JP2001064700A - Cleanser for aluminum-based metal material and method for cleansing the material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject cleanser which can efficiently remove stain substances and foreign matters adhered to surfaces without corroding Al-based metal materials to be cleansed, by using an alkaline aqueous solution containing specific components. SOLUTION: This cleanser for aluminum-based metal materials comprises (A) an alkali builder (for example, an alkali metal hydroxide, an alkali metal silicate, or an alkali metal phosphate), (B) an organic sulfonic acid compound (for example, 1-hydroxyethylidene-1,1-diphosphoric acid), (C) a surfactant (preferably at least one of nonionic surfactants and anionic surfactants), and (D) a Ca compound and/or a Ba compound (preferably at least one of the hydroxide, carbonate, hydrochloride and nitrate of Ca or Ba). The contents of the components A, B, and C are preferably 1 to 100 g/liter, 0.05 to 1.5 g/liter, and 0.1 to 3 g/liter, respectively, and the content of the component D is 0.1 to 2 moles based on the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent and a cleaning method for an Al-based metal material, and more particularly to an Al to be cleaned.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent and a cleaning method capable of efficiently cleaning and removing contaminants and foreign substances such as oils and fats and abrasion powder attached to the surface of the base metal material without corroding the base metal material itself.

[0002]

2. Description of the Related Art Halogenated hydrocarbon-based cleaning agents have been used for cleaning the surface of Al-based metal materials such as Al and various Al alloys containing Al.
Recently, cleaning using an alkaline aqueous solution has become widespread from the viewpoints of economy, environmental safety, workability, and cleaning effect.

[0003] In other words, the surface of the Al-based metal material has an oxide film which is easily soluble in alkalis, and also oils and metal powders adhered in the processing step, which are compared with the alkaline cleaning agent. This is because it can be easily removed.

[0004] Various alkaline detergents are known, and typical ones are sodium metasilicate, sodium orthophosphate, sodium hydroxide, potassium hydroxide and the like. Among these alkaline detergents, sodium metasilicate can clean the surface of the Al-based metal material to some extent efficiently without corroding the surface if the pH is about 11 or less. There is a problem that the surface of the material is significantly corroded, and sodium orthophosphate has a problem that a black foreign substance called a smut is generated on the surface of the Al-based metal material in the cleaning step, thereby significantly deteriorating the appearance. Sodium hydroxide and potassium hydroxide have high degreasing power, but hydroxide film grows on the surface of Al-based metal material, or alkali-insoluble impurities and alloy components remain on the surface as smut. Problem is pointed out.

In general, it has been confirmed that an alkaline cleaning agent exhibits a higher detergency in a higher pH range. However, a metal to be cleaned has an erosion limit for alkali, and Al has a erosion limit of about pH10. ing. In consideration of these facts, Al-based metal materials have been developed as alkaline detergents that exhibit high detergency without causing as much erosion of the substrate surface as one of them.
A cleaning agent as described in JP 111465 is disclosed. However, even with this alkali cleaning agent, if cleaning is performed in a high alkalinity region of pH 12 or more, corrosion of the Al-based metal material surface occurs, and it is inevitable that appearance deterioration such as smut occurs.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation,
A cleaning agent that can be used to clean the base metal material, which can efficiently clean and remove impurities such as oils and foreign substances adhering to the surface without suppressing surface corrosion and causing problems such as smut. Another object of the present invention is to provide a cleaning method capable of efficiently cleaning an Al-based metal material.

[0007]

The cleaning agent for an Al-based metal material according to the present invention, which can solve the above-mentioned problems, comprises:
(a) alkali builder, (b) organic phosphonic acid compound, (c)
A surfactant and (d) a Ca compound and / or a Ba compound, preferably (a) an alkali builder: 1 to 100 g / l, (b) an organic phosphonic acid compound: 0.05 to 1 g / l, (c) Surfactant: 0.1 to 3 g / liter, and (d) Ca compound and / or Ba compound: An alkaline aqueous solution containing 0.1 to 2 mol of the above organic phosphonic acid compound. have.

