JP2007100201A - Aluminum alloy sheet for forming, method for producing the same and method for working aluminum alloy sheet for forming - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aluminum alloy sheet for forming whose formability can be improved by improving its lubricity when being fed with lubricating oil without deteriorating the cleanliness of the lubricating oil; to provide a method for producing the same; and to provide a method for working the aluminum alloy sheet. <P>SOLUTION: The aluminum alloy sheet 1 for forming has an aluminum alloy sheet 2 and a hydrated oxide film 3 on the surface thereof. The hydrated oxide film 3 satisfies the relation of A2/A1≥0.1 provided that the maximum value of the absorbance in the vicinity of 1,100 cm<SP>-1</SP>is defined as A1 and the maximum value of the absorbance in the vicinity of 1,350 cm<SP>-1</SP>is defined as A2 in Fourier Transform Infrared Spectroscopy. In the production of the aluminum alloy sheet 1 for forming, the aluminum alloy sheet 2 is brought into contact with an alkali treatment liquid, so as to remove a natural oxide film, and is thereafter brought into contact with a hydrothermal treatment liquid heated to ≥50°C without performing desmut treatment, so as to form the hydrated oxide film 3. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a forming aluminum alloy plate having a hydrated oxide film on its surface, a method for producing the same, and a processing method for the forming aluminum alloy plate.

  Conventionally, steel has been used for transport panel materials such as automobiles, materials for home appliances, IT cases and the like. However, in recent years, as a part of environmental or energy saving measures, there has been a strong demand for weight reduction or miniaturization. Therefore, the material is changing from steel to aluminum (hereinafter, including aluminum alloy), and it is becoming mainstream particularly in IT cases.

  In general, in order to apply aluminum to these applications, like steel, processing lubricant is pre-applied to processing materials or supplied during press molding to improve friction lubricity with the press mold and improve press formability. The current situation is that it is increasing.

  However, aluminum has the drawback that the material itself does not stretch as much as steel, and its formability is inferior to steel. In order to compensate for this, the lubricating oil used at the time of molding has been improved. However, in general, a lubricating oil excellent in lubricity tends to have higher viscosity or higher oiliness. When such a lubricating oil is used, not only the workability is deteriorated, but also cleaning in a subsequent process becomes difficult, and the quality may be deteriorated. In addition, the production efficiency may be reduced and the environmental load may increase. Therefore, the improvement of the lubricating oil is not necessarily a preferable measure.

  On the other hand, in order to obtain high moldability, a method of applying a resin film to aluminum in advance, that is, a plate material commonly called a precoated aluminum plate has been developed (see Patent Documents 1 to 4).

However, in the precoated aluminum plate, a precoat film is unnecessary after molding, but there is a problem that an appropriate means for easily removing the precoat film has not been developed yet. For this reason, it has been particularly difficult to apply to applications such as automobile panels that require painting or baking after molding.
As described above, it was industrially difficult to improve the press formability of the aluminum plate material without imposing a load on the subsequent cleaning process.

JP 2004-17454 A JP 2004-17455 A JP 2005-66439 A JP 2005-74790 A

  The present invention has been made in view of such conventional problems, and it is possible to improve the formability by improving the lubricity when the lubricant is supplied without deteriorating the washability of the lubricant. An object of the present invention is to provide a forming aluminum alloy plate that can be formed, a method for producing the same, and a method for processing the aluminum alloy plate.

A first invention is an aluminum alloy plate for molding having an aluminum alloy plate and an Al hydrated oxide film formed on the surface of the aluminum alloy plate,
The hydrous oxide film is in the Fourier transform infrared spectroscopy measurement (FT-IR), a peak of the absorption spectrum in the vicinity of wave number 1100 cm ^-1 and near the wave number 1350 cm ^-1, the absorption spectrum in 1100 cm ^-1 vicinity The forming aluminum alloy satisfying the relationship of A2 / A1 ≧ 0.1, where A1 is the maximum absorbance at the peak and A2 is the maximum absorbance at the peak of the absorption spectrum in the vicinity of 1350 cm ^−1. It exists in a board (Claim 1).

