JPH0967600A - Metal surface cleaner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a metal surface cleaner which removes tightly adhering or glued organic or inorganic foreign matters and makes surface perfectly clean by including a metal sulfonate and a specific semipolar organic boron surfactant in a hydrophilic solvent. SOLUTION: A metal surface cleaner containing (B) a methanesulfonic acid and (C) a semipolar organic boron surfactant represented by the formula (wherein one or more of R1-4 is a 8-22C acyl or hydrogen: p, q, x and y are each a value of 0-40 and 0<=n1 p+q+n2 x+<=40 and n1 is 0 or 3 at m1 =0, n2 is 0 or 3 at m2 =0, n2 =1 at m2 =1) in (A) a hydrophilic solvent is made by putting and dissolving B and C in A by mixing. The solvent A is water, methanol, glycols, etc. The surfactant C is a di(polyol)borate obtained by the esterification of a hydroxyl-containing polyhydric alcohol and boric acid, di(γ- lauroyloxypolyoxyethylene glycerol) borate obtained from a carboxylic acid, etc. The use of this cleaning agent ensures a pure surface of a metal.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a treating agent for cleaning and regenerating a metal surface.

[0002]

2. Description of the Related Art Conventionally, the plating industry has been known as an industry in which it is necessary to create a cleaned metal surface in advance, and it is possible to remove organic and inorganic impurities adhering or adhering to an object to be plated. As a method of collectively removing the fluorocarbon, cleaning with a fluorine-based or chlorine-based solvent such as Freon 113, methyl chloroform, and trichloroethylene has been widely performed. Moreover, in order to remove the oxide layer on the surface, an acid cleaning method or an electrolytic alkali cleaning method has been adopted.

On the other hand, in the cleaning from the viewpoint of regenerating the metal surface, there is peeling of the coating layer for the purpose of reusing resources and washing of the peeled surface. Again, for this, solvent washing is used for the coating film which can be conventionally dissolved. Further, the coating film having no solubility was subjected to a physical treatment such as a sandblast method.

Further, the work in which the cleaning of the metal surface is indispensable in the process includes welding and brazing operations, and in the past, it has been common to clean the surface by physical surface polishing. Met.

[0005]

However, the use of the fluorine-based or chlorine-based solvent, which has always been incorporated in the process in the plating industry and the like, is designated as an environmentally destructive substance, so that its use is greatly restricted. Nowadays, a cleaning agent to replace it is urgently needed, and various researches have been conducted on using several solvents, acids, alkalis, surfactants, etc. alone or in combination as a cleaning agent, and some market introductions. However, currently known ones do not have the ability to completely clean all kinds of adhered oils and greases, and it is almost impossible to remove troublesome buff residue. For this reason, not only does it hinder the plating operation in the subsequent process, but also many defective plated products are produced, which has caused a great deal of confusion as a whole industry.

[0006] Also, in the business of recovering metal cloth by removing the coating film by peeling the coating film for the purpose of reusing resources,
At present, cleaning work is complicated because there is no method that can achieve various purposes with low cost, simply, and by one means, and it is limited in terms of location and equipment. However, the number of cases that have been adopted is small and it is difficult.

On the other hand, in the cleaning of the metal surface during the welding or brazing operation, a chemical treatment method has been developed so far that the removal of organic impurities and the removal of surface oxide can be carried out completely at the same time. Therefore, in most cases, physical polishing treatment is carried out. However, although the surface is cleaned, polishing scratches are formed in a wide area, which is not preferable in appearance.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is of organic or inorganic nature that physically and firmly adheres to itself or is chemically bonded on the surface. Smooth removal of impurities all at once, regardless of their type and composition, and at the same time making the metal surface a completely clean surface,
The present invention also provides a useful metal surface cleaning agent that can be simply prepared.

That is, the present invention relates to a compound of general formula I with methanesulfonic acid in a hydrophilic solvent.