In the present invention, the above-mentioned component (b), that is, an organic phosphonic acid compound, is particularly preferably 1-hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,2,3. 4-
It is at least one selected from tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and salts thereof.

The component (c), that is, a surfactant is preferably at least one of a nonionic surfactant and an anionic surfactant, and the component (d) is particularly preferably Ca or Ba. At least one selected from the group consisting of hydroxides, carbonates, hydrochlorides, and nitrates, wherein the pH of the alkaline aqueous solution is adjusted to 12 or more, without causing corrosion of the Al-based metal material to a high level. Detergent power.

[0010] When the cleaning agent is used, impurities and foreign matters such as oil and metal powder on the surface of the Al-based metal material are efficiently cleaned and removed without generating contaminating corrosion products such as smut on the surface. Can be

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, the detergent of the present invention comprises (a) an alkali builder, (b) an organic phosphonic acid compound, (c) a surfactant and (d) a Ca compound and / or An alkaline detergent for cleaning Al-based metal materials containing a Ba compound. By incorporating these four components as essential components, even when cleaning is performed in a highly alkaline region of pH 12 or more, water on the surface of the Al-based metal material is reduced. It exhibits the function of efficiently cleaning and removing foreign substances and impurities such as oils and fats and metal powder adhering to the surface without causing surface property deterioration phenomena such as growth of oxide films and formation of smut and the like. In the following, the action, preferred content, examples of preferred components and the like of each component will be described in detail.

The alkali builder specified as the component (a) is a main component of alkali washing, and specific compounds include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide. Alkali metal silicates such as sodium orthosilicate, potassium orthosilicate, sodium metasilicate and potassium metasilicate;
Examples thereof include alkali metal phosphates such as sodium phosphate and tribasic potassium phosphate. These can be used alone, or two or more of them can be used in combination as needed.

The preferred concentration of these alkali builders in the detergent is 1 g / l or more and 100 g / l or less. When the concentration is less than 1 g / l, the pH of the detergent does not rise to 12 or more, and a satisfactory degreasing effect is obtained. It is difficult to obtain. The degreasing and detergency increases as the alkali builder concentration increases, but its action is about 100%.
It is saturated at g / l, and even if the concentration is further increased, no further effect of improving the detergency can be obtained. Therefore, it is preferable to suppress the concentration to about 100 g / l or less from the viewpoint of economy. In consideration of both detergency and economy, the lower limit of the alkali builder concentration is more preferably 5 g / l, and the more preferable upper limit is 50 g / l.

Next, the organic phosphonic acid compound specified as the component (b) suppresses the formation of black smut generated on the surface of the Al-based metal material, the formation of a hydroxide layer on the surface of the cleaning, and the metal segregated on the surface of the metal material. It is a component that exerts an action such as removal of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and aminotrimethylene phosphonic acid represented by the following formulas (1) to (4). (NT
P), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), ethylenediaminetetramethylenephosphonic acid, or an acid such as hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, or an alkali metal salt thereof. For example, these can be used alone or in combination of two or more as necessary.

[0015]

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In order to effectively exert the above-mentioned action of these organic phosphonic acid compounds, the concentration of the organic phosphonic acid compound in the detergent should be in the range of 0.05 g / liter to 1.5 g / liter. If the concentration is lower than this, the effect of inhibiting the surface corrosion of the Al-based metal material tends to be insufficient, and even if it is contained in a high concentration exceeding 1.5 g / liter, the effect of inhibiting the corrosion tends to show a decreasing tendency. . A more preferable concentration of the organic phosphonic acid compound for effectively exhibiting the corrosion inhibiting action is 0.05 g / liter or more and 1.0 g / liter or less.

Next, the surfactant used as the component (c) is an important component for enhancing the detergency and in particular for enhancing the degreasing action, and its action is particularly nonionic among surfactants. It is more effectively exerted by surfactants or anionic surfactants.

Specific examples of the nonionic surfactant include:
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl ether;
And sorbitan alkylates such as sorbitan laurate. Specific examples of the anionic surfactant include alkylbenzene sulfonate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkyl ether sulfate, and salts thereof (alkali metal salts). Ammonium salts; amine salts such as triethylamine, triethanolamine and diisopropylamine), and two or more of these can be used in combination, if necessary.

