ions, a chelate dispersant, if necessary a surfactant, and further an oxidizing agent for the metal ions reduced by cleaning. The chelate dispersant in the acid cleaning solution has the effect of inhibiting the formation of a sludge from the oxidized metal, thus permitting the preparation of a sludge-free aqueous acid cleaning solution.
Description
Technical Field
The present invention relates to an aqueous acid cleaning solution for aluminum-based metals and a method for cleaning the same, and more particularly to an aqueous acid cleaning solution and a method for cleaning the same, which are capable of satisfactorily removing lubricating oil, aluminum powder, and the like adhering to the surface of aluminum during molding.
Background
Products having an aluminum surface are generally produced by a forming operation called press forming and ironing (hereinafter, called DI processing) using, for example, an aluminum container for beverages made of aluminum-based metal, i.e., aluminum or an aluminum alloy. In this molding operation, a lubricant is applied to the metal surface, and the resulting container has aluminum powder (dirt) adhered to the inner wall thereof. Such containers are generally protected on their surface after this by, for example, chemical conversion treatment or painting. Therefore, before the chemical conversion treatment or the like, the above lubricating oil or dirt must be removed from the metal surface to be purified.
In this surface cleaning, a pickling agent is generally used which washes the metal surface by moderately corroding the metal surface. As such a pickling agent, a detergent of chromic acid type or hydrofluoric acid type has been frequently used. In particular, a hydrofluoric acid-based detergent is excellent in that it can be acid-washed at a low temperature (about 50 ℃ C.). However, since the above-mentioned detergents are harmful substances and strict wastewater discharge regulations, development of a chromium-free and fluorine-free low-temperature pickling technique has been desired in recent years.
Such a chromium-free and fluorine-free pickling technique is proposed in Japanese patent publication No. Hei 3-50838 "aluminum surface detergent" and Japanese patent publication No. Hei 3-65436 "method for controlling aluminum surface detergent".
Japanese patent publication No. Hei 3-50838 "aluminum surface detergent" and Japanese patent publication No. Hei 3-65436 "method for controlling aluminum surface detergent" disclose a detergent containing iron ions as a corrosion accelerator in place of fluorine ions in an acid cleaning agent containing no or a small amount of fluorine ions and having a pH of 2 or less adjusted with sulfuric acid and/or nitric acid, and a method for controlling the oxidation-reduction potential of a cleaning bath and further controlling the concentration of iron ions in the bath.
In the usual case of the use of a magnetic tape,the corrosion reaction of aluminum in the pickling solution changes aluminum into aluminum ions (Al)3+) And H in the washing solution+Is reduced to 1/2H2The negative electrode reaction composition (1). Therefore, if iron (Fe) is added to the pickling solution3+) Then the Fe is added3+Reduction to Fe2+The positive electrode reaction of (2) with the above-mentioned H+The reduction of (a) takes place simultaneously, thus promoting the corrosion reaction of the aluminium.
In addition, the oxidation-reduction potential of the washing bath and thus in the washing bath is controlled by the oxidizing agentIron ion concentration, thereby performing corrosion reaction of aluminum, for which increased Fe can be suppressed2+And the concentration of Fe can be adjusted2+Is oxidized into Fe3+。
However, since the pickling agents disclosed in the above-mentioned Japanese patent publication No. Hei 3-50838 and Japanese patent publication No. Hei 3-65436 contain iron ions, when an acidic aqueous solution is diluted, precipitates (sludge) of iron ions, particularly hydroxides, are generated. Further, in the pre-washing step which is a pre-treatment step in the washing method, sludge adheres to the heating part of the water tank, which is a problem.
Disclosure of the invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide an aqueous acid cleaning solution for aluminum-based metals, which contains oxidized metal ions as a corrosion promoter but does not contain harmful fluorine ions and chromium ions, and a method for cleaning the same.
To achieve the above object, the aqueous aluminum-based metal pickling solution of the present invention is characterized by containing an inorganic acid in an amount capable of lowering the pH to 2, an oxidized metal ion and a chelating dispersant.
The aqueous aluminum-based metal pickling solution of the present invention is characterized by containing an inorganic acid, an oxidized metal ion, a surfactant and a chelating dispersant in such amounts that the pH can be lowered to 2 or lower.
The present invention also provides a method for washing an aluminum surface, comprising using an aqueous aluminum metal washing solution containing at least one inorganic acid selected from the group consisting of inorganic acids having a pH of less than 2, an oxidized metal ion, a chelate-fractional agent, and a surfactant according to the requirement for degreasing, supplying the "oxidized metal ion and an oxidizing agent" or the "oxidizing agent" to the aqueous aluminum metal washing solution, and measuring the redox potential of the aqueous solution to maintain and control the concentration of the oxidized metal ion in the aqueous aluminum metal washing solution.
The aqueous acid cleaning solution may be used as it is as a cleaning bath for cleaning an aluminum-based metal material, but may be obtained by diluting a concentrated aqueous solution of the aqueous acid cleaning solution with an appropriate amount of water to a concentration within a use range.
First, sulfuric acid and nitric acid are examples of the inorganic acid.