Embedded image (However, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or an acyl group having a total of 8 to 22 carbon atoms, and 0 ≦ p ≦ 40, 0 ≦ q ≦
40,0 ≦ x ≦ 40, 0 ≦ y ≦ 40, and 0 ≦ n ₁
p + q + n ₂ x + y ≦ 40, m ₁ and m ₂ are 0 or 1, and in the relationship between m ₁ and n _{1 and} the relationship between m ₂ and n ₂ , when m ₁ = 0, n ₁ = 0 Or 3, m
_{When 1} = 1, n ₁ is also 1. When m ₂ = 0, n ₂ = 0
Or 3, when m ₂ = 1 then n ₂ is also 1 and R
_{At least one of 1} , R ₂ , R ₃ and R ₄ is an acyl group. ) 1 of the semipolar organoboron surfactants represented by
It is a metal surface cleaning agent characterized by containing one or more kinds.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The predetermined semipolar organoboron surfactant constituting the metal surface cleaning agent of the present invention will be described. The predetermined semipolar organoboron surfactant has 3 to 6 adjacent hydroxyl groups. Di (polyol) borate 1 obtained by contacting 2 mol of a polyhydric alcohol having a total of 3 to 6 carbon atoms with 1 mol of boric acid or a boric acid triester of a lower alcohol to carry out an esterification reaction or a transesterification reaction A carboxylic acid having a total of 8 to 22 carbon atoms is reacted with at least 1 mol per mol (Production Process A), or 1 to 1 mol of the above di (polyol) borate.
After adding 40 moles of ethylene oxide, it is produced by reacting a carboxylic acid having a total of 8 to 22 carbon atoms in a minimum of 1 mole (Production Method B) (Oil Chemistry, Vol. 22, 4).
Page 26 and Yugaku Kagaku, Vol. 28, p. 285), where R ₁ , R ₂ , R ₃ and R ₄ in the general formula I are acyl groups, the total number of carbon atoms in the acyl groups is 8 Less than or 23
When it is above and when p + q + x + y is larger than 40, the peeling action of the coating film component on the metal surface in the state of being mixed with methanesulfonic acid is remarkably reduced, which is not preferable.

Typical examples of predetermined semipolar organic boron surfactants are shown below by structural formulas.

[0012]

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[Chemical 6]

[Chemical 7]

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[Chemical 12]

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[Chemical 15] Next, the metal surface cleaning agent of the present invention comprising a combination of methanesulfonic acid and a predetermined semipolar organic boron surfactant will be described. The metal surface cleaning agent of the present invention can be used in a closed or open stirring device, for example. , Water and / or lower alcohols such as methanol, ethanol and isopropanol, ethylene glycol, propylene glycol,
1,3-butanediol, glycols such as diethylene glycol, ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether,
Propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether, di Glycol ethers such as propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diglymes such as diethylene glycol diethyl ether, hydrophilic solvents such as acetone, furfural, dioxane, etc. After turning over species or two or charged with one or more methanesulfonic acid and certain semi-polar organic boron surfactant, normal pressure 0-1
It is obtained by mixing at 50 ° C., preferably 20 to 80 ° C., and uniformly dissolving.

Further, if desired, further addition of other acids or surfactants will be acceptable.

In this case, methanesulfonic acid is contained in an amount of 5 to 50 (weight)% in the ratio of methanesulfonic acid and the predetermined semipolar organic boron surfactant, and the predetermined semipolar organic boron surfactant is 50% by weight. When it is contained in an amount of ˜95 (important)%, the surface cleaning action of the metal becomes particularly effective.

In the present invention, the unique strong interfacial adsorptive power exhibited by a given semipolar organic boron surfactant makes it possible to efficiently and uniformly dissociate the strongly dissociative proton (H ⁺ ) peculiar to methanesulfonic acid to the metal surface. On the other hand, the impurities that have been separated from the metal surface are transferred to the hydrophilic solvent without being reattached, so that the surface is completely cleaned in a short time and a pure metal surface appears. Guessed.

[0016]

Embodiments of the present invention will be described below. "%" Described in these examples means% by weight,
"Parts" means parts by weight. For the structural formulas of the predetermined semipolar organic boron surfactants used, refer to the structural formulas (1) to (13) above.

Example 1 In a glass lining tank, mixing was carried out at room temperature for 30 minutes to obtain 20% methanesulfonic acid, 20% predetermined semipolar organic boron surfactant (5), 20% diethylene glycol monobutyl ether, and After producing the metal surface cleaning agent of the present invention consisting of 40% of water, 1 kg of it was charged in another container and heated to an internal temperature of 80 ° C.
And Then, after printing, aluminum cans with printed surface (however,
20 pieces of 5 cm x 5 cm pieces handled by Nippon Coca-Cola Co., Ltd. are put in, and 50 r for 30 minutes at 80 ° C.
After stirring and contacting at a rotation speed of pm, the treated aluminum piece was taken out, rinsed with pure water at room temperature for 10 seconds, and checked for removability of the printed surface, cleanliness of the metal surface, and presence of gloss retention. It was

For comparison tests, the following two compositions were prepared at the same time and subjected to the same test.

Composition of Comparative Test Example I: A homogeneous solution consisting of 20% p-toluenesulfonic acid, 20% tri {lauryloxypoly (12) oxyethylene} borate, 20% diethylene glycol monobutyl ether and 40% water.

Comparative Test Example II: Methanesulfonic acid 20
%, Poly (12) oxyethylene glycol monolaurate 20%, diethylene glycol monobutyl ether 20% and water 40%.

The results are shown in Table 1, and it was confirmed that the metal surface cleaning agent of Example 1 of the present invention showed good performance.

[0022]

[Table 1]

Example 2 In the same manner as in Example 1, metal surface cleaning agents each containing methanesulfonic acid and a predetermined semipolar organic boron surfactant were prepared in the proportions shown in Table 2, and then each of them was prepared. For 1 kg, 20 pieces of surface-printed aluminum cans (however, products handled by Kirin Co., Ltd.) after use were made into small pieces of 5 cm x 5 cm, and charged, and agitated and contacted at 75 ° C for 1.5 hours at a rotation speed of 20 rpm. Let

Subsequently, the treated aluminum piece is taken out,
After rinsing and washing with normal temperature water for 10 seconds, the presence or absence of removability of the printed surface and cleanliness of the metal surface was examined.

[0025]

[Table 2]

The results are shown in Table 3 or the production examples 2 to 2 of the present invention.
The excellent performance of the metal surface cleaning agent of No. 6 was confirmed.

[0027]

[Table 3]

Example 3 In the same manner as in Example 1, metal surface cleaning agents each containing methanesulfonic acid and a predetermined semipolar organic boron surfactant were prepared in the proportions shown in Table 4, and then each of them was prepared. 20 pieces of 5 cm × 5 cm pieces of surface-printed iron cans (handling by Suntory Co., Ltd.) after use were put into 1 kg, and they were agitated and contacted at 80 ° C. for 1 hour at a rotation speed of 50 rpm.

Subsequently, the treated iron piece was taken out and rinsed and washed with normal temperature water for 10 seconds, and the presence or absence of removability of the printed surface and cleanliness of the metal surface was examined.

[0030]

[Table 4]

Also, as a comparative test, the above-mentioned Example 1 was used.
The compositions of Comparative Test Examples I and II tested in 1. were selected and tested simultaneously.

Results are shown in Table 5.
It was confirmed that the metal surface cleaning agent of No. 11 showed good performance even on the iron surface.

[0033]

[Table 5]

Example 4 In the same manner as in Example 1, metal surface detergents each containing methanesulfonic acid and a predetermined semipolar organic boron surfactant were prepared in the proportions shown in Table 6, and then each was prepared. 20 kg
Each was taken in a separate device and kept heated to 50 ° C. Next, while moving the liquid through air at a flow rate of 30 liters / min, make an iron cart caster cover (external diameter 4
5 mm, inner diameter 14 mm, thickness 5.5 mm)
Twenty samples with buff residue attached to the area of No. 4 were put in and contacted for 1 minute.

Subsequently, the treated sample was taken out, rinsed with normal temperature water for 1 second and washed, and the peeling property of the buff residue was examined.
Furthermore, chromium plating was performed under the condition of current density of 5 A / dm, and the homogeneity was observed to check whether or not the metal surface had cleanliness.

[0036]

[Table 6]

For the comparative test, the following four kinds of compositions were prepared at the same time and subjected to the same test.

Composition of Comparative Test Example III: A homogeneous solution consisting of 2% p-toluenesulfonic acid, 32% of the specified semipolar organic boron surfactant (5), 26% diethylene glycol monobutyl ether and 40% water.

Composition of Comparative Test Example IV: From 3% sulfuric acid, 31% of the specified semipolar organoboron surfactant (13), 16.5% ethylene glycol, 16.5% diethylene glycol monobutyl ether and 33% water. Homogeneous solution.

Composition of Comparative Test Example V A homogeneous solution of 2% methanesulfonic acid, 32% poly (12) oxyethylene glycol monolaurate, 26% diethylene glycol monobutyl ether and 40% water.

Composition of Comparative Test Example VI: Methanesulfonic acid 20%, glycerin monocaprylate 1%, sorbitol monolaurate 2%, poly (10) oxyethylene glycerin ether monooleate 10%,
Poly (20) oxyethylene diglycerin ether dipalmitate 7%, ethyl alcohol 10%,
A homogeneous solution consisting of 10% methyl ethyl ketone and 40% water.

The results are shown in Table 7, which is the production example 12 of the present invention.
The superior performance of ~ 16 metal surface cleaners was confirmed.

[0043]

[Table 7]

Example 5 20 kg of each of the metal surface cleaning agents of Production Examples 12 to 16 of the present invention shown in Table 6 used in Example 4 were placed in an ultrasonic cleaner (manufactured by Ultrasonic Generator Co., Ltd.) and kept at 20 ° C. room temperature. After that, the ultrasonic device was activated. Among them, iron cart caster cover (outer diameter 45 mm, inner diameter 14 mm, thickness 5.5 mm)
Buffing was attached to an area of 1/4 of the surface of the above, and 20 samples in which the machine oil (cutting oil Miyagawa 246) was attached to the whole were put in and contacted for 40 seconds.

Subsequently, the treated sample was taken out, rinsed and rinsed with water at room temperature for 1 second, and the peelability of buff residue and the removability of machine oil were examined.

Further, chromium plating was performed under the condition of current density of 7 A / dm, and the homogeneity thereof was observed to check whether the metal surface had cleanliness.

Subsequently, the treated sample was taken out, rinsed and washed with normal temperature water for 1 second, and the peeling property of buff residue and the removability of mechanical oil were examined.

Further, chromium plating was performed under the condition of current density of 7 A / dm, and the homogeneity thereof was observed to examine whether or not the metal surface had cleanliness.

Also, as a comparative test, the above-mentioned Example 4 was used.
The compositions of Comparative Test Examples III, IV, V and VI tested in 1. were selected and tested simultaneously.

The results are shown in Table 8, which is the same as Production Example 12 of the present invention.
It was confirmed that -16 metal surface cleaners showed good performance.

[0051]

[Table 8]

Example 6 Production Examples 12 to 1 of the present invention shown in Table 6 used in Examples 4 and 5
20 kg of each of the metal surface cleaning agents of 6 were placed in an ultrasonic cleaner, and the temperature was kept constant at 20 ° C., after which the ultrasonic device was activated. In it, a brass insulator cap (diameter 5 mm, depth 10 mm with screw hole outer diameter 40 mm, maximum thickness 17)
(20 mm in diameter) with buff residue attached to 1/4 of the surface and lithium grease (Gold No. 0 manufactured by Tokyo Fuji Kosan Co., Ltd.) attached to the screw holes. Then, they were contacted for 1 minute.

Subsequently, the treated sample was taken out, rinsed with room temperature water for 1 second and washed, and the peelability of buff residue and the grease removability were examined.

Further, chromium plating was applied under the condition of 7 A / dm, and the homogeneity was observed to check whether or not the metal surface had cleanliness.

Also, as a comparative test, the above-mentioned Example 4 was used.
And the compositions of Comparative Test Examples III-VI tested in 5 and 5,
Tested at the same time.

The results are shown in Table 9 and are shown in Production Example 12 of the present invention.
It was confirmed that -16 metal surface cleaners showed good performance.

[0057]

[Table 9]

Example 7 In the same manner as in Example 1, metal surface detergents each containing methanesulfonic acid and a predetermined semipolar organic boron surfactant were prepared at the ratios shown in Table 10, and then the respective metal surface detergents were prepared. 1 kg
On the other hand, two copper plates (100 mm × 100 mm, thickness 2 mm) were put in and brought into contact with each other at 40 ° C. for 3 minutes under an inflow of N ₂ gas at a flow rate of 30 l / min.

Subsequently, the treated sample was taken out, rinsed with normal temperature water for 1 second and washed, and then dried by contacting it with N ₂ gas at room temperature.

Thereafter, with respect to the treated copper plate sample, boric acid: borax = 1: 1 (weight ratio) at 700 ° C. under the condition that the clearance between joints is 0.35 mm and the overlap margin is 4.2 mm. ) The mixture was used as a flux for flame brazing with BAg-1 silver brazing, and the fluidity and swirling property of the molten brazing were observed to examine the degree of cleanliness of the copper plate surface.

[0061]

[Table 10]

For comparison tests, the following two compositions were prepared at the same time and subjected to the same test.

Composition of comparative test example VII: p-toluenesulfonic acid 2%, predetermined semipolar organoboron surfactant (5) 38%, ethyl alcohol 40%, isopropyl alcohol 12%, dioxane 4% and lactic acid. Ethyl 4%
Homogeneous solution consisting of.

Composition of Comparative Test Example VIII: 2% methanesulfonic acid, 38% poly (24) oxyethylene glycerol ether dioleate, isopropyl alcohol 40%, furfuryl alcohol 10% and water 10
% Homogeneous solution.

The results are shown in Table 11, which is the same as Production Example 1 of the present invention.
The excellent performance showing the completeness of oxide film removal of 7 to 21 metal surface cleaning agents was confirmed.

[0066]

[Table 11]

[0067]

As described above, according to the present invention,
Using a system in which methanesulfonic acid and an organic boron surfactant exhibiting a semi-polar structure are mixed and dissolved in a hydrophilic solvent as a metal surface detergent, the dramatic penetration and expansion power produced are strong protons. As a result of (H ⁺ ) being uniformly and efficiently spread to the interface between the pure metal and the foreign substance, various coating components and adhering components which have been difficult or impossible to peel can be easily removed. As a result, the expected highly accurate pure metal surface can be reliably formed.

Therefore, the practice of the present invention not only contributes to the stabilization of the processing of metal products, but can also contribute greatly to the point that it can be applied as a simple method for reusing resources.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C11D 3:43 3:34) (72) Inventor Koji Matsumoto 34-8 Iwabuchicho, Kita-ku, Tokyo

Claims (4)

[Claims] 1. Methanesulfonic acid and a compound of general formula I in a hydrophilic solvent (However, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or an acyl group having a total of 8 to 22 carbon atoms, and 0 ≦ p ≦ 40, 0 ≦ q ≦
40,0 ≦ x ≦ 40, 0 ≦ y ≦ 40, and 0 ≦ n ₁
p + q + n ₂ x + y ≦ 40, m ₁ and m ₂ are 0 or 1, and in the relationship between m ₁ and n _{1 and} the relationship between m ₂ and n ₂ , when m ₁ = 0, n ₁ = 0 Or 3, m
_{When 1} = 1, n ₁ is also 1. When m ₂ = 0, n ₂ = 0
Or 3, when m ₂ = 1 then n ₂ is also 1 and R
_{At least one of 1} , R ₂ , R ₃ and R ₄ is an acyl group. ) 1 of the semipolar organoboron surfactants represented by
A metal surface cleaner comprising one or two or more species. 2. The metal surface cleaning agent according to claim 1, wherein the semipolar organic boron surfactant is di {γ-lauroyloxypoly (n = 12) oxyethyleneglycerin} borate. 3. The metal surface cleaning agent according to claim 1, wherein the semipolar organic boron surfactant is di {γ-oleoyloxypoly (n = 12) oxyethyleneglycerin} borate. 4. The ratio of methanesulfonic acid to a semipolar organic boron surfactant is 5 to 50% by weight in the former and 50 to 95% by weight in the latter. The described metal surface cleaner.