The preferred concentration for effectively exerting the action of these surfactants is 0.1 g / d in the detergent.
Liter or more and 3 g / liter or less, and 0.1 g /
If the concentration is less than 1 liter, a satisfactory cleaning effect is hardly obtained, and even if the concentration is excessively increased to more than 3 g / liter, no further effect of improving the cleaning power is exhibited, so that it is economically wasteful. The concentration of the surfactant is more preferably 0.5 g / L or more and 2.5 g / L or less in consideration of detergency and economy.

Further, the Ca compound and / or the Ba compound used as the component (d) is a component which exerts an action of suppressing the surface corrosion of the Al-based metal material by a complex action with the organic phosphonic acid compound. Examples thereof include calcium carbonate, calcium hydroxide, barium carbonate and the like. Among these, Ca compounds, especially calcium hydroxide and calcium carbonate, which exert the above-mentioned corrosion inhibiting action more effectively, have a pH of 1 by containing these alone or, if necessary, two or more.
Corrosion of the Al-based metal material can be suppressed even in a high alkalinity region of 2 or more, and as a result, an excellent cleaning effect under high alkalinity conditions can be effectively exhibited.

A preferable content for effectively exerting the action of the Ca compound and / or the Ba compound is in the range of 0.1 to 2 mol with respect to the organic phosphonic acid compound. The effect of inhibiting the elution of aluminum ions during washing is insufficient, so that the corrosion inhibiting effect intended in the present invention is not effectively exerted. Conversely, if the content exceeds 2 mol, the supersaturated state is caused in the detergent. And cause white smut. The content of these compounds is more preferably 0.5 mol or more and 1.5 mol or less with respect to the organic phosphonic acid compound in order to efficiently suppress corrosion of the Al-based metal material surface without generating white smut or the like.

When industrial water, well water, river water, tap water, or the like is used as the water for preparing the detergent of the present invention, the Ca component contained therein is not changed.
(d) It can be effectively used as a component. Then, for example, when the HEDP is used as the organic phosphonic acid compound and a washing solution containing the HEDP at a concentration of 0.06 g / liter is prepared, if the Ca content in the water is about 10 ppm, the Ca The action is effectively exerted, and the above-mentioned action and effect can be sufficiently exerted only by the Ca compound contained in water without adding any additional Ca compound as long as it contains 50 ppm or more of Ca.

The detergent of the present invention is an alkaline aqueous solution containing the above four components (a) to (d) as essential components,
It is desirable that the pH be 12 or more. The pH is
In particular, the pH is adjusted by the concentration of the alkali builder. If necessary, the pH can be adjusted using an appropriate amount of an acid or an alkali.

As described above, in the case of a conventional alkaline cleaning agent for an Al-based metal material, if the pH of the cleaning agent is increased to 10 or more, corrosion of the surface of the Al-based metal material occurs. As a result, the degreasing and cleaning effect was insufficient and a satisfactory cleaning effect could not be obtained. By coexisting a phosphonic acid compound and a Ca compound and / or a Ba compound, even when the pH of the cleaning solution is increased to 12 or more, corrosion of the surface of the Al-based metal material and generation of smut accompanying the same can be prevented. In combination with the combination of activators,
An excellent degreasing and cleaning effect can be obtained.

In the cleaning composition of the present invention, in addition to the above four components, if necessary, a defoaming agent, a cleaning aid such as carbitol, a dissolution aid such as alcohol, ethylene glycol and glycol ether, a sodium benzoate. It is also effective to incorporate a corrosion inhibitor such as sodium sebacate, sodium gluconate, benzotriazole and the like to effectively exert their respective functions.

The method of preparing the detergent according to the present invention is not particularly limited, and the above-mentioned components are added simultaneously to water, or sequentially added in an arbitrary order and uniformly mixed, or adjusted to an appropriate concentration. The above components in an aqueous alkali builder solution
(b), (c), (d) are added as a solid component or as an arbitrary solution simultaneously or in any order, and if necessary, pH
Any method such as an adjustment method may be adopted.