Examples of the oxidizing metal ion include iron ion (Fe)3+) Metavanadate ion (VO)3 -) Cerium ion (Ce)4+) Cobalt ion (Co)5+) Tin ion (Sn)4+) And the like. Preferably iron ion (Fe)3+) Metavanadate ion (VO)3 -). When the metal has a plurality of valences, the oxidized metal ion refers to a metal ion having a higher valence.
Examples of the iron ion supply source include water-soluble iron salts such as iron sulfate, iron nitrate, and iron perchlorate. Examples of the source of metavanadate ions include sodium metavanadate, potassium metavanadate, and ammonium metavanadate. Examples of the source of cerium ions include ammonium cerium sulfate. Examples of the source of cobalt ions include cobalt sulfate and cobalt ammonium sulfate. Examples of the source of the tin ions include tin sulfate and tin nitrate.
The chelating dispersant used in the present invention is a compound which can form a chelate with an oxidant metal ion, stabilize an oxidative metal ion in a strongly acidic aqueous solution, and improve the dispersibility of the oxidative metal ion in the strongly acidic aqueous solution. Preference is given to using phosphonic acid compounds. As the preferable phosphonic acid compound, 1-hydroxyethylidene-1, 1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), and the like can be used.
As the surfactant, any of nonionic, cationic, anionic and zwitterionic surfactants used in the past can be used. Among them, nonionic types such as ethoxylated alkylphenols, hydrocarbon derivatives, rosin acid derivatives, ethoxylated primary alcohols, modified polyethoxylated alcohols and the like are particularly preferable.
In addition, as the decomposition inhibitor of the surfactant, bromide ion and/or polyhydric alcohol are preferably added.
Examples of the bromide ion supply source include 47% aqueous HBr, potassium bromide, sodium bromide, ammonium bromide, and iron bromide.
The polyhydric alcohol is preferably an alcohol in which at least 2 hydroxyl groups are bonded to adjacent carbon atoms in the main chain in 1 molecule, and examples thereof include 1, 2-ethylene glycol (ethylene glycol), 1, 2-propylene glycol (propylene glycol), 1, 2-pentanediol, 1, 2-butanediol, 1, 2-glycerol (glycerol) as a dihydric alcohol, 1, 2, 3-glycerol (glycerol), 1, 2, 4-butanetriol as a trihydric alcohol, and 1, 2, 3, 4-butanetetraol as a tetrahydric alcohol.
In general, when iron ions are used as the oxidized metal ions as the washing proceeds and the time elapses, the iron ions are as follows To become ferrous ions, the redox potential decreases (known as bath aging), and the corrosion-promoting effect is no longer present on the aluminum surface. For the metavanadate ion, the washing bath is likewise aged with time. In this case, when iron ions are used as the oxidized metal ions, iron ions can be supplied as needed, and an ORP control oxidizing agent can be added as needed to oxidize ferrous ions into iron ions. Examples of the ORP-controlling oxidizing agent in this case include an oxidizing agent capable of generating hydrogen peroxide (H)2O2) Persulfates (e.g., NaS)2O8 2-) Ozone (O)3) Cerium compounds (e.g., cerium ammonium sulfate: (NH)4)4Ce(SO4)4) Nitrite (e.g., NaNO)2、KNO2) Metavanadate ion (VO)3 -) And the like. Further, such an oxidizing agent is disclosed in Japanese patent publication No. Hei 3-65436. The ORP is referred to as oxidation-reduction potential (ORP).
The aqueous acid washing solution of the present invention using an inorganic acid is preferably adjusted to a pH of 2 or less. More preferably, the pH of the aqueous acid washing solution is 0.6 to 2. If the pH exceeds 2, the corrosion rate of the aluminum surface is extremely low, and the effectiveness of the cleaning bath is difficult to be exhibited. On the other hand, if the pH is less than 0.6, the economy is poor, and the amount of chemical conversion carried over to the next step is increased, which causes a chemical conversion failure.
The content of the oxidized metal ion in the aqueous acid washing solution is preferably 0.05 to 4g/L, more preferably 0.2 to 2 g/L. When the content of the oxidized metal ion is less than 0.05g/L, the amount of corrosion is insufficient and the desmutting properties tend to be lowered. On the other hand, when the content exceeds 4g/L, the detergency is not poor but it is not economical.
The chelating dispersant is preferably contained in the acidic aqueous solution in an amount of 0.05 to 5g/L, more preferably 0.1 to 2 g/L. If the amount is less than 0.05g/L, chelation is insufficient, and hydroxide of the oxidized metal is formed, resulting in precipitation (sludge) in the aqueous solution. Further, a hydroxide of an oxidized metal ion is fixed to the heating portion in the preliminary washing step. When the washing method of the present invention is carriedout in a shower manner, clogging of the spray valve and nozzle hole occurs. When the amount exceeds 5g/L, the chelate dispersibility is not poor, but it is uneconomical.
The surfactant is preferably contained in the pickling aqueous solution in an amount of 0.1 to 10g/L, more preferably 0.5 to 2 g/L. When the content of the surfactant is less than 0.1g/L, detergency, particularly degreasing properties tend to be lowered. On the other hand, when the content exceeds 10g/L, the detergency is not poor but it is not economical.