In the first invention, the most noteworthy, the hydrous oxide film is in the Fourier transform infrared spectroscopy measurement (FT-IR), the wave number 1100 cm ^-1 and near the wave number 1350 cm ^-1 vicinity absorption spectrum Assuming that the maximum absorbance at the peak of the absorption spectrum near 1100 cm ⁻¹ is A1, and the maximum absorbance at the peak of the absorption spectrum near 1350 cm ⁻¹ is A2, A2 / A1 ≧ 0.1 That is to satisfy the relationship. Thus, in the FT-IR, the forming aluminum alloy plate having the hydrated oxide film showing the characteristic peak as described above on the surface of the aluminum alloy plate has a low surface friction coefficient. Therefore, the forming aluminum alloy plate can improve formability in, for example, press forming without using a lubricating oil. Further, since the moldability can be improved without using a lubricant, it is not necessary to remove the lubricant by washing after molding.

  Further, the forming aluminum alloy plate can be used for forming by applying lubricating oil. In this case, the hydrated oxide film exhibits excellent affinity with the lubricating oil, and the formability of the forming aluminum alloy plate can be improved even with a relatively small amount of lubricating oil. Further, since the amount of the lubricating oil can be suppressed, it becomes easy to remove the lubricating oil by washing or the like after the molding.

A second invention is a method for producing an aluminum alloy plate for molding having an aluminum alloy plate and a hydrated oxide film of Al formed on the surface of the aluminum alloy plate,
An alkali treatment step of contacting the alkali treatment liquid made of an alkaline aqueous solution on the surface of the aluminum alloy plate to remove the natural oxide film and generating smut;
In the alkali treatment step, without performing desmut treatment for removing the smut generated on the surface of the aluminum alloy plate, the aluminum alloy plate is contacted with water having a temperature of 50 ° C. or higher or a hydrothermal treatment solution made of an alkaline aqueous solution. And a hot water treatment step of forming the hydrated oxide film on the surface of the aluminum alloy plate. (Claim 8)

  Conventionally, when forming a hydrated oxide film, the smut generated when the natural oxide film on the aluminum alloy plate is removed by alkali treatment is removed by acid treatment, etc., and then reacted with water to hydrate. An oxide film was generated. On the other hand, in the present invention, the hydrated oxide is formed without removing the smut.

That is, in the alkali treatment step, the surface of the aluminum alloy plate is brought into contact with an alkali treatment liquid made of an alkaline aqueous solution to remove the natural oxide film and generate smut. In the hot water treatment step, water or an alkaline aqueous solution having a temperature of 50 ° C. or more is applied to the aluminum alloy plate without performing a desmut treatment for removing the smut generated on the surface of the aluminum alloy plate in the alkali treatment step. The hydrated oxide film is formed on the surface of the aluminum alloy plate by contacting with a hot water treatment liquid.
The hydrated oxide formed as described above can reduce the friction coefficient of the surface of the aluminum alloy plate. Therefore, the forming aluminum alloy plate can improve formability in, for example, press forming without using a lubricating oil. Further, since the moldability can be improved without using a lubricant, it is not necessary to remove the lubricant by washing after molding.

  Moreover, the said aluminum alloy plate for shaping | molding obtained by the manufacturing method of this invention can show the affinity with which the said hydrated oxide film | membrane was excellent with lubricating oil. Therefore, when applying lubricating oil and using it for shaping | molding, the moldability of the said aluminum alloy plate for shaping | molding can be improved with a comparatively small amount of lubricating oil. Further, since the amount of the lubricating oil can be suppressed, it becomes easy to remove the lubricating oil by washing or the like after the molding.

  According to a third aspect of the present invention, there is provided a processing method for a forming aluminum alloy plate, wherein the forming aluminum alloy plate according to any one of claims 1 to 7 is subjected to press forming.

  In the processing method of the present invention, press forming is performed using the forming aluminum alloy plate of the first invention. Therefore, the said aluminum alloy plate for shaping | molding can be shape | molded by a higher extending | stretching rate using the above-mentioned outstanding moldability which the said aluminum alloy plate for shaping | molding has. Further, when the molding is performed using the lubricating oil, the amount of the lubricating oil can be reduced, so that the lubricating oil after the molding can be easily removed.

Next, a preferred embodiment of the present invention will be described.
The forming aluminum alloy plate of the present invention includes an aluminum alloy plate and an Al hydrated oxide film formed on the surface of the aluminum alloy plate. The aluminum alloy plate can be obtained by rolling to a predetermined thickness.

