JPH0565493A - Deformation processing lubricant of aluminum alloy or nonferrous metal - Google Patents

Abstract

PURPOSE:To obtain the subject deformation processing lubricant containing an alkylphosphonic acid derivative synthesized from an olefin having a double bond at alpha-position of its specific carbon number and phosphorous acid, etc., in a diluent, having excellent lubricating property and rustproof property and free from deterioration of degreasing properties. CONSTITUTION:Benzoyl peroxide, etc., is added as a catalyst to an olefin (e. g.1-octene) having a double bond at the alpha-position of its 6-60C and at least one kind of phosphorous acid, hypophosphoric acid and dialkyl phosphite, etc., in a solvent such as dioxane and the olefin is reacted with the above-mentioned phosphorus compound at 60-80 deg.C for 10hr. Then the unreacted raw material is removed by solvent extraction and the solvent is distilled off to afford an alkylphosphonic acid derivative of the formula (R1 is 6-60C alkyl; R2 and R3 are H, 1-18C alkyl, oxyalkylene, alkali metal or alkaline earth metal) e.g., octly phosphonic acid. Then the alkylphosphonic acid derivative is added to a diluent (e.g. kerosene) at an amount of 1.0-100wt.% and mixed to provide the objective deformation processing lubricating oil for aluminum alloys or nonferrous metals.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum alloy, non-ferrous metal pressing, drawing, extruding, drawing and ironing plastic working lubricant. More specifically, a single oil is used for lubricity, rust prevention and degreasing. It is intended to provide a plastic working lubricant having a wide range of excellent properties and excellent performance.

[0002]

2. Description of the Related Art In general, aluminum alloy sheet press working lubricants include mineral oil as a base oil, naphthenic acid, petroleum sulfonate,
Alkyl carboxylic acids, aliphatic alcohols, synthetic esters, fats and oils, or their metal salts and alkyl phenols are generally added.

However, due to the improvement of environmental problems against global warming, the saving of petroleum resources, and the rise of petroleum prices, it is desired to improve the fuel consumption of automobiles. Efforts are being made to improve fuel efficiency.

Aluminum alloy sheets have been investigated in place of the current high-strength steel sheets, but press formability is difficult and problems such as press cracking and generation of aluminum alloy powder occur due to insufficient lubrication. Lubricating oil applied to aluminum alloy sheets has also been required to have multifunctional properties.

In these aluminum alloys, magnesium, silicon, etc. are added to aluminum in order to improve the specific strength. If other elements are added, the workability becomes extremely poor, the rigidity is low, and scratches easily occur. Further, spot weldability is required to assemble the product after processing. If a large amount of lubricant remains on the surface of the aluminum alloy in order to maintain the workability, the conductivity of heat and electricity deteriorates and the weldability deteriorates. Therefore, there is a demand for a lubricant that can be plastically processed with a very thin film.

After the spot welding, the lubricating film is removed from the surface of the processed aluminum alloy by an automatic cleaning device, and the surface is treated and painted. In order to prevent these post-treatments from being adversely affected, it is necessary for the lubricating film to be washable.

If the lubricating film has good washability, the subsequent surface treatment is excellent, the coatability is excellent, and the adhesion of the coating film is excellent.
Increases product value without causing problems such as peeling. These cleaning steps are performed in a short time, and since the aluminum alloy is rich in chemical reactivity, it is performed with a weak alkaline cleaning agent.
Therefore, in order to remove the lubricant film, the lubricant itself needs to have a structure that dissolves in water or is easily emulsified.

Also, aluminum alloy plate and coil manufacturers apply lubricants to these surfaces before shipping, or apply lubricants to these surfaces before plastic working and leave them for a long time. Is estimated. During this time, it is necessary for the aluminum alloy surface not to be corroded in order to improve the post process,
It is also an essential condition.

That is, not only lubricity but also rust prevention, degreasing properties, etc. can be mentioned, and no single press oil satisfying all of them has been obtained at present. In view of such a current situation, it is an object of the present invention to provide a novel press lubricant that is excellent in rust prevention as well as in lubricity with a single oil and is easy to degrease.

[0010]

The problem to be solved by the present invention is to eliminate the drawbacks of the above-mentioned conventional plastic working oils such as aluminum alloy press oil and drawing oil. More specifically, the aluminum alloy sheet has excellent lubricity in the step of forming an aluminum alloy sheet, for example, a pressing step, and also has excellent rust resistance, and has the same or more degreasing properties as conventional press oils. To develop plastic working oil. Further, conventional commercial phosphoric acid esters have poor hydrolysis resistance, and the formation of inorganic phosphoric acid is unavoidable, which causes corrosion of aluminum alloys. Further, it is thermally unstable, easily decomposes at a relatively low temperature, and inorganic phosphoric acid is produced quickly, causing corrosion.

[0011]

Means for Solving the Problems In the present invention, as a result of extensive studies to solve the above problems, a specific compound was synthesized, and the compound was added to a base oil such as mineral oil in an amount of 1.0 to 100% by weight. , Finding that the above problems can be solved,
The present invention has been completed.

That is, it has an excellent press forming lubricity which cannot be obtained by a plastic working oil such as a conventional aluminum alloy press oil,
Further, it is required that the plastic working oil such as the conventional aluminum alloy press oil has the same or more rust prevention and degreasing properties.

[0013]

INDUSTRIAL APPLICABILITY In the present invention, a compound synthesized from an olefin having 6 to 60 carbon atoms and having a double bond at the α-position, and phosphorous acid, hypophosphorous acid, or dialkyl phosphite The basic idea is to use the alkylphosphonic acid derivative shown in 1] as a base oil (mineral oil) alone or in combination with other auxiliary agents.

[0014]

[Chemical 1]

(Wherein R ₁ is a C _{6 to} C ₆₀ linear or branched alkyl group, and R ₂ or R ₃ is H or C
_{1 to} C ₁₈ linear or branched alkyl group, oxyalkylene group, alkali metal or alkaline earth metal)

In the present invention, the specific compound represented by the above [Chemical formula 1] is further reacted with at least one of the compounds represented by the following compounds (1) and (2) to (3). Also included are embodiments in which the product is included in the base oil alone or with other auxiliaries. Compound (1)

[0017]

[Chemical 2]

(Wherein R ₄ , R ₅ , and R ₆ are all or two or one is H or a C _{1 to} C ₁₈ straight-chain or branched alkyl group, or R ₆ is R ₇ —O—R ₈ And the rest is H. R ₇ is a C _{1 to} C ₆ linear or branched alkyl group, and R ₈ is a C _{1 to} C ₁₈ linear or branched alkyl group).

Compound (2) Amino alcohol

Compound (3)

[0021]

[Chemical 3]

(R ₁₅ is an alkyl group having ₁ to ₁₈ carbon atoms,
R ₁₄ , ₁₆ , ₁₇ , and ₁₈ are H or an alkyl group)

[0023]

In the present invention, at least one of the compounds of the above [Chemical formula 1] and compounds (1) to (3) is used.
By using the seed, it becomes an oil agent having excellent lubricity with respect to aluminum or aluminum alloy, rust preventive property, and easy to degrease. More specifically, in the plastic working oil composition of the present invention, a reaction product of the above [Chemical formula 1] and at least one of the compounds of (1) to (3) is a base oil such as kerosene, spindle oil, machine oil, etc. 1.0% for low boiling point solvents such as toluene.
Those added in an amount of up to 100% by weight exhibit superior lubricity and rust prevention properties to the additive-free base oil and commercial aluminum alloy press oil. This is because an adsorption film of an alkylphosphonic acid derivative, which is a reaction product of the above-mentioned formula [Chemical formula 1] and at least one of the compounds of (1) to (3), is uniformly formed on the surface of the aluminum alloy, and water, halogen, inorganic It is said that it is a tough material that is not destroyed even by a corrosive factor such as acid.

Further, as shown in the following experimental examples, the compound of the present invention is excellent in hydrolysis resistance and thermal decomposition resistance, is hard to generate inorganic phosphoric acid, and is excellent in corrosion.

[0025]

Experimental Example The characteristics of the additives shown in Table 1 below were measured.

[0026]

[Table 1]

<Hydrolysis resistance> Method: 100 g of 10% KOH aqueous solution was added to 2 g of the sample, and the mixture was heated under reflux at 95 ° C. for 10 hours, extracted with ether, and the phosphorus content of the oil layer and the water layer was measured to determine the inorganic phosphorus compound. Was used as an index of hydrolysis resistance. The results are shown in Table 1.

A:

[Chemical 4]

B:

[Chemical 5]

C:

[Chemical 6] As is clear from Table 1, the compounds of the present invention are chemically more stable than commercially available phosphoric acid esters. This is due to the difference in the atoms that bond with phosphorus, and with the P-C bond,
This is due to the difference in the bond energy of the P-O-C bond.

<Thermal stability>

[0032]

[Figure 1]

In FIG. 1, 1 is the compound A of the present invention (Reference Example 6), 2 is a commercially available phosphate ester B, and 3 is a commercially available phosphate ester C. Weight loss measurement with thermobalance

Measurement conditions: Sample 10 to 15 mg Temperature rising rate 5 ° C / min Temperature range Room temperature to 700 ° C N ₂ gas amount 100 ml / min

<Lubricity>

[0036]

[Fig. 2]

The numbers in FIG. 2 indicate the same as in FIG. Friction coefficient measurement by Soda type pendulum type oiliness test

Measurement conditions: temperature range 40 to 280 ° C. test ball SUJ-2 (φ3 / 16 inch) test rod SUJ-2

The alkylphosphonic acid derivative which is the above-mentioned specific compound used in the present invention is not particularly limited in its production method, but it is produced, for example, by the following method.

An olefin having 6 to 60 carbon atoms and having a double bond in the α-position, and at least one of phosphorous acid, hypophosphorous acid and dialkyl phosphite are used in an amount of 1.0 to 2.0 with respect to the olefin. After mixing them in moles, a radical initiator such as benzoyl peroxide or azobisisobutyronitrile is used as a catalyst, and the reaction is carried out in a nitrogen atmosphere at 60 to 150 ° C. for 4 to 20 hours to obtain an alkylphosphonic acid or an alkylphosphonic acid dialkyl ester. To get Alkylphosphonic acid dialkyl esters can be further prepared with a suitable catalyst such as concentrated hydrochloric acid,
The alkylphosphonic acid monoalkyl ester or alkylphosphonic acid can be obtained by hydrolysis in the presence of concentrated alkaline water. Then addition of alkylene oxide,
It can be an amination or amine salt, a condensation with amino alcohol or a salt with amino alcohol, an alkali metal salt or an alkaline earth metal salt.

The reaction conditions are shown in more detail below.

(A) Alkylene oxide addition reaction 1 mol of alkylphosphonic acid or alkylphosphonic acid monoalkyl ester was placed in an autoclave, and 0.5-2% by weight of an alkali such as potassium hydroxide was added as a catalyst to the autoclave. Nitrogen-substituted, 0.5-10 mol of one kind of ethylene oxide, propylene oxide, etc. is pressed in while stirring, the temperature is raised, the reaction is carried out at 50-200 ° C. for 1-20 hours, and filtration is carried out if necessary. , An alkylene oxide adduct is obtained.

(B) Salt with amine or amino alcohol Into a reactor equipped with a thermometer, a stirrer and a reflux condenser, 1 mol of alkylphosphonic acid or alkylphosphonic acid monoalkyl ester is added, and alkylamine or alkanolamine is added. 0.5 to 2.0 mol is added, and the mixture is stirred at 100 to 150 ° C. for 1 to 5 hours to obtain an alkylamine salt or an alkanolamine salt.

(C) Alkali metal or alkaline earth metal salt 1 mol of alkylphosphonic acid or alkylphosphonic acid monoalkyl ester was placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and sodium hydroxide or hydroxide was added. 0.5-1.0 mol of magnesium is added and the reaction is carried out at 100-150 ° C for 1-5 hours to obtain an alkali metal or alkaline earth metal salt.

Examples of the olefin having a double bond at the α-position used in the present invention include 1-hexene, 1-octene, 1-decene, 1-dothecene, 1-tridecene, 1-
Tetradecene, 1-pentadecene, 1-hexadecene,
Carbon number 6 such as 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene
Each α-olefin of 60 to 60 is mentioned, and an olefin having 12 to 60 carbon atoms is preferable. When the carbon number is 5 or less, the boiling point and the flash point are low, and the yield in synthesis is extremely low. Carbon number 6
If it exceeds 0, the melting point is extremely high and the solubility is poor, which is not preferable.

Examples of the dialkyl phosphite include dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, dihexyl phosphite, di-2 ethylhexyl phosphite, didecyl phosphite, didodecyl phosphite, ditetradecyl phosphite. Phyto, dihexadecyl phosphite, dioctadecyl phosphite, etc. are mentioned, Preferably it is a C1-C8 dialkyl phosphite. Carbon number 9
The above dialkyl phosphites are not preferable because they are easily hydrolyzed.

The alkylene oxide has an alkylene group having about 2 to 6 carbon atoms, and ethylene oxide and propylene oxide are particularly preferable.

Amines used for amination and amine salts include ammonia, methylamine, dimethylamine,
Trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine,
Tripropylamine, isopropylamine, diisopyropyramine, triisopropylamine, butylamine,
Dibutylamine, tributylamine, pentylamine,
Hexylamine, heptylamine, octylamine, 2
-Ethylhexylamine, decylamine, dodecylamine, tetradecylamine, octadecylamine may be mentioned, with preference given to primary alkylamines. Also, H ₂ N
In the amine represented by _{-R 7 -0-R 8, R} 7 is 1 to 3 carbon atoms, R ₈ is preferably from 6 to 18 carbon atoms. The compound having 5 or 6 carbon atoms of R ₇ is not preferable in view of the high unit price of the commercially available synthetic product. R ₈ having 19 or more carbon atoms has a high melting point and tends to have poor solubility. The number of added moles is about 1 to 10,
If it is more than this range, the solubility decreases.

Examples of amino alcohols include monoethanolamine, diethanolamine, triethanolamine, propanolamine, isopropanolamine,
N, N-dimethylpropanolamine, N, N-diethylpropanolamine, butanolamine, neopentanolamine are preferable.

As the polyamine, ethylenediamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N, N-dimethylaminopropylamine, N, N-diethylaminopropylamine are preferred.

As the alkali metal and alkaline earth metal, Na, K, Ca, Ba, Mg and the like are preferable.

The compound of the present invention has no effect at 1.0% by weight or less, and the compound of the present invention is a known additive such as sulfonates, esters, alcohols, metal soaps,
It can be commonly used as an antioxidant.

[0053]

EXAMPLES In order to facilitate understanding of the present invention, reference examples as synthetic examples are shown below, and examples using the synthetic products are shown. However, the following synthetic examples and examples limit the present invention in any way. Not a thing.

[0054]

Reference Example 1 1-octene (1.0 mol), phosphorous acid (2.0 mol) and 500 ml of dioxane as a solvent.
Was charged into a reactor equipped with a thermometer, a stirrer, a nitrogen gas introduction tube, a dropping funnel, and a reflux condenser, and benzoyl peroxide (0.1 mol) was dissolved as catalyst in 50 g of 1-octene. In addition, 1 at 60-80 ° C
Reaction was carried out for 0 hours, unreacted phosphorous acid and unreacted 1-octene were removed by solvent extraction, and the solvent was further distilled off to obtain octylphosphonic acid. Neutralization number 580 (calculated value 584).

[0055]

[Reference Example 2] An olefin having 16 carbon atoms (1.0 mol) and diisopropyl phosphite (1.2 mol) were placed in a reactor equipped with a thermometer, a stirrer, a nitrogen gas introducing pipe, a dropping funnel, and a reflux cooling pipe. And slowly add benzoyl peroxide (0.2 mol) as a catalyst in a nitrogen gas atmosphere.
The reaction was carried out at 00 to 150 ° C. for 8 hours to obtain an alkylphosphonic acid diisopropyl ester having 16 carbon atoms.

[0056]

Reference Example 3 In the same manner as in Reference Example 2, an alkylphosphonic acid diisopropyl ester having 28 carbon atoms was prepared.
The mixture was stirred for 15 hours under azeotropy with% hydrochloric acid, washed with water and purified to obtain an alkylphosphonic acid monoisopropyl ester having 28 carbon atoms. Neutralization number 116 (calculated value 109).

[0057]

[Reference Example 4] The number of carbon atoms was 30 to 5 in the same manner as in Reference Example 1.
0 alkylphosphonic acid was obtained and further in an autoclave,
Using potassium hydroxide (1 wt%) as a catalyst, 1 mol of ethylene oxide was added to obtain monohydroxyethyl alkylphosphonate having 30 to 50 carbon atoms. Neutralization number 79 (calculated value 72).

[0058]

[Reference Example 5] The number of carbon atoms was 30 to 5 in the same manner as in Reference Example 3.
Alkylphosphonic acid monoisopropyl ester of 0 was obtained, 1 mol of laurylamine was added to 1 mol thereof, and the mixture was heated with stirring at 80 to 100 ° C. for 1 hour to give 30 carbon atoms.
˜50 lauryl amine salt of alkylisopropylphosphonate monoisopropyl was obtained.

[0059]

[Reference Example 6] The number of carbon atoms was 20 to 28 in the same manner as in Reference Example 1.
To give 1 mole of N, N
-Add 1 mol of diethyl propanolamine and add 100-
It is heated and stirred at 130 ° C. for 5 hours to be condensed to have 20 to 20 carbon atoms.
28 alkylphosphonic acid mono (diethylamino) propanol ester was obtained.

[0060]

[Reference Example 7] The number of carbon atoms was 20 to 28 in the same manner as in Reference Example 3.
To obtain monoisopropyl alkylphosphonate, 0.5 mole of magnesium hydroxide was added to 1 mole of the same, and
The mixture was heated and stirred at 0 to 130 ° C. for 3 hours to obtain an alkylphosphonic acid monoisopropyl mono-Mg salt having 20 to 28 carbon atoms.

[0061]

[Reference Example 8] After applying the test solution prepared in Reference Example 6 to a test piece (aluminum # 5052), contact it with
Left for days. The film thickness was 2μ. After that, a performance test was conducted.

[0062]

Examples 1 to 7 Plastic working oils were prepared by blending the respective components shown in Table 2 below in predetermined amounts. However, all the weight percentages are shown in the table.

[0063]

[Table 2]

<Lubricity test> 1. Bowden-type adhesion sliding test Method / Condition: Test piece: Aluminum (# 5052)
Plate Rubbing ball; SUJ-2, 3/16 inch φ test temperature; 100 ° C load; 3Kg sliding speed; 3.88mm / sec lubrication; 2 drops under sliding; 50 round trips Evaluation: 5 round trips Table 3 shows the results of the 50th friction coefficient measurement.
Shown in.

2. Pressability test (cylindrical deep drawing test) Test piece: Aluminum alloy (# 5052)
Plate blank diameter (D): φ70 to φ85 (thickness 0.8
mm) Punch diameter (dp): φ40 (flat head punch) Punch shoulder radius (rp): R4.2 Dice diameter (dd): φ41.6 Dice shoulder radius (rd): R8.7 Wrinkle pushing force: 10.0 Kg / cm ² Punch speed (m / min): 0.3, 40.0 Sample oil: 3 g / m ² coating (amount of lubrication additive film) Evaluation: It left for 24 hours after application and was used for the test, and evaluated by the limiting drawing ratio. Good lubricity is obtained when the blank is narrowed to a high limit drawing ratio. The test results are shown in Table 3. (Note) Limiting draw ratio (LDR) = blank diameter / punch diameter

<Cleanability test> Method / conditions: test piece; aluminum alloy (# 505
2) Plate Sample oil: 3 g / m ² applied (film amount of lubrication additive) Leave period: 7 days hanging and suspended Degreasing method; Spray degreasing detergent; Commercial detergent mainly composed of phosphate 2% concentration, temperature 60 ° C, spray pressure 1.5 Kg / cm ² ,
Time 1 minute Judgment evaluation; After spray degreasing, soak in running water for 1 minute and judge degreasing rate by water leak method. The results are shown in Table 3.

<Corrosion test of aluminum alloy> Condition: 60 ° C. × 90% (humidity) for 7 days Test piece: Aluminum alloy (# 5052) plate Method: After polishing the test piece with # 1000 emery paper, a sample It was applied by dipping in oil, and after being vertically drained for 24 hours, it was further semi-immersed in sample oil, covered with an aluminum foil, and air holes were made at several places for use in the test. Evaluation: The corrosion state of the unimmersed part and the immersed part was observed.
The results are shown in Table 3.

[0068]

[Table 3]

However, the method of judging each physical property in Table 3 is as follows. Anticorrosion test ○: No change Detergency: ○: Degreased area 95% or more △: Slight whitening △; Degreased area 80 to 95% ×; Black discoloration ×; Degreased area 80% or less (Note) Comparative Example 1: Commercial phosphoric acid Ester B

The composition of the commercial press oil shown in Comparative Example 2 is the following estimated composition. 1. Ester-based additive: 20.0% 2. Alcohol-based additive ……………… 10.0% 3. Sulfonate-based additive: 3.0% 4. Antioxidant …………………… 0.5% 5. Naphthene type light lubricating oil ………… 66.5% Viscosity: 12 cst (40 ℃)

As is clear from the results shown in Table 3, the product of the present invention exhibits excellent lubricity, cleanability and anticorrosion property with respect to the aluminum alloy.

[0072]

[Brief description of drawings]

[0073]

[Figure 1]

FIG. 1 is a graph showing thermal stability.

[0075]

[Fig. 2]

FIG. 2 is a graph showing the coefficient of friction.

1 ... Compound of the present invention 2 ... Commercial phosphoric acid ester B 3 ... Commercial phosphoric acid ester C

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10M 137: 12) C10N 30:00 A 8217-4H 30:06 30:12 40:24 A 8217- 4H (72) Inventor Toshi Yokoyama 41-2 Sennichicho, Yamatokoriyama City, Nara Prefecture

Claims (3)

[Claims] 1. The following general formula synthesized from an olefin having 6 to 60 carbon atoms and having a double bond at the α-position, and at least one of phosphorous acid, hypophosphorous acid and dialkyl phosphite. A plastic working lubricant of an aluminum alloy or a non-ferrous metal, wherein the diluent contains the alkylphosphonic acid derivative represented by Chemical formula 1] in an amount of 1.0 to 100% by weight. [Chemical 1] (However, R ₁ is a C ₆ -C ₆₀ linear or branched alkyl group, R ₂
Or both R _3's represent either H or a C _{1 to} C ₁₈ linear or branched alkyl group, an oxyalkylene group, an alkali metal, or an alkaline earth metal) 2. The following general formula synthesized from an olefin having 6 to 60 carbon atoms and having a double bond at the α-position, and at least one of phosphorous acid, hypophosphorous acid and dialkyl phosphite. 1] The reaction product of the alkylphosphonic acid derivative represented by 1] with at least one of the compounds represented by the following (1) to (3) is contained in a diluent in an amount of 1.0 to 100% by weight. Aluminum alloy or non-ferrous metal plastic working lubricant. (Wherein R ₁ is a C _{6 to} C ₆₀ linear or branched alkyl group, and R ₂ or R ₃ is H or C ₁ to
A C ₁₈ linear or branched alkyl group, an oxyalkylene group,
Alkali metals and alkaline earth metals are shown) Compound (1) Amine represented by [Chemical Formula 2] (However, R ₄ , R ₅ , and R ₆ are all or two or one is H
Or a C _{1 to} C ₁₈ linear or branched alkyl group, or R ₆ is R
Alkoxyl groups represented by ₇ -O-R _8, the remainder are H. R ₇ is a C ₁ -C ₆ linear or branched alkyl group, and R ₈ is C
_{1- C18} linear or branched alkyl group) Compound (2) Amino alcohol Compound (3) Polyamine represented by [Chemical Formula 3] (However, R ₁₄ , R ₁₆ , R ₁₇ , and R ₁₈ are H or have a carbon number of C ₁ to
C ₁₈ alkyl group, R ₁₅ represents a C ₁ -C ₁₈ alkyl group carbon atoms) 3. A lubrication wherein the plastic working lubricant composition according to claim 1 or 2 is applied to an aluminum alloy or a non-ferrous metal plate or a coil thereof such that the dry film thickness is 0.1 to 10.0 μm. Aluminum alloy or non-ferrous metal plate or coil with coating.