The amount of bromide ions in the aqueous acid washing solution is preferably 0.002 to 0.1 g/L. When the content of bromide ion is less than 0.002g/L, the effect of the surfactant for inhibiting the oxidative decomposition reaction tends to be low, and even if it exceeds 0.1g/L, no more excellent effect is obtained in inhibiting the oxidative decomposition reaction of the surfactant.
1 polyol having at least 2 hydroxyl groups in its molecule bonded to adjacent carbon atoms in the main chain, preferably 0.1 to 5g/L, more preferably 0.2 to 3g/L in the acid washing aqueous solution. When the content of the polyol having the above structure is less than 0.1g/L, the effect of suppressing the decomposition reaction tends to be insufficient. On the other hand, when the content exceeds 5g/L, the detergency is not poor but it is not economical, and the load of wastewater treatment is increased due to the increase of the concentration of the polyhydric alcohol.
The oxidation-reduction potential (ORP) of the pickling bath is preferably controlled to be 0.5-0.8V (reference Ag/AgCl). When the pickling bath is less than 0.5V, the amount of oxidized metal ions is insufficient, and the amount of corrosion on the aluminum surface tends to decrease. On the other hand, if it exceeds 0.8V, the economical efficiency is poor. More preferably 0.55 to 0.7 (reference Ag/AgCl).
In the acid bath, if only new metal ions are supplied when iron ions are used as oxidized metal ionsFresh iron ion (Fe)3+) Then ferrous ion (Fe)2+) As a result, the acid bath is muddy and precipitates are formed by ferrous ions, which deteriorates the handling property of the treatment. Further, the iron ions are carried into the next step of the treatment object such as the aluminum can taken out from the pickling bath, and the precipitation is generated in the next step, thereby adversely affecting the chemical conversion treatment. Therefore, if the "oxidized metal ion and the oxidizing agent" or the "oxidizing agent" are replenished, the above-mentioned problem can be solved if the oxidation-reduction potential (ORP) is maintained and controlled within the above-mentioned range.
The method for pickling the surface of aluminum of the present invention may be any of a spray method and a dipping method. In addition, the treatment temperature is preferably 35 to 80 ℃ and more preferably 50 to 70 ℃ when pickling is performed. If the treatment temperature exceeds 80 ℃, the corrosion is excessive and the treatment bath is aged in advance, and if the temperature is lower than 35 ℃, the corrosion amount is insufficient and the decontamination properties are deteriorated.
The pickling treatment time is preferably 30 to 300 seconds. If the treatment time exceeds 300 seconds, the corrosion is excessive and the treatment bath is aged early, and if the treatment time is less than 30 seconds, the corrosion amount is insufficient and the desmutting property is deteriorated. More preferably 45 to 120 seconds.
The aluminum surface washed with the pickling agent of the present invention may be subjected to, for example, a phosphate chemical conversion treatment after being washed with water according to a conventional method.
According to the present invention, particularly, by using a chelate dispersant, a chelate is formed in an acidic aqueous solution by an oxidized metal ion and a chelate stabilizer, and the dispersibility of the oxidized metal ion in the acidic aqueous solution is improved, whereby the occurrence of hydroxide precipitation (sludge) of the oxidized metal ion can be prevented. Thus, sludge is not generated, and a satisfactory cleaning effect of the surface of the aluminum-based metal can be achieved.
Best mode for carrying out the invention
The present invention will be specifically described below with reference to examples and comparative examples. Examples 1 to 16 and comparative examples 1 to 4
(1) The processed object is:
a no-lid container to which lubricating oil and dirt adhere, which is obtained by subjecting an aluminum plate of 3004 alloy to DI processing.
(2) A detergent:
the aqueous acid pickling solutions were used in the amounts described in the examples and comparative examples shown in table 1 below.
(3) The treatment conditions are as follows:
the container is treated by spraying various detergents at 70-75 ℃ for 60 seconds, then is sprayed and washed by tap water for 15 seconds, then is sprayed and washed by deionized water for 5 seconds, and is dried at 95 ℃.
(4) Evaluation of detergency:
the following items were tested. The results are shown in tables 1 and 2.
(a) Appearance:
the color of the dried container was visually checked. The degree of whitening was evaluated on the basis of the following 5 grades, assuming that the appearance was good when the degreased and decontaminated matter was complete and had a sufficiently corroded white appearance.
◎ all are white
○ part is light gray
△ light gray overall
X: part being grey
X: all being grey
(b) Water wettability:
the container after the spray water washing was shaken 3 times to remove water, and after the container was left standing for 30 seconds while facing upward, the water-wet area (%) of the outer surface of the container was measured.
(c) Decontamination property:
a transparent adhesive tape was adhered to the inner surface of the dried container, and then peeled off and adhered to a white table cloth, and the white color of the surface to which the adhesive tape was adhered was compared with the other portions of the table cloth. The results were evaluated on the following 5 grades depending on the degree of contamination, as good as the case of completely removing the contamination without causing contamination.
5: no pollution
4: trace amount of pollution
3: micro-pollution
2: moderate pollution
1: massive pollution
(5) Sludge prevention:
the detergent used for evaluation of detergency was diluted 20 times with water, heated by an electric heater (60 ℃ C., 1 day), and evaluated for sludge fixation state at the electric heater portion on a 3-stage basis.