Further, in the first invention, the hydrous oxide film shows the Fourier transform infrared spectroscopy measurement (FT-IR), near the wave number 1100 cm ^-1 and near wavenumber 1350 cm ^-1 to the peak of the absorption spectrum. When the maximum absorbance at the peak of the absorption spectrum near 1100 cm ⁻¹ is A1, and the maximum absorbance at the peak of the absorption spectrum near 1350 cm ⁻¹ is A2, the relationship of A2 / A1 ≧ 0.1 is satisfied. .
The wave number 1100 cm ^-1 vicinity means a wave number 1100 ± 50 cm ^-1. Also, the wave number 1350 cm ¹ near means wavenumber 1350 ± 50 cm ^1.
If the specific wave number does not show an absorption spectrum peak or if A2 / A1 <0.1, the hydrated oxide film may not be able to sufficiently reduce the friction coefficient of the surface of the aluminum alloy plate. . In this case, the affinity between the hydrated oxide film and the lubricating oil may not be sufficiently improved. As a result, it may be difficult to sufficiently improve the moldability. More preferably, A2 / A1 ≧ 1 or more is preferable, and A2 / A1 ≧ 1.5 is more preferable.

In the second invention, the forming aluminum alloy sheet is manufactured by performing the alkali treatment step and the hot water treatment step.
In the alkali treatment step, the surface of the aluminum alloy plate is brought into contact with an alkali treatment solution made of an alkaline aqueous solution to remove the natural oxide film and generate smut.
The said alkali treatment process can be performed continuously, for example in the manufacturing process of an aluminum alloy plate. In this case, lubricating oil such as rolling oil is present on the surface of the aluminum alloy plate, but by performing the alkali treatment step, the natural oxide film can be removed as described above, and these oil components can be removed. Can be degreased. Of course, as the aluminum alloy plate, for example, an alloy plate from which the oil component has been removed in advance, such as a commercially available aluminum alloy plate, can also be used.

Moreover, the said alkali treatment liquid consists of alkaline aqueous solution. Specifically, for example, an aqueous sodium hydroxide solution, sodium silicate, sodium borate or the like can be used.
Moreover, as the alkali treatment liquid, it is preferable to use an alkaline aqueous solution having a pH of 8 or more. In this case, in the alkali treatment step, it becomes easier to remove the natural oxide film using the alkali treatment liquid and generate a smut.

Moreover, in the said hot water treatment process, the hot water treatment which consists of water or alkaline aqueous solution with a temperature of 50 degreeC or more to the said aluminum alloy plate, without performing the desmut treatment which removes the said smut produced | generated on the surface of the said aluminum alloy plate The liquid is contacted to form the hydrated oxide film on the surface of the aluminum alloy plate.
As described above, in the hydrothermal treatment step, the hydrated oxide film is formed without performing the desmut treatment, and thus the hydrated oxide film can contain smut. The smut can form a continuous or discontinuous layer (smut layer). The hydrated oxide film may be formed on the smut layer, or may be formed in a state where the hydrated oxide film and the smut layer are mixed. Further, the smut may not be layered but may be dispersed in the hydrated oxide film.

By the hot water treatment step, the Fourier transform infrared spectroscopy measurement (FT-IR), a peak of the absorption spectrum in the vicinity of wave number 1100 cm ^-1 and near the wave number 1350 cm ^-1, and the absorption spectrum in 1100 cm ^-1 vicinity Forming a hydrated oxide film satisfying the relationship of A2 / A1 ≧ 0.1, where A1 is the maximum absorbance at the peak and A2 is the maximum absorbance at the peak of the absorption spectrum in the vicinity of 1350 cm ^−1. Can do.

The hydrothermal treatment liquid is made of water having a temperature of 50 ° C. or higher or an alkaline aqueous solution having a temperature of 50 ° C. or higher.
When the temperature of the hot water treatment liquid is less than 50 ° C., it may be difficult to sufficiently form a hydrated oxide film. More preferably, water having a temperature of 80 ° C. or higher or an alkaline aqueous solution may be used.
Further, in order to grow the hydrated oxide film faster, it is preferable to use a hydrothermal treatment liquid composed of an alkaline aqueous solution in the hydrothermal treatment step. As the alkaline aqueous solution, for example, a triethanolamine aqueous solution, an ammonia aqueous solution, a sodium aluminate aqueous solution, or the like can be used. Further, the alkaline aqueous solution used as the hot water treatment liquid preferably has a pH of 8 or less.