There is no particular limitation on the method of cleaning the surface of the Al-based metal material using the cleaning agent, and any method such as a method of immersing the Al-based metal material in the cleaning agent, a water spraying method and a spraying method can be used. It is possible to employ a method of contacting the surface of the metal material to be treated by a method. In this case, it is not necessary to further heat in the washing step, and it is sufficient to wash at room temperature, but if the ambient temperature is too low, a moderate It is also possible to increase the cleaning effect by heating the water. The washing time is not particularly limited, but if the contact time with the washing liquid is less than 5 seconds, there is a tendency for insufficient degreasing and insufficient removal of surface oxides and smut, so even when performing continuous washing, preferably 5 seconds or more, More preferably, it is desirable to secure a contact time of about 20 seconds or more. It is also effective to use the cleaning agent in combination with mechanical polishing such as buffing and to perform mechanical surface polishing and surface cleaning in parallel. Particularly, the polishing agent of the present invention has a corrosive effect on Al-based metal materials. Is extremely low, so that it can be effectively used even in a case where mirror finishing is performed in combination with such mechanical polishing.

After the surface has been cleaned with the cleaning agent, the components of the cleaning agent are removed by washing with water and, if necessary, by washing with an alcohol, ketone, ether or the like, followed by drying. A base metal material can be obtained.

There is no particular limitation on the type of Al-based metal material to which the present invention is applied. In short, as long as Al is contained as a metal component, not only pure Al but also Al and other metals, For example, Mg, Mn, Fe, Si, Zn, Cu, Cr
It can be applied to all alloy materials such as plates, bars, pipes, wires, shapes, etc.
It can be used regardless of its shape and dimensions.

[0030]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention is not limited thereto. Modifications may be made and all of them are included in the technical scope of the present invention.

Examples and Comparative Examples Detergents having the compositions shown in Tables 1 to 4 (substantially water) were prepared, and the performance of each as a detergent was examined by the following methods. The result was obtained.

[Test Al-based metal material] Al alloy (A105
0P) plate (40 mm ^W × 60 mm ^L × 1.5 mm ^t ), the surface of the Al alloy plate is wet-polished with a # 320 water-resistant abrasive paper, and then washed with distilled water, cold methanol and acetone in this order. And subjected to a corrosion cleaning test.

[Corrosion Washing Test] The weighed Al alloy plate was immersed in each washing solution at 25 ° C. for 1 hour, taken out, washed with water, washed with methanol and acetone, dried, and weighed to obtain a corrosion amount (mg). Was measured, the corrosion inhibition rate was determined by the following formula, and the degree of surface discoloration was visually evaluated according to the following criteria. Corrosion inhibition rate (%) = [(corrosion in blank test−corrosion in cleaning agent) / corrosion in blank test] × 100 Appearance evaluation: ：: no discoloration is observed, ：: white A small amount of smut is observed. Δ: Blackening is observed on a part of the surface. X: Blackening is observed on the entire surface.

In Tables 1 to 4, the abbreviations of the compounds used as the organic phosphonic acid are as follows: HEDP: 1-hydroxyethylidene-1,1-diphosphonic acid NTP: aminotrimethylene phosphonic acid PBTC: 2- Phosphonobtan-1,2,4-tricarboxylic acid In Examples 4, 9, 10 and Comparative Examples 4, 9, 10 the final pH was adjusted with acetic acid.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6]

As is clear from Tables 1, 2, and 5, all of the cleaning liquids satisfying the requirements of the present invention have a small amount of corrosion loss during cleaning and are excellent in corrosion inhibition, and the surface after cleaning is beautiful. No adhesion of smut or the like was observed. On the other hand, Tables 3, 4, and 6 are comparative examples lacking any of the requirements specified in the present invention, and comparative examples 1, 2, 3, 8, 12
Nos. 18 to 18 all have a poor corrosion inhibition rate and markedly deteriorated surface appearance. In Comparative Examples 4, 9, and 10, the corrosion loss was obtained by using a common alkali builder together with an appropriate amount of a surfactant, and the pH was 12 or less even without adding an organic phosphonic acid or Ca or Ba salt. Therefore, the corrosion loss is small, but the degreasing and cleaning action for oils and fats is poor, and the original cleaning power cannot be exhibited. Also in these systems p
When H was increased to 13 or more to increase the detergency (Comparative Examples 5 to 5)
8) The surface corrosion becomes remarkable and the surface appearance becomes poor.

Comparative Example 11 is an example in which an organic phosphonic acid was not used in combination, in which the corrosion inhibition rate was slightly insufficient and the appearance was deteriorated. Comparative Example 12 is an example in which neither the Ca compound nor the Ba compound was added, and also the appearance was significantly deteriorated. Comparative Examples 13 to 18 are examples in which magnesium hydroxide or aluminum hydroxide was used in place of the Ca or Ba compound. Reference Examples 1 and 2 are examples in which the amount of Ca (OH) ₂ is out of the preferred range, the corrosion inhibition rate is slightly insufficient, and the appearance is slightly poor. In addition, in Reference Examples 3 to 6, the addition amount of the organic phosphonic acid compound was slightly excessive or slightly insufficient, so that the corrosion inhibiting effect was insufficient and the surface appearance was not good.

[0043]

The present invention is constituted as described above, and comprises alkali builder, organic phosphonic acid, a surfactant and a Ca compound and / or a Ba compound as detergent components.
By containing the components as essential components, pH 12
It has become possible to provide a cleaning agent that exhibits high cleaning power without causing corrosion deterioration of the Al-based metal material even in the above-described highly alkaline region.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 3/04 C11D 3/04 3/10 3/10 3/36 3/36 C23G 1/22 C23G 1 / 22 5/00 5/00 (72) Inventor Toshio Fujita 3-3-3 Hinagahigashi, Yokkaichi-shi, Mie Chubu Kirest Co., Ltd. Yokkaichi Plant (72) Inventor Arimatsu Ipparu 3 Hinagahi, Yokkaichi-shi, Mie 3-3-3 Chubu Kyrest Co., Ltd. Yokkaichi Plant (72) Inventor Kyoko Hashimoto 3-3-3 Hinagahigashi, Yokkaichi City, Mie Prefecture Chubu Kyrest Co., Ltd. Yokkaichi Plant F-term (reference) 4H003 AC09 BA12 DA09 DB02 EA14 EA15 EA16 EA16 EA19 EA21 EB24 FA04 FA15 FA28 4K053 PA10 QA04 QA07 RA21 RA22 RA23 RA25 RA26 RA27 RA28 RA31 RA63 RA64

Claims (7)

[Claims] 1. A cleaning agent for cleaning an Al-based metal material, comprising: (a) an alkali builder, (b) an organic phosphonic acid compound, (c) a surfactant, and (d) a Ca compound and / or Al comprising an alkaline aqueous solution containing a Ba compound
Cleaning agent for base metal materials. (2) (a) alkali builder: 1 to 100 g / l, (b) organic phosphonic acid compound: 0.05 to 1.5 g / l, (c) surfactant: 0.1 to 3 g / l, And (d) a Ca compound and / or a Ba compound: an Al aqueous solution containing 0.1 to 2 mol based on the organic phosphonic acid compound.
Cleaning agent for base metal materials. 3. The Al-based metal material according to claim 1, wherein the component (d) is at least one selected from the group consisting of hydroxides, carbonates, hydrochlorides, and nitrates of Ca or Ba. Cleaning agent. 4. An organic phosphonic acid compound comprising: 1-hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid, hexamethylene Diamine tetramethylene phosphonic acid, diethylene triamine pentamethylene phosphonic acid,
The cleaning agent for an Al-based metal material according to any one of claims 1 to 3, wherein the cleaning agent is at least one member selected from the group consisting of: 5. The cleaning agent according to claim 1, wherein the surfactant is at least one of a nonionic surfactant and an anionic surfactant. 6. The cleaning agent for an Al-based metal material according to claim 1, which has a pH of 12 or more. 7. An Al-based cleaning agent according to claim 1, wherein the cleaning agent is brought into contact with an Al-based metal material to clean the surface thereof without corroding the Al-based metal material. Cleaning method for base metal material.