3: no sludge fixation
2: only a little sludge fixation
1: the sludge is fully fixed
The evaluation results are shown below. The acid bath base was 75% sulfuric acid, 67.5% nitric acid, and iron (Fe)3+) From 41% iron (Fe) sulfate2(SO4)3) Supply of Ce4+From cerium sulphate (Ce (SO)4)2) And (4) supplying.TABLE 1
Nonionic pH of inorganic acid oxidized metal chelating dispersant
Metal ion surfactant
H2SO4HNO3Fe3+Ce4+Kind of kind
(g/l) (g/l) (g/l) (g/l) example 112.5-1.0-A1.0- - -0.9212.5-1.0-B1.0- - -0.9312.5-1.0-A1.0-1.0 ①*11.0 ②*21.0 0.9 4 12.5 - 1.0 - B 1.0 ① 1.0 ② 1.0 0.9 5 12.5 - 1.0 - C 1.0 ① 1.0 ② 1.0 0.9 6 - 12.5 1.0 - A 1.0 ① 1.0 ② 1.0 0.9 7 10.0 2.5 1.0 - A 1.0 ① 1.0 ② 1.0 0.9 8 12.5 - 0.2 - A 1.0 ① 1.0 ② 1.0 0.9 9 12.5 - 0.2 - A 0.1 ① 1.0 ② 1.0 0.9 10 12.5 - 1.0 - A 1.0 ③*31.0 ② 1.0 0.9 11 5.0 - 1.0 - A 1.0 ① 1.0 ② 1.0 1.8 12 12.5 - 1.0 - A 1.0 ① 0.25 ② 0.25 0.9 13 12.5 - 4.0 - A 5.0 ① 1.0 ② 1.0 0.9 14 12.5 - 1.0 - A 0.5 ① 1.0 ② 1.0 0.9
B0.51512.5-0.05-A0.05 ① 1.0 ② 1.00.91610.02.5-1.0A 1.0 ① 1.0.0 1.0 ② 1.00.9 comparative example 112.5-1.0- - -0.9212.5-1.0- - - ① 1.0 ② 1.00.9312.5-0.2- - - ① 1.0.0 1.0 ② 1.00.943.0-1.0- - - ① 1.0.0 1.0 ② 1.02.5
Note)*Nonyl phenol EO adduct (①)
*Hydrocarbon derivative (②)
*3 rosin acid derivative (③)
*4: a … 1-hydroxyethylidene-1, 1-diphosphonic acid
B … Aminotris (methylenephosphonic acid)
C … ethylenediaminetetraacetic acid (methylene phosphonic acid)
In example 14 of table 1, 2 chelating dispersants were used. TABLE 2
Evaluation results
Preventive detergency against sludge
(%) appearance Water wetting decontamination Properties
(%) examples
1 3 ○ 80 4
2 3 ○ 80 4
3 3 ◎ 100 5
4 3 ◎ 100 5
5 3 ◎ 100 5
6 3 ◎ 100 5
7 3 ◎ 100 5
8 3 ○ 100 4
9 3 ○ 100 4
10 3 ◎ 100 5
11 3 ○ 100 5
12 3 ◎ 100 5
13 3 ◎ 100 5
14 3 ◎ 100 5
15 3 ○ 100 4
163 ◎ 1005 comparative example
1 1 △ 0 1
2 1 ◎ 100 5
3 2 ○ 100 4
41 △ 803 example 17
A detergent prepared by adding 0.04g/L bromide ion to the detergent of example 3 was tested in the same manner as in example 3. As a result, the evaluation items were all good as in example 3.
From these results, it was found that the pickling agent and the washing bath for aluminum-based metals of the present invention can provide a good cleaning effect without using fluorine ions. Example 18 (Performance Change according to ORP value)
TABLE 3
1.0 g/L1-hydroxyethylidene-1, 1-diphosphonic acid
H2SO412.5g/L
Fe2+1.0g/L
Nonylphenol EO adduct 1.0g/L
Hydrocarbon derivatives 1.0g/L
Changing the H in the aqueous solution (water temperature 70 ℃ C.)2O2The ORP was evaluated for the performances at 0.60, 0.50 and 0.45V (Ag/AgCl reference).
TABLE 4 ORP (vs. Ag/AgCl) appearance Water wettability (%) decontamination
0.60V ◎ 100 5
0.50V ○ 100 4
Examples 19 to 24 of 0.45V △ 1003
(1) The processedobject is:
a no-lid container to which lubricating oil and dirt adhere, which is obtained by subjecting an aluminum plate of 3004 alloy to DI processing.
(2) A detergent:
for the aqueous acid pickling solution used in the following "(4) evaluation of oxidation efficiency", an aqueous acid pickling solution was used in which ferrous ions in the aqueous washing solution were oxidized to ferric ions with hydrogen peroxide.
(3) The treatment conditions are as follows:
the containers were treated with various detergents by spraying at 70 ℃ for 60 seconds, then rinsed with tap water for 15 seconds followed by deionized water for 5 seconds, and dried at 95 ℃.
(4) Evaluation of oxidation efficiency:
hydrogen peroxide was added dropwise to an aqueous acid pickling solution in an amount described in examples shown in table 5 below while heating and stirring at 70 ℃. Ferrous ion (Fe)2+) Total oxidation to iron ion (Fe)3+) The oxidation efficiency was calculated by the following equation, using the theoretically required amount of hydrogen peroxide as a and the amount required for the implementation as b.
Oxidation efficiency (a/b) × 100 (%)
◎：80～100(％)
○：60～80(％)
(5) Evaluation of detergency:
the following items were tested. The results are shown in Table 6. Further, the appearance, water wettability and soil release properties were determined according to the evaluation criteria used in the evaluation of examples 1 to 16 and comparative examples 1 to 4. TABLE 5
Inorganic acidoxidation type chelating nonionic oxidative decomposition reaction pH
Metal ion dispersants*3Additive for inhibiting surfactant
H2SO4Fe3+Species additive species
(g/l) (g/l) (g/l) (g/l) (g/l) (g/l) example 1912.51.0A ①*1②*2Bromide ion 0.9
1.01.01.00.022012.51.0A ① ② Bromide 0.9
1.01.01.00.22112.51.0A ① ② ethylene glycol 0.9
1.01.01.00.52212.51.0A ① ② ethylene glycol 0.9
1.01.01.03.02312.51.0A ① ② Glycerol 0.9
1.01.01.00.52412.51.0A ① ② Glycerol 0.9
1.0 1.0 1.0 3.0
Note)*Nonyl phenol EO adduct (①)
*Hydrocarbon derivative (②)
*3: a … 1-hydroxyethylidene-1, 1-diphosphonic acidTABLE 6
Evaluation results
Determination of detergency from Oxidation efficiency
Appearance water wettability decontamination property
(％) (％)
Examples
19 ○ ◎ 100 5
20 ◎ ◎ 100 5
21 ○ ◎ 100 5
22 ◎ ◎ 100 5
23 ○ ◎ 100 5
24 ◎ ◎ 1005
As described above, according to the pickling agent for aluminum-based metals, the cleaning bath, and the cleaning method thereof of the present invention, it is possible to remove lubricating oil and dirt adhering to the surface of aluminum without containing harmful chloride ions and fluoride ions that cause pollution to the working environment, and to smoothly perform chemical conversion treatment or coating operation, thereby achieving cleaning.
Possibility of industrial utilization
In the case of producing an article having an aluminum surface, such as an aluminum container for beverages made of aluminum-based metal, i.e., aluminum or aluminum alloy, by a forming operation (hereinafter, referred to as DI processing) called press forming and ironing, the present invention is applicable to an aqueous cleaning solution for removing lubricating oil and aluminum powder (dirt) adhering to the metal surface and a cleaning method thereof.
Statement of amendment according to treaty clause 19
The process of claims 1, 2 and 15 wherein the chelating dispersant is specifically composed of a phosphonic acid compound.
As an example of the introduction (Japanese examined patent publication (Kokoku) No. 3-656436), a description is given of the incorporation of a chelating agent into an aluminum surface detergent at column 5, lines 20 to 25, and the chelating agent is specified.
The present invention uses a chelate dispersant composed of a phosphonic acid compound to form a chelate with an oxidized metal ion in order to stabilize the oxidized metal ion in an aqueous solution under a strong acid, and can obtain the effects of improving dispersibility in an aqueous solution undera strong acid, suppressing the oxidized metal from forming a hydroxide, and thereby preventing the generation of a precipitate (sludge) in the aqueous solution.
Claims
Modification according to article 19 of the treaty
1. An aqueous acid pickling solution for aluminum-based metals, characterized by containing an inorganic acid in an amount capable of lowering the pH to 2, an oxidized metal ion and a chelating dispersant composed of a phosphonic acid compound.
2. An aqueous acid pickling solution for aluminum-based metals, characterized by containing an inorganic acid in an amount capable of lowering the pH to 2, an oxidized metal ion, a chelating dispersant comprising a phosphonic acid compound, and a surfactant.
3. An aqueous acid pickling solution for aluminum-based metals, characterized in that in the aqueous acid pickling solution according to claim 1 or claim 2, the oxidized metal ions are iron ions, metavanadate ions or cerium ions.
4. An aqueous acid pickling solution for aluminum-based metals, characterized in that the concentration of the oxidized metal ions in the aqueous acid pickling solution of claim 1 or claim 2 is 0.05 to 4 g/l.
5. An aqueous acid pickling solution for aluminum-based metals, characterized in that the inorganic acid is sulfuric acid or nitric acid in the aqueous acid pickling solution according to claim 1 or claim 2.
6. An aqueous acid pickling solution for aluminum-based metals, characterized in that the pH of the aqueous acid pickling solution of claim 1 or claim 2 is 0.6 to 2.
(deletion)
8. An aqueous acid pickling solution for aluminum-based metals, characterized in that in the aqueous acid pickling solution according to claim 1 or claim 2,the chelating dispersant is at least 1 phosphonic acid compound selected from the group consisting of 1-hydroxyethylidene-1, 1-diphosphonic acid, aminotri (methylenephosphonic acid) and ethylenediaminetetra (methylenephosphonic acid).
9. An aqueous acid pickling solution for aluminum-based metals, characterized in that the concentration of the chelating dispersant in the aqueous acid pickling solution of claim 1 or claim 2 is 0.05 to 5 g/L.
10. An aqueous acid pickling solution for aluminum-based metals according to claim 1 or 2, wherein said surfactant is at least 1 nonionic surfactant selected from the group consisting of ethoxylated alkylphenols, hydrocarbon derivatives and rosin acid derivatives.
11. An aqueous acid pickling solution for aluminum-based metals, characterized in that the concentration of the surfactant in the aqueous acid pickling solution of claim 1 or claim 2 is 0.1 to 10 g/L.
12. An aqueous acid pickling solution for aluminum-based metals, characterized in that bromine ions and/or a polyhydric alcohol are further added to the aqueous acid pickling solution according to claim 1 or claim 2.
13. An aqueous pickling solution for aluminum-based metals, characterized in that the amount of bromine ions added to the aqueous pickling solution of claim 12 is 0.002 to 0.1 g/L.
14. An aqueous pickling solution for aluminum-based metals, characterized in that the amount of the polyhydric alcohol added is 0.1 to 5g/L to the aqueous pickling solution of claim 12.
15. A method for washing an aluminum surface, characterized in that an aqueous pickling solution containing at least 1 kind of inorganic acid selected from the group consisting of inorganic acids having a pH value of less than 2, an oxidized metal ion, a chelating dispersant consisting of a phosphonic acidcompound, and a surfactant according to the requirement for degreasing is used, and the oxidized metal ion concentration in the aqueous pickling solution is maintained and controlled by measuring the oxidation-reduction potential of the aqueous solution.
16. A method for pickling an aluminum-based metal, according to claim 15, wherein said oxidized metal ions are iron ions, metavanadate ions or cerium ions.
17. A method for pickling an aluminum-based metal, characterized in that the concentration of the oxidized metal ion in the aqueous acid solution of claim 15 is 0.05 to 4 g/L.
18. A method for pickling an aluminum-based metal, according to claim 15, wherein the inorganic acid is sulfuric acid or nitric acid.
19. A method for pickling an aluminum-based metal, characterized in that the aqueous pickling solution according to claim 15 has a pH of 0.6 to 2.
(deletion)
21. A method for pickling an aluminum-based metal, characterized in that in the aqueous pickling solution according to claim 15, the chelating dispersant is at least 1 phosphonic acid compound selected from the group consisting of 1-hydroxyethylidene-1, 1-diphosphonic acid, aminotri (methylenephosphonic acid) and ethylenediaminetetra (methylenephosphonic acid).
22. A method for pickling an aluminum-based metal, characterized in that, in the aqueous pickling solution according to claim 15, the concentration of the chelating dispersant in the aqueous acidic solution is 0.05 to 5 g/L.
23. A method of pickling an aluminum-based metal, characterized in that in the aqueous pickling solution according to claim 15, the surfactant is at least 1 nonionic surfactant selected from the group consisting of ethoxylated alkylphenols, hydrocarbon derivatives and rosin acid derivatives.
24. A method for pickling an aluminum-based metal, characterized in that the concentration of the surfactant in the aqueous acid solution of claim 15 is 0.1 to 10 g/L.
25. A method for pickling an aluminum-based metal, characterized in that bromide ions and/or a polyhydric alcohol are further added to the aqueous pickling solution according to claim 15.
26. A method for pickling an aluminum-based metal, characterized in that the bromine ion is added in an amount of 0.002 to 0.1g/L to the aqueous pickling solution according to claim 25.
27. A method for pickling an aluminum-based metal, characterized in that the amount of the polyhydric alcohol added to the aqueous pickling solution of claim 25 is 0.1 to 5 g/L.
28. A method for pickling an aluminum-based metal, characterized in that, in the aqueous pickling solution according to claim 15, the oxidation-reduction potential (ORP) of the pickling bath is 0.55 to 0.7 (Ag/AgCl reference).
29. A method for pickling an aluminum-based metal, characterized in that in the aqueous pickling solution according to claim 15, said oxidizing agent is H2O2。
Claims (29)
1. An aqueous acid pickling solution for aluminum-based metals, characterized by containing an inorganic acid in an amount capable of lowering the pH to 2, an oxidized metal ion and a chelating dispersant.
2. An aqueous acid pickling solution for aluminum-based metals, characterized by containing an inorganic acid in an amount capable of lowering the pH to 2, an oxidized metal ion, a chelating dispersant and a surfactant.
3. An aqueous acid pickling solution for aluminum-based metals, characterized in that in the aqueous acid pickling solution according to claim 1 or claim 2, the oxidized metal ions are iron ions, metavanadate ions or cerium ions.
4. An aqueous acid pickling solution for aluminum-based metals, characterized in that the concentration of the oxidized metal ions in the aqueous acid pickling solution of claim 1 or claim 2 is 0.05 to 4 g/L.
5. An aqueous acid pickling solution for aluminum-based metals, characterized in that the inorganic acid is sulfuric acid or nitric acid in the aqueous acid pickling solution according to claim 1 or claim 2.
6. An aqueous acid pickling solution for aluminum-based metals, characterized in that the pH of the aqueous acid pickling solution of claim 1 or claim 2 is 0.6 to 2.
7. An aqueous acid pickling solution for aluminum-based metals, characterized in that the chelating dispersant is a phosphonic acid compound in the aqueous acid pickling solution according to claim 1 or claim 2.
8. An aqueous acid pickling solution for aluminum-based metals, characterized in that in the aqueous acid pickling solution according to claim 1 or claim 2, the chelating dispersant is at least 1 phosphonic acid compound selected from the group consisting of 1-hydroxyethylidene-1, 1-diphosphonic acid, aminotri (methylenephosphonic acid) and ethylenediaminetetra (methylenephosphonic acid).
9. An aqueous acid pickling solution for aluminum-based metals, characterized in that the concentration of the chelating dispersant in the aqueous acid pickling solution of claim 1 or claim 2 is 0.05 to 5 g/L.
10. An aqueous acid pickling solution for aluminum-based metals according to claim 1 or 2, wherein said surfactant is at least 1 nonionic surfactant selected from the group consisting of ethoxylated alkylphenols, hydrocarbon derivatives and rosin acid derivatives.
11. An aqueous acid pickling solution for aluminum-based metals, characterized in that the concentration of the surfactant in the aqueous acid pickling solution of claim 1 or claim 2 is 0.1 to 10 g/L.
12. An aqueous acid pickling solution for aluminum-based metals, characterized in that bromine ions and/or a polyhydric alcohol are further added to the aqueous acid pickling solution according to claim 1 or claim 2.
13. An aqueous pickling solution for aluminum-based metals, characterized in that the amount of bromine ions added to the aqueous pickling solution of claim 12 is 0.002 to 0.1 g/L.
14. An aqueous pickling solution for aluminum-based metals, characterized in that the amount of the polyhydric alcohol added is 0.1 to 5g/L to the aqueous pickling solution of claim 12.
15. A method for washing an aluminum surface, characterized in that an aqueous pickling solution containing at least 1 kind of inorganic acid selected from the group consisting of inorganic acids in an amount such that the pH value is less than 2, an oxidized metal ion, a chelating dispersant, and a surfactant according to the requirement for degreasing is used, and the oxidized metal ion concentration in the aqueous pickling solution is maintained and controlled by measuring the oxidation-reduction potential of the aqueous solution.
16. A method for pickling an aluminum-based metal, according to claim 15, wherein said oxidized metal ions are iron ions, metavanadate ions or cerium ions.
17. A method for pickling an aluminum-based metal, characterized in that the concentration of the oxidized metal ion in the aqueous acid solution of claim 15 is 0.05 to 4 g/L.
18. A method for pickling an aluminum-based metal, according to claim 15, wherein the inorganic acid is sulfuric acid or nitric acid.
19. A method for pickling an aluminum-based metal, characterized in that the aqueous pickling solution according to claim 15 has a pH of 0.6 to 2.
20. A method for pickling an aluminum-based metal, characterized in that in the aqueous pickling solution according to claim 15, the chelating dispersant is a phosphonic acid compound.
21. A method for pickling an aluminum-based metal, characterized in that in the aqueous pickling solution according to claim 15, the chelating dispersant is at least 1 phosphonic acid compound selected from the group consisting of 1-hydroxyethylidene-1, 1-diphosphonic acid, aminotri (methylenephosphonic acid) and ethylenediaminetetra (methylenephosphonic acid).
22. A method for pickling an aluminum-based metal, characterized in that, in the aqueous pickling solution according to claim 15, the concentration of the chelating dispersant in the aqueous acidic solution is 0.05 to 5 g/L.
23. A method of pickling an aluminum-based metal, characterized in that in the aqueous pickling solution according to claim 15, the surfactant is at least 1 nonionic surfactant selected from the group consisting of ethoxylated alkylphenols, hydrocarbon derivatives and rosin acid derivatives.
24. A method for pickling an aluminum-based metal, characterized in that the concentration of the surfactant in the aqueous pickling solution of claim 15 is 0.1 to 10g/L in the acidic aqueous solution.
25. A method for pickling an aluminum-based metal, characterized in that bromide ions and/or a polyhydric alcohol are further added to the aqueous pickling solution according to claim 15.
26. A method for pickling an aluminum-based metal, characterized in that the bromine ion is added in an amount of 0.002 to 0.1g/L to the aqueous pickling solution according to claim 25.
27. A method for pickling an aluminum-based metal, characterized in that the amount of the polyhydric alcohol added to the aqueous pickling solution of claim 25 is 0.1 to 5 g/L.
28. A method for pickling an aluminum-based metal, characterized in that, in the aqueous pickling solution according to claim 15, the oxidation-reduction potential (ORP) of the pickling bath is 0.55 to 0.7 (Ag/AgCl reference).
29. A method for pickling an aluminum-based metal, characterized in that in the aqueous pickling solution according to claim 15, said oxidizing agentis H2O2。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP256346/94 | 1994-10-21 | ||
| JP25634694A JP3192562B2 (en) | 1993-11-05 | 1994-10-21 | Aqueous cleaning aqueous solution of aluminum-based metal and cleaning method thereof |
| JP256346/1994 | 1994-10-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1170443A true CN1170443A (en) | 1998-01-14 |
| CN1063236C CN1063236C (en) | 2001-03-14 |
Family
ID=17291407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95196828A Expired - Fee Related CN1063236C (en) | 1994-10-21 | 1995-06-12 | Aqueous acid cleaning solution for aluminum metal and method for cleaning the metal |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0789094A4 (en) |
| KR (1) | KR100231390B1 (en) |
| CN (1) | CN1063236C (en) |
| WO (1) | WO1996012832A1 (en) |
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| CN101205609B (en) * | 2006-12-18 | 2010-08-11 | 比亚迪股份有限公司 | Composition for magnesium alloy surface activation |
| CN102373340A (en) * | 2010-08-23 | 2012-03-14 | 北京化工大学 | Method for reclaiming aluminum powder from composite propellant |
| CN104593793A (en) * | 2015-02-12 | 2015-05-06 | 佛山市仁昌科技有限公司 | Neutralization solution for surface pretreatment of aluminum and aluminum alloy |
| CN105579619A (en) * | 2013-09-27 | 2016-05-11 | 日涂表面处理化工有限公司 | Method for treating surface of aluminum can |
| CN105908239A (en) * | 2016-05-31 | 2016-08-31 | 刘洪建 | Processing method capable of improving surface strength of aluminum and aluminum alloy |
| CN106835165A (en) * | 2017-03-06 | 2017-06-13 | 上海赛敏环保科技有限公司 | Aluminium alloy removes mildew cleaning agent and Cleaning application method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4303365B2 (en) * | 1998-07-30 | 2009-07-29 | 日本ペイント株式会社 | Cleaning aqueous solution of aluminum metal and cleaning method thereof |
| JP2001226790A (en) * | 2000-02-15 | 2001-08-21 | Nippon Paint Co Ltd | Acidic cleaning solution for aluminum material and cleaning method therefor |
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| FR2941241B1 (en) * | 2009-01-22 | 2011-05-27 | Airbus France | CHROME HEXAVALENT CHROME STRIPPING METHOD AND SOLUTION OF AN ALUMINUM OR ALUMINUM ALLOY SURFACE AND PROCESSING METHOD COMPRISING AT LEAST ONE STRIPPING STEP THEREFOR. |
| DE102012104951A1 (en) * | 2012-06-08 | 2013-12-12 | Stockmeier Chemie GmbH & Co.KG | Use of a phosphonic acid and / or phosphonic acid derivative-containing solution in the degreasing of metal surfaces, degreasing solution and method for degreasing a metal surface |
| KR101629336B1 (en) * | 2015-09-02 | 2016-06-10 | (주)아인스 | Method for cleaning aluminum member |
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| DE2841641C2 (en) * | 1978-09-25 | 1986-07-03 | Henkel KGaA, 4000 Düsseldorf | Use of alkyl monophosphonic acids as corrosion inhibitors |
| JPS61106783A (en) * | 1984-10-30 | 1986-05-24 | Nippon Paint Co Ltd | Cleaner for surface of aluminum |
| JPS61231188A (en) * | 1985-04-04 | 1986-10-15 | Nippon Paint Co Ltd | Method for controlling aluminum surface cleaning agent |
| JPH0273983A (en) * | 1988-09-07 | 1990-03-13 | Nippon Parkerizing Co Ltd | Acidic washing solution for aluminum |
| JPH0273983U (en) * | 1988-11-24 | 1990-06-06 | ||
| JPH0365436A (en) * | 1989-07-31 | 1991-03-20 | Iseki & Co Ltd | Power transmission device in micro-sized shovel car |
| JPH07122152B2 (en) * | 1990-06-19 | 1995-12-25 | 日本パーカライジング株式会社 | Acid cleaning solution for aluminum |
| JPH04304392A (en) * | 1991-03-31 | 1992-10-27 | Nippon Nohyaku Co Ltd | Cleaning agent for aluminum fin |
| DE69404711T2 (en) * | 1993-03-26 | 1998-01-15 | Nippon Paint Co Ltd | Use of an acidic, aqueous cleaning solution for aluminum and aluminum alloys and cleaning methods |
| JP2947695B2 (en) * | 1993-07-30 | 1999-09-13 | 日本ペイント株式会社 | Aqueous cleaning aqueous solution of aluminum-based metal and cleaning method thereof |
-
1995
- 1995-06-12 EP EP95921156A patent/EP0789094A4/en not_active Withdrawn
- 1995-06-12 CN CN95196828A patent/CN1063236C/en not_active Expired - Fee Related
- 1995-06-12 WO PCT/JP1995/001171 patent/WO1996012832A1/en active IP Right Grant
- 1995-06-12 KR KR1019970702506A patent/KR100231390B1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| WO1996012832A1 (en) | 1996-05-02 |
| KR100231390B1 (en) | 1999-12-01 |
| EP0789094A1 (en) | 1997-08-13 |
| CN1063236C (en) | 2001-03-14 |
| KR970707324A (en) | 1997-12-01 |
| EP0789094A4 (en) | 1998-01-14 |
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