In the present invention, the hydrated oxide film preferably has a thickness of 0.6 to 10 μm (claim 2).
Moreover, in the said hydrothermal treatment process, it is preferable to form the said hydrated oxide film | membrane with a thickness of 0.6-10 micrometers (Claim 9).
When the thickness of the hydrated oxide film is less than 0.6 μm, the above-described effect of improving the formability by the hydrated oxide film may not be sufficiently obtained. On the other hand, even if the hydrated oxide film is formed with a thickness exceeding 10 μm, the improvement effect such as moldability is hardly obtained any longer, the time for performing the hot water treatment becomes longer than necessary, and the production efficiency is lowered. There is a fear.

A lubricating film made of lubricating oil, solid lubricant, wax or the like can be formed on the forming aluminum alloy plate. Moreover, the said aluminum alloy plate for shaping | molding can be shape | molded, supplying lubricating oil at the time of shaping | molding.
As described above, when a lubricating film is formed or when lubricating oil is used during forming, the hydrated oxide film of the forming aluminum alloy plate can strongly adsorb the lubricating component, thereby further improving the formability. Can do. Since the hydrated oxide film has irregularities on the surface on the order of μ (see FIG. 4), it is easy to trap lubricating oil, solid lubricant, wax, etc., and can improve the lubricity during molding. It is. In addition, the hydroxyl group of the hydrated oxide film strongly adsorbs highly polar lubricating components contained in lubricants, solid lubricants, and waxes, making it difficult to remove the lubricity even under severe molding conditions. This is because the lubricity can be maintained.

As said lubricating oil, what contains mineral oil, synthetic oil, etc. can be used. As the solid lubricant, for example, one or more selected from graphite, molybdenum disulfide, PbO, Na ₂ MoO ₄ , tetrafluoroethylene resin, phthalocyanine, and the like can be used. In addition, as the wax, for example, one or more selected from carnauba, lanolin, polyethylene, paraffin, and microstalin can be used.

Moreover, when forming the said lubricous membrane | film | coat, it is preferable that the adhesion amount is 0.1-10 g / m < ² >.
When the adhesion amount of the lubricating film is less than 0.1 g / m ² , there is a possibility that the merit by forming the lubricating film is not sufficiently exhibited. On the other hand, if it exceeds 10 g / m ² , it may be difficult to remove the lubricating film by washing after molding.

Therefore, the forming aluminum alloy plate has a lubricating film composed of at least one selected from a lubricating oil, a solid lubricant, and a wax on the hydrated oxide film, and the adhesion amount of the lubricating film Is preferably 0.1 to 10 g / m ² . Further, a lubricating film forming agent comprising at least one selected from a lubricating oil, a solid lubricant, and a wax is applied on the hydrated oxide film, and a lubricating film of 0.1 to 10 g / m ² is formed. It is preferable to have a lubricating film forming step to be formed (claim 10).

Moreover, it is preferable that the said lubricating oil contains 1 or more types chosen from ester, a fatty acid, alcohol, fats and oils as an oil-based agent (Claim 4 and Claim 11).
Moreover, it is preferable that the said lubricating oil contains a sulfur type compound or / and a phosphorus type compound as an extreme pressure agent (Claim 5 and Claim 12).
When the lubricating oil contains the oily agent or / and the extreme pressure agent, the oily agent or / and the extreme pressure agent having polarity are adsorbed with a strong adsorption force with the hydroxyl group of the hydrated oxide film. Thus, it is possible to form the above-described strong lubricating film excellent in boundary lubricity. As a result, it is possible to further improve the formability of the forming aluminum alloy plate. In addition, adhesion of aluminum wear powder during molding can be suppressed.

  As the alcohol used in the oily agent, for example, an alcohol having 12 to 18 carbon atoms in the alkyl group can be used. Specific examples include lauryl alcohol, myristyl alcohol, palmitic alcohol, oleyl alcohol, and stearyl alcohol. These can be used alone, or two or more kinds can be mixed and used. When the total number of carbon atoms is less than 11, the odor becomes so strong that the working environment may be deteriorated. Further, the boundary lubricity may not be sufficiently improved. On the other hand, if the total number of carbons exceeds 18, it tends to harden in the winter and the handling may be difficult. Lauryl alcohol or oleyl alcohol is more preferable from the viewpoint of boundary lubricity, environment, handling, price, and the like.

  Moreover, as a fatty acid, the higher fatty acid whose total carbon number of an alkyl group is 11-17 can be used, for example. Specifically, for example, linear saturated acids such as capric acid, undecanoic acid, lauric acid, tridecanoic acid, demilitinic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, behenic acid, palmitoleic acid, oleic acid, There are unsaturated fatty acids such as linoleic acid, linolenic acid and ricinoleic acid. More preferably, lauric acid, myristic acid, palmitic acid, oleic acid and the like are preferable in consideration of lubricity, workability, long-term stability and cost. In the fatty acid, when the total number of carbon atoms is less than 11, it may be difficult to sufficiently improve the boundary lubricity. On the other hand, when it exceeds 17, it tends to harden in the winter season and the handling may be difficult.

  Examples of the fat include soybean oil, rapeseed oil, palm oil, coconut oil, lard and beef tallow. Among these, palm oil and palm oil are preferable from the viewpoint of operability.

Examples of esters that can be used include fatty acid esters and synthetic esters.
As the fatty acid ester, for example, a fatty acid ester represented by a general formula R3-COO-R4 (wherein R3 is an alkyl group having 7 to 17 carbon atoms and R4 is an alkyl group having 1 to 4 carbon atoms) can be used.
When the number of carbon atoms in R3 is less than 7, it may be difficult to sufficiently improve the lubricity. Moreover, there is a possibility that adhesion of aluminum wear powder cannot be sufficiently suppressed. Furthermore, the odor becomes tight and the working environment may be deteriorated. On the other hand, when the number of carbon atoms in R3 exceeds 17, the drying property is deteriorated and it becomes difficult to dry, and the melting point becomes high and the material is easily solidified at room temperature, which may deteriorate the workability. Most preferably, R3 has 17 carbon atoms.

  On the other hand, when the number of carbon atoms in R4 exceeds 4, the drying property is deteriorated and the melting point becomes high, and there is a possibility that it is easy to solidify at room temperature. Therefore, in this case, additional heating equipment is required, and workability may be deteriorated.

  Specific examples of fatty acid esters include, for example, methyl caprylate, ethyl caprylate, propyl caprylate, butyl caprylate, methyl pelargonate, ethyl pelargonate, propyl pelargonate, butyl pelargonate, methyl caprate, ethyl caprate, caprine Propyl acid, butyl caprate, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, methyl myristate, ethyl myristate, propyl myristate, butyl myristate, methyl palmitate, ethyl palmitate, propyl palmitate , Butyl palmitate, methyl stearate, ethyl stearate, propyl stearate, butyl stearate, methyl oleate, ethyl oleate, propyl oleate, butyl oleate, etc. A.

Moreover, as said synthetic ester, neopentyl glycol ester, trimethylol propane ester, pentaerythritol ester etc. can be used, for example. These can be used alone or in combination of two or more.
In addition, the fatty acid which comprises these synthetic ester may be a linear thing, or may have a branch. The synthetic ester may be either a full ester or a partial ester.

  Specific examples of the neopentyl glycol ester include neopentyl glycol capric acid monoester, neopentyl glycol capric acid diester, neopentyl glycol ester, neopentyl glycol linolenic acid monoester, neopentyl glycol linolenic acid diester, Neopentyl glycol stearic acid monoester, neopentyl glycol stearic acid diester, neopentyl glycol oleic acid monoester, neopentyl glycol oleic acid diester neopentyl glycol ester, neopentyl glycol isostearic acid monoester, neopentyl glycol isostearic acid diester, neo Pentyl glycol palm oil fatty acid monoester, neopentyl glycol palm Fatty acid diester, neopentyl glycol beef tallow fatty acid monoester, neopentyl glycol beef tallow fatty acid diester, neopentyl glycol palm oil fatty acid monoester, neopentyl glycol palm oil fatty acid diester neopentyl glycol ester, neopentyl glycol 2 mol, dimer acid 1 mol There are complex esters of 2 moles of oleic acid.

  Examples of the trimethylol propane ester include trimethylol propane capric acid monoester, trimethylol propane capric acid diester, trimethylol propane capric acid triester, trimethylol propane linolenic acid mono ester, trimethylol propane linolenic acid diester, trimethylol. Propanelinolenic acid triester, trimethylolpropane stearic acid monoester, trimethylolpropane stearic acid diester, trimethylolpropane stearic acid triester, trimethylolpropane oleic acid monoester, trimethylolpropane oleic acid diester, trimethylolpropane oleic acid triester Esters, trimethylolpropane isostearic acid monoester, trimethylo Propane isostearic acid diester, trimethylolpropane isostearic acid triester, trimethylolpropane palm oil fatty acid monoester, trimethylolpropane palm oil fatty acid diester, trimethylolpropane palm oil fatty acid triester, trimethylolpropane beef tallow fatty acid monoester, Trimethylolpropane beef tallow fatty acid diester, trimethylolpropane beef tallow fatty acid triester, trimethylolpropane palm oil fatty acid monoester, trimethylolpropane palm oil fatty acid diester, trimethylolpropane palm oil fatty acid diester, trimethylolpropane 2 mol dimer acid 1 There are complex esters of 4 mol of oleic acid.

  Examples of pentaerythritol include pentaerythritol capric acid monoester, pentaerythritol capric acid diester, pentaerythritol capric acid triester, pentaerythritol capric acid tetraester, pentaerythritol linolenic acid monoester, pentaerythritol linolenic acid diester, pentaerythritol. Linolenic acid triester, pentaerythritol linolenic acid tetraester, pentaerythritol stearate monoester, pentaerythritol stearate diester, pentaerythritol stearate triester, pentaerythritol stearate tetraester, pentaerythritol oleate monoester, pentaerythritol oleate Diester, pe Taerythritol oleic acid triester, pentaerythritol oleic acid tetraester, pentaerythritol isostearic acid monoester, pentaerythritol isostearic acid diester, pentaerythritol isostearic acid triester, pentaerythritol isostearic acid tetraester, pentaerythritol palm oil fatty acid monoester, Pentaerythritol Palm Oil Fatty Acid Diester, Pentaerythritol Palm Oil Fatty Acid Triester, Pentaerythritol Palm Oil Fatty Acid Tetraester, Pentaerythritol Beef Fatty Acid Monoester, Pentaerythritol Beef Fatty Acid Diester, Pentaerythritol Beef Fatty Acid Triester, Pentaerythritol Beef Fatty Acid Tetraester, pentaerythrito Palm oil fatty acid monoester, pentaerythritol palm oil fatty acid diester, pentaerythritol palm oil fatty acid triester, pentaerythritol palm oil fatty acid tetraester, complex ester of 2 mol of trimethylolpropane, 1 mol of dimer acid, 6 mol of oleic acid, etc. .

  Among various synthetic esters such as the above-mentioned neopentyl glycol ester, trimethylol propane ester, and pentaerythritol ester, oleic acid, isostearic acid, coconut oil fatty acid, and tallow fatty acid ester are more preferable.

The synthetic ester preferably has 11 to 17 carbon atoms on the fatty acid side.
If the number of carbon atoms is less than 11, the lubricity may be reduced.
On the other hand, when the number of carbon atoms exceeds 17, the viscosity further increases in winter and the like, and in some cases, it may solidify, so that it may be necessary to warm and dissolve during mixing.

  Examples of the extreme pressure agent include sulfur compounds such as sulfurized esters, sulfurized lard, and sulfurized esters, phosphoric acid esters or thio compounds thereof, phosphonic acids having an alkyl group having 1 to 8 carbon atoms, an alkylallyl group, or an aryl group. In addition, one or more of alkyl phosphonate and tolyl phosphate (tricresyl phosphate) can be used. The content of the extreme pressure agent in the lubricating oil is preferably 1 to 10 wt%.

Next, the lubricating oil contains 0.01 or more amine derivatives selected from amines, alkanolamines, aliphatic polyamines, aromatic amines, alicyclic amines, heterocyclic amines, and alkylene oxide adducts thereof. It is preferable to contain -2.0weight% (Claim 6 and Claim 13).
The amine derivative has an effect of improving the dispersibility of the aluminum wear powder and also has an effect of suppressing the adhesion of the aluminum wear powder to the mold. Therefore, as described above, when the lubricating oil contains the amine derivative, it is possible to reduce the frequency of mold maintenance work for removing the aluminum wear powder from the mold and to improve the production efficiency.

  Examples of the amine derivative include aliphatic amines, aliphatic polyamines, aromatic amines, alicyclic amines, heterocyclic amines, and alkylene oxide adducts thereof. Moreover, a hydroxyl group and an ether group may be contained. The added alkylene oxide can be obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, α-olefin oxide, styrene oxide, and the like. The polymerization form such as alkylene oxide to be added is not particularly limited, and may be homopolymerization of one type of alkylene oxide, random copolymerization of two or more types of alkylene oxide, block copolymerization, random / block copolymerization, or the like. .

  Specific examples of the amine derivatives include methylamine, ethylamine, butylamine, caprylamine, laurylamine, stearylamine, oleylamine, tallowamine dimethylamine, diethylamine, dioctylamine, butyloctylamine, distearylamine, dimethyloctylamine, dimethyl Aliphatic amines such as decylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dimethylbehenylamine, dilaurylmonomethylamine, trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N- Methylethanolamine, N, N-dimethylethanolamine, N-ethylethanolamine, N, N-diethylethanolamine N-isopropylethanolamine, N, N-diisopropylethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylisopropanolamine, N, N-dimethylisopropanolamine, N-ethylisopropanolamine, N, N- Diethylisopropanolamine, N-isopropylisopropanolamine, N, N-diisopropylisopropanolamine, mono-n-propanolamine, di-n-propanolamine, tri-n-propanolamine, N-methyln-propanolamine, N, N-dimethyln -Propanolamine, N-ethyl n-propanolamine, N, N-diethyl n-propanolamine, N-isopropyl n-propanolamine, N, -Diisopropyl n-propanolamine, monobutanolamine, dibutanolamine, tributanolamine, N-methylbutanolamine, N, N-dimethylbutanolamine, N-ethylbutanolamine, N, N-diethylbutanolamine, N-isopropyl Alkanol amines such as butanolamine, N, N-diisopropylbutanolamine, aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetraamine, hexamethylenediamine, and cured beef tallow propylenediamine, aromatic amines such as aniline, dimethylaniline, and diethylaniline , N-cyclohexylamine, N, N-dicyclohexylamine, N, N-dimethyl-cyclohexylamine, N, N-diethyl-cyclohexylamine Cycloaliphatic amines such as N, N-di (3-methyl-cyclohexyl) amine, N, N-di (2-methoxy-cyclohexyl) amine, N, N-di (4-bromocyclohexyl) amine, pyrrolidine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Pipecoline, 2,6-Pipecoline, 3,5-Lupetidine, Piperazine, Homopiperazine, N-methylpiperazine, N-ethylpiperazine, N-propyl Piperazine, N-methylhomopiperazine, N-acetylpiperazine, N-acetylhomopiperazine, 1- (chlorophenyl) piperazine, N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethylpiperazine, N-aminopropylpiperazine, N-aminoethylmorpholine, N-aminopropyl Ruhorin, N- aminopropyl-2-pipecoline, N- aminopropyl-4-pipecoline, and 1,4-bis heterocyclic amines such as (aminopropyl) piperazine Ageraru.

  The amine derivative preferably has a hydrocarbon group having 4 or more carbon atoms having a branched chain from the viewpoint of solubility in oil. Moreover, when the total number of carbon atoms exceeds 20, there is a possibility that the amount of residual oil in the subsequent process increases. For this reason, the amine derivative preferably has 4 to 20 carbon atoms. In addition, when an alkylene oxide adduct is used as the amine derivative, the number of moles of alkylene oxide added is usually preferably 1 to 6. More preferably, 1-4 is good. When the added mole number of alkylene oxide exceeds 6, the solubility in the base oil may be deteriorated.

  When the content of the amine derivative in the lubricating oil is less than 0.01% by weight, the effect of suppressing the adhesion of the aluminum wear powder may not be sufficiently obtained. On the other hand, when it exceeds 2.0% by weight, the effect of suppressing the adhesion of the aluminum wear powder can be further maintained, but the effect of the oily agent or the extreme pressure agent that can be contained in the lubricating oil. May be damaged.

The lubricating oil preferably contains 0.1 to 5.0% by weight of sodium dioctylsulfosuccinate or / and an oxygen-containing compound having one or more quaternary carbons in the molecule. 14).
Similar to the amine derivative, the sodium dioctylsulfosuccinate and the oxygen-containing compound have the effect of improving the dispersibility of the aluminum wear powder and the effect of suppressing the adhesion of the aluminum wear powder to the mold. Therefore, when the lubricating oil contains sodium dioctylsulfosuccinate or / and an oxygen-containing compound having one or more quaternary carbons in the molecule as described above, the metal that removes the aluminum wear powder from the mold. The frequency of mold maintenance work can be reduced and the production efficiency can be improved.

Specific examples of sodium dioctylsulfosuccinate include sodium di-2-ethylhexylsulfosuccinate.
Examples of the oxygen-containing compound having one or more quaternary carbons in the molecule include an alkylene oxide adduct of a polyhydric alcohol or a hydrocarbyl ether thereof. In addition, as the oxygen-containing compound, one oxygen-containing compound selected from these may be used alone, or a mixture of two or more oxygen-containing compounds having different structures may be used.

Moreover, as the polyhydric alcohol alkylene oxide adduct having one or more quaternary carbons in the molecule and the polyhydric alcohol constituting the hydrocarbyl ether, those having 2 to 6 hydroxyl groups are preferable.
Specific examples of such a polyhydric alcohol include neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, dipentaerythritol, 2-butyl-2-ethyl-1.3- Examples include propanediol, 2-methyl-2-propyl-1,3-propanediol, and 2,2-diethyl-1,3-propanediol.

  The alkylene oxide adduct of the polyhydric alcohol and the alkylene oxide constituting the hydrocarbyl ether are preferably those having 2 to 6 carbon atoms. More preferably, it has 2 to 4 carbon atoms. Specific examples of the alkylene oxide having 2 to 6 carbon atoms include ethylene oxide, propylene oxide, 1,2-epoxybutane (α-butylene oxide), 2,3-epoxybutane (β-butylene oxide), 1 , 2-epoxy-1-methylpropane, 1,2-epoxyheptane, 1,2-epoxyhexane and the like.

  The polymerization form of alkylene oxide or the like is not particularly limited, and may be homopolymerization of one type of alkylene oxide or the like, random copolymerization of two or more types of alkylene oxide, block copolymerization, random / block copolymerization, or the like. . Moreover, when adding an alkylene oxide to the polyhydric alcohol which has 2-6 hydroxyl groups, you may add to all the hydroxyl groups, and you may add to only one part hydroxyl group.

  Alkylene oxide adducts of polyhydric alcohols having one or more quaternary carbons in the molecule and some or all terminal hydroxyl groups of the alkylene oxide adducts constituting the hydrocarbyl ethers were hydrocarbyl etherified. Things can be used. The hydrocarbyl group mentioned here represents a hydrocarbon group having 1 to 24 carbon atoms.

  Examples of the hydrocarbon group having 1 to 24 carbon atoms include an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkylcycloalkyl having 6 to 11 carbon atoms. Groups, aryl groups having 6 to 10 carbon atoms, alkylaryl groups having 7 to 18 carbon atoms, arylalkyl groups having 7 to 12 carbon atoms, and the like.

  Specific examples of the alkyl group having 1 to 24 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, Linear or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched Decyl group, linear or branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, straight Linear or branched hexadecyl group, linear or branched heptadecyl group, linear or branched octadecyl group, linear or branched nonadecyl group, linear or branched icosyl group, linear or branched Weird Cosyl group, straight or branched docosyl, straight or branched tricosyl group, a tetracosyl group of straight or branched.

Examples of the alkenyl group having 2 to 24 carbon atoms include a vinyl group, a linear or branched propenyl group, a linear or branched butenyl group, a linear or branched pentenyl group, and a linear or branched hexenyl group. Group, linear or branched heptenyl group, linear or branched octenyl group, linear or branched nonenyl group, linear or branched decenyl group, linear or branched undecenyl group, linear or Branched dodecenyl group, linear or branched tridecenyl group, linear or branched tetradecenyl group, linear or branched pentadecenyl group, linear or branched hexadecenyl group, linear or branched heptadecenyl group , Linear or branched octadecenyl group, linear or branched nonadecenyl group, linear or branched icocenyl group, linear or branched henicosenyl group, linear or branched Of docosenyl group, a linear or branched tricosenyl group, a tetracosenyl group of straight or branched.
Examples of the cycloalkyl group having 5 to 7 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

  Examples of the alkylcycloalkyl group having 6 to 11 carbon atoms include a methylcyclopentyl group, a dimethylcyclopentyl group (including all structural isomers), a methylethylcyclopentyl group (including all structural isomers), and a diethylcyclopentyl group (all ), Methylcyclohexyl group, dimethylcyclohexyl group (including all structural isomers), methylethylcyclohexyl group (including all structural isomers), diethylcyclohexyl group (including all structural isomers) ), Methylcycloheptyl group, dimethylcycloheptyl group (including all structural isomers), methylethylcycloheptyl group (including all structural isomers), diethylcycloheptyl group (including all structural isomers), etc. There is.

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.
Examples of the alkylaryl group having 7 to 18 carbon atoms include tolyl groups (including all structural isomers), xylyl groups (including all structural isomers), ethylphenyl groups (including all structural isomers), direct Chain or branched propylphenