JP6526980B2 - Cleaning composition for aluminum metal - Google Patents

Description

  The present invention relates to a cleaning composition for aluminum-based metals.

  Aluminum-based metals such as aluminum metals and aluminum alloys are attracting attention as materials for reducing the weight of iron and the like. When a product made of such an aluminum-based metal is formed, a lubricant is usually applied to the surface of a mold or an aluminum-based metal, and after forming, the lubricant is removed using a cleaning agent. It is As such a detergent, there are a detergent using an alkali component (for example, Patent Documents 1 to 3), a detergent using an acid component (Patent Documents 4 and 5), and the like.

Japanese Patent Laid-Open No. 2004-123979 Unexamined-Japanese-Patent No. 2004-175871 JP 2007-2014 A Unexamined-Japanese-Patent No. 2002-332581 JP 2007-197775 A

  However, in the cleaning of aluminum-based metals formed under high temperature and high pressure such as forging, with a cleaning agent using an alkali component as in Patent Documents 1 to 3, a strong lubricant adhered to the metal surface by heat or pressure. It turned out that the denatured substance can not be removed. Further, cleaning with an acid-based cleaning agent as in Patent Documents 4 and 5 causes corrosion to the aluminum-based metal, which causes problems such as reduction in strength and dimensional change.

  Therefore, the present invention provides a cleaning composition which is excellent in the cleaning property and in which the erosion to the aluminum-based metal is suppressed.

Aluminum metal detergent composition it is according to the present invention, an organic monosulfonic acid (a), and, glycine, alanine, valine, leucine, isoleucine, serine, threonine, arginine, asparagine, lysine, glutamine, tryptophan, aspartic acid And at least one amino acid (b) selected from the group consisting of glutamic acid, cysteine, methionine, histidine, proline, phenylalanine and tyrosine, and having a pH of 6 or less .

  The method for cleaning an aluminum-based metal according to the present invention uses an aqueous solution containing the cleaning composition for an aluminum-based metal.

  According to the present invention, an excellent cleaning effect can be obtained while suppressing the erosion of the aluminum-based metal surface.

<Organic monosulfonic acid (a)>
The cleaning composition for an aluminum-based metal according to the present embodiment (hereinafter sometimes simply referred to as a cleaning composition) contains an organic monosulfonic acid (a).

  As the organic monosulfonic acid (a), for example, sulfo on an aliphatic carbon atom such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, hydroxymethanesulfonic acid, hydroxyethanesulfonic acid, and hydroxypropanesulfonic acid And compounds having a group, and compounds having a sulfo group on an aromatic carbon atom such as phenolsulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, and cumenesulfonic acid. These may be used alone or in combination of two or more. Among these, compounds having a sulfo group on an aromatic carbon atom are preferable because they can further suppress the erosion on aluminum-based metals.

  As one embodiment of the organic monosulfonic acid (a), a compound represented by the following general formula (1) may be used.

R ¹ -SO ₃ H (1)
In formula (1), R ¹ is a linear or branched alkyl group or hydroxyalkyl group having 1 to 9 carbon atoms (more preferably 1 to 4 carbon atoms), or 6 to 18 carbon atoms (more preferably Represents an aryl group or a hydroxyaryl group which is 6 to 13, more preferably 6 to 10). Here, a hydroxyalkyl group is an alkyl group having a hydroxyl group as a substituent, and a hydroxyaryl group is an aryl group having a hydroxyl group as a substituent. The compound represented by the formula (1) is an example of a compound having a sulfo group on the above aliphatic carbon atom when R ¹ is an alkyl group or a hydroxyalkyl group, and when R ¹ is an aryl group or a hydroxyaryl group These are examples of compounds having a sulfo group on the aromatic carbon atom.

<Amino acid (b)>
The detergent composition according to the present embodiment contains an amino acid (b).

  Amino acid (b) is a compound having an amino group and a carboxyl group in the molecule. Preferred are α-amino acids, for example, glycine, alanine, valine, leucine, isoleucine, serine, threonine, arginine, asparagine, lysine, glutamine, tryptophan, aspartic acid, glutamic acid, cysteine, methionine, histidine, proline, phenylalanine, and Tyrosine etc. are mentioned. These may be used alone or in combination of two or more.

  Among these, the amino acid (b) is preferably a compound represented by the following general formula (2) because the cleaning property is more excellent and the erosion of the aluminum-based metal surface can be further suppressed.

式（２）中、Ｒ²は、水素原子、炭素数１〜５の直鎖もしくは分岐鎖のアルキル基、または炭素数１〜５の直鎖もしくは分岐鎖のヒドロキシアルキル基を示す。Ｒ²は、より好ましくは、水素原子、炭素数１〜３のアルキル基、または炭素数１〜３のヒドロキシアルキル基を示す。

In formula (2), R ² represents a hydrogen atom, a linear or branched alkyl group of 1 to 5 carbon atoms, or a linear or branched hydroxyalkyl group of 1 to 5 carbon atoms. R ² more preferably represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms.

Specific examples of the compound represented by the formula (2) are as follows:
· Wherein R ² is a hydrogen atom;
Glycine R ² is an alkyl group having 1 to 5 carbon atoms (the number in carbon atoms of R ² in parentheses);
Alanine (1), valine (3), leucine (4), isoleucine (4)
· Wherein R ² is a hydroxyalkyl group having 1 to 5 carbon atoms (the number in carbon atoms of R ² in parentheses);
Serine (1), threonine (2)

  In the detergent composition according to the present embodiment, the content of the amino acid (b) is preferably 5 to 1000 parts by mass with respect to 100 parts by mass of the organic monosulfonic acid (a). Within such a range, the cleaning property is more excellent, and the erosion of the aluminum-based metal surface can be further suppressed. The lower limit of the content of the amino acid (b) per 100 parts by mass of the organic monosulfonic acid (a) is more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and the upper limit is 500 parts by mass or less The content is more preferably 300 parts by mass or less, and even more preferably 200 parts by mass or less.

<Oxyalkylene monool (c)>
The detergent composition according to the present embodiment may further contain oxyalkylene monool (c). By containing the oxyalkylene monool (c), the washability is further excellent.

  The oxyalkylene monool (c) is a compound having at least one oxyalkylene group and one hydroxyl group in the molecule, and examples thereof include an alkylene oxide adduct of monool and the like.

  As a specific example of the oxyalkylene monool (c), a compound represented by the following general formula (3) is preferable from the viewpoint of being excellent in the cleaning property.

R ³ -O- (AO) _n -H (3)
In formula (3), R ³ represents a hydrocarbon group having 6 to 30 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n is the average added mole number of the oxyalkylene group, It is a number of 1-100.

R ³ is preferably an aliphatic hydrocarbon group having 6 to 18 carbon atoms, and is preferably a linear or branched alkyl group having 6 to 18 carbon atoms. In addition, the carbon number of R ³ is preferably 8 to 14, and more preferably 10 to 12 because the cleaning property is further excellent and the rinse property after cleaning is also excellent.

  From the same reason, n in the formula (3) is preferably 2 or more, more preferably 5 or more. Further, n is preferably 30 or less, more preferably 15 or less, and still more preferably 10 or less.

(AO) _n in the formula (3) may be a random adduct or a block adduct of oxyalkylene groups having different carbon numbers. (AO) _n preferably contains 50 to 100% by mass, and more preferably 70 to 100% by mass of an oxyethylene group, because the cleaning property is further excellent and the rinsing property after cleaning is also excellent.

  In the cleaning agent composition which concerns on this embodiment, it is preferable that content of oxyalkylene monool (c) is 5-1000 mass parts with respect to 100 mass parts of organic monosulfonic acid (a). By setting it in such a range, the washability becomes more excellent. The lower limit of the content of the oxyalkylene monool (c) per 100 parts by mass of the organic monosulfonic acid (a) is more preferably 20 parts by mass or more, still more preferably 50 parts by mass or more, and the upper limit is 500 parts by mass It is more preferably part or less, still more preferably 300 parts by mass or less.

  The content of the oxyalkylene monool (c) is also preferably 5 to 1000 parts by mass with respect to 100 parts by mass of the amino acid (b). By setting it in such a range, the washability becomes more excellent. The lower limit of the content of oxyalkylene monool (c) per 100 parts by mass of amino acid (b) is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and the upper limit is 500 parts by mass or less It is more preferable that

<Organic phosphonic acid (d)>
The detergent composition according to the present embodiment may further contain an organic phosphonic acid (d). By containing the organic phosphonic acid (d), the cleaning property is further excellent. Either one or both of the organic phosphonic acid (d) and the oxyalkylene monool (c) may be blended.

  Examples of organic phosphonic acid (d) include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), ethanehydroxy-1 , 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotris (methylenephosphonic acid) (NTMP), 3-carboxy-3-phosphonohexane The acid (PBTC) and ethylenediaminetetrakis (methylene phosphonic acid) (EDTMP) and the like can be mentioned. These may be used alone or in combination of two or more.

  Among these, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or nitrilotris (methylene phosphonic acid) (NTMP) are more preferable because the washing properties are further excellent.

  In the detergent composition according to the present embodiment, the content of the organic phosphonic acid (d) is preferably 5 to 1000 parts by mass with respect to 100 parts by mass of the organic monosulfonic acid (a), and the cleaning property is It will be better. The lower limit of the content of the organic phosphonic acid (d) per 100 parts by mass of the organic monosulfonic acid (a) is more preferably 20 parts by mass or more, still more preferably 40 parts by mass or more, and the upper limit is 500 parts by mass The content is more preferably the following, further preferably 300 parts by mass or less, and may be 200 parts by mass or less.

  The content of the organic phosphonic acid (d) is also preferably 5 to 1000 parts by mass with respect to 100 parts by mass of the amino acid (b), and the cleaning property is more excellent. The lower limit of the content of the organic phosphonic acid (d) per 100 parts by mass of the amino acid (b) is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, and the upper limit is 500 parts by mass or less More preferably, it is 300 parts by mass or less.

  The content of the organic phosphonic acid (d) is preferably 5 to 1000 parts by mass with respect to 100 parts by mass of the oxyalkylene monool (c), and the cleaning property is further improved. The lower limit of the content of the organic phosphonic acid (d) relative to 100 parts by mass of the oxyalkylene monool (c) is more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and the upper limit is 500 parts by mass The content is more preferably the following, further preferably 300 parts by mass or less, and may be 200 parts by mass or less.

<Other ingredients>
The detergent composition according to the present embodiment may be an aqueous solution. That is, an aqueous solution obtained by dissolving the organic monosulfonic acid (a) and the amino acid (b) described above, preferably together with an oxyalkylene monool (c) and / or an organic phosphonic acid (d) as optional components, in water It may be.

  In the detergent composition according to the present embodiment, known additives can be used as long as the effects are not inhibited. Examples of known additives include the following.

-Metal ion blocking agent other than the above (d) (chelant):
For example, L-glutamic acid diacetic acid, methylglycine diacetic acid, gluconic acid, glycolic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylenediaminetetra And amine hexaacetic acid, hydroxyethyl iminodiacetic acid, triethylenetetramine hexaacetic acid, citric acid and malic acid.

Water soluble high boiling point solvent:
The solvent whose solubility in 25 ° C to 100 mass parts of water is 100 mass parts or more, and whose boiling point in 1 atmosphere is 100 ° C or more. For example, alcohol solvents, glycol ether solvents, and pyrrolidone solvents can be mentioned.

Defoamer:
For example, silicone antifoaming agents, higher alcohol antifoaming agents, polyglycol antifoaming agents, and mineral oil antifoaming agents may be mentioned.

  In addition, preservatives, rust inhibitors, antioxidants, pH adjusters, nonionic surfactants other than the above (c), anionic surfactants, cationic surfactants, amphoteric surfactants, fluorosurfactants You may add an agent etc.

  The detergent composition according to the present embodiment is preferably an acidic detergent composition, where the acidity means that the pH at normal temperature (23 ° C.) is 6 or less, more preferably 4 or less.

<Method of using detergent composition>
The detergent composition according to the present embodiment may be used after diluting it with water. Although the concentration after dilution is not particularly limited, it is preferable that the concentration of the organic monosulfonic acid (a) is 0.1 to 10% by mass from the viewpoint of washing properties. The concentration of each component of the amino acid (b), oxyalkylene monool (c) and organic phosphonic acid (d) can be set according to the ratio to the above-mentioned organic monosulfonic acid (a).

  In order to wash the aluminum-based metal using an aqueous solution containing the cleaning composition, the aqueous solution may be brought into contact with the surface of the aluminum-based metal. The cleaning method is not particularly limited, and for example, known methods such as immersion cleaning, ultrasonic cleaning, brush cleaning, scrub cleaning, jet cleaning, spray cleaning and hand cleaning can be used. The washing temperature is not particularly limited, and usually can be set appropriately at 10 to 80 ° C. The washing time is not particularly limited, and usually can be appropriately set in 1 minute to 24 hours.

  The aluminum-based metals to be cleaned include aluminum metals as well as aluminum alloys. Examples of the aluminum alloy include aluminum-copper, aluminum-manganese, aluminum-magnesium, aluminum-magnesium-silicon, aluminum-zinc-magnesium, and aluminum-zinc-magnesium-copper, etc. is there.

  The present embodiment can be preferably used for cleaning an aluminum-based metal (hereinafter sometimes referred to as an aluminum-based metal molded article) molded by applying a lubricant, that is, after the aluminum-based metal is molded, It is preferably used for cleaning to remove deposits such as lubricants and their modified products from the surface. More specifically, it is used for cleaning aluminum-based metal moldings formed under high temperature and high pressure such as forging. The aluminum-based metal molded article thus washed can be subjected to chemical conversion treatment and coating treatment after being washed with water according to a known method.

  The type of lubricant is not particularly limited. For example, black lubricants whose main component is graphite or molybdenum disulfide, carboxylic acid compounds, phosphoric acid compounds, synthetic mica, white lubricants whose main component is boron nitride, etc. are generally used. Can be used to clean aluminum-based metals formed by applying various lubricants.

  The cleaning agent composition according to the present embodiment is not limited to the cleaning after the above molding, and can be used for cleaning various products, parts, molded articles, and devices made of aluminum-based metals.

  Next, although it demonstrates based on an Example and a comparative example, this invention is not limited to these Examples.

(Examples 1 to 15, Comparative Examples 1 to 6)
Based on the description in Table 1, a cleaning agent composition was obtained by mixing the respective raw materials at a predetermined ratio (mass ratio). The “isodecyl alcohol 7EO adduct” in Table 1 is obtained by adding 7 moles of ethylene oxide to isodecyl alcohol. The "lauryl alcohol 8EO2PO adduct" is obtained by randomly adding 8 moles of ethylene oxide and 2 moles of propylene oxide to lauryl alcohol.

  Using the obtained detergent composition, the detergency and the erodibility were evaluated by the following method.

(1) Detergency (black lubricating oil)
A black lubricant (trade name: Delta Forge, manufactured by Henkel Corp.) was applied to an aluminum alloy (aluminum-magnesium-silicon, JIS aluminum alloy No. A6061, size: 25 mm × 70 mm × 2 mm). The sample was heated at 450 ° C. for 10 minutes to obtain a soiled test piece. Using the obtained test pieces, a washing test was performed under the following conditions (I) to (IV).

  A transparent sheet (25 mm × 70 mm) in which 5 mm wide grids were described was placed on the upper and lower surfaces of the test pieces after the cleaning test to count the unstained squares, and the ratio (%) was calculated. Evaluation was performed on the following basis based on the said ratio.

:: 100%
○: 98% or more and less than 100% ×: 95% or more and less than 98% ××: less than 95%

(I) Washing at 25 ° C. A mixture of 40 g of the detergent composition and 160 g of water was adjusted to 25 ° C., and the above test piece was immersed for 6 hours. Subsequently, the test piece was dipped and rinsed in 200 g of ion-exchanged water at 25 ° C. for 3 minutes, and then the test piece was taken out and dried at 80 ° C. for 20 minutes.

(II) Washing at 50 ° C. The same operation as in (I) above was performed except that the temperature of the washing solution was set to 50 ° C.

(III) Ultrasonic Cleaning at 40 ° C. A mixture of 20 g of the cleaning composition and 180 g of water was used as a cleaning liquid. The above cleaning solution was put in an ultrasonic cleaner and adjusted to 40 ° C., and the above test piece was immersed and cleaned for 10 minutes under the conditions of 38 kHz and 300 W. Subsequently, the test piece is immersed in an ultrasonic cleaner charged with 200 g of ion-exchanged water at 40 ° C., rinsed for 3 minutes under conditions of 38 kHz and 300 W, and further charged with 200 g of ion-exchanged water at 25 ° C. The test pieces were immersed and rinsed for 3 minutes at 38 kHz and 300 W, and then the test pieces were dried at 80 ° C. for 20 minutes.

(IV) Ultrasonic cleaning at 60 ° C. The same operation as in (III) above was performed except that the temperature of the washing solution was set to 60 ° C.

(2) Washability (White Lubricant)
A white lubricant (trade name: Hot Aqualube AL-85F, made by Daido Chemical Industries, Ltd.) is applied to an aluminum alloy (aluminium-zinc-magnesium-copper, JIS aluminum alloy number A 7075, size: 25 mm x 70 mm x 2 mm) did. The sample was heated at 450 ° C. for 10 minutes to obtain a soiled test piece. It evaluated by the method similar to said (1) detergency (black lubricating oil) using the obtained test piece.

(3) Erosion Ammonia (JIS aluminum alloy No. A1050, size: 25 mm × 70 mm × 2 mm) and aluminum alloy (aluminum-magnesium-silicon, JIS aluminum alloy No. A6061, size: 25 mm × 70 mm × 2 mm) are degreased with methanol The test piece was obtained by carrying out.

  The above test piece was immersed in a mixed solution of 20 g of the cleaning composition and 180 g of water for 6 hours. In addition, the temperature of the liquid mixture was performed on 25 degreeC and two conditions of 60 degreeC. At this time, the generation of air bubbles from the surface of the test piece was confirmed. Subsequently, the test piece was immersed in ion exchange water (25 ° C.) for 3 minutes, further immersed in another ion exchange water (25 ° C.) for 3 minutes, and then dried at 80 ° C. for 20 minutes. The surface of the test piece was visually observed to confirm the presence or absence of a change before and after the test. In addition, the weight change rate before and after the test was calculated.

  The results are as shown in Table 2. In Comparative Examples 3 and 4 in which sulfuric acid was used alone or in combination of sulfuric acid and citric acid, the corrosion to aluminum and aluminum alloy was large, and the cleaning property was also inferior in the cleaning property particularly at low temperature. In Comparative Examples 1 and 2 in which the organic monosulfonic acid (a) was used, although the erosion was improved as compared with Comparative Examples 3 and 4, the effect was insufficient because the amino acid (b) was not used in combination. And the cleaning properties were also inadequate. On the other hand, Comparative Examples 5 and 6 using an alkali component are inferior in the cleaning property, and in Comparative Example 5 where the alkali component is sodium hydroxide, the effect of suppressing the erosion on aluminum and aluminum alloy was also insufficient. .

  On the other hand, when it was Examples 1-15 which used the organic monosulfonic acid (a) and the amino acid (b) together, it was excellent also in the washability, suppressing the corrosion with respect to aluminum and aluminum alloy. From the comparison between Example 6 and Examples 2 and 5, as the organic monosulfonic acid (a), an aromatic such as toluenesulfonic acid or phenolsulfonic acid is preferred to an aliphatic sulfonic acid such as methanesulfonic acid. The sulfonic acid was more effective in suppressing the erosion on aluminum. As shown in Examples 9 to 15, by further adding oxyalkylene monool (c) and / or organic phosphonic acid (d) to organic monosulfonic acid (a) and amino acid (b), it is possible to wash it. The further improvement effect of

Claims (5)

Organic monosulfonic acid (a), and,
At least one selected from the group consisting of glycine, alanine, valine, leucine, isoleucine, serine, threonine, arginine, asparagine, lysine, glutamine, tryptophan, aspartate, glutamic acid, glutamic acid, cysteine, methionine, histidine, proline, phenylalanine, and tyrosine Species amino acids (b)
The cleaning agent composition for aluminum-type metals which is 6 and whose pH is 6 or less .   The cleaning composition for an aluminum-based metal according to claim 1, wherein the amino acid (b) is contained in an amount of 5 to 1000 parts by mass with respect to 100 parts by mass of the sulfonic acid (a).   Furthermore, the cleaning composition for aluminum-type metals of Claim 1 or 2 containing oxyalkylene monool (c).   Furthermore, the cleaning composition for aluminum-type metals of any one of Claims 1-3 containing organic phosphonic acid (d).   The washing | cleaning method of aluminum-type metal using the aqueous solution containing the cleaning agent composition for aluminum-type metals of any one of Claims 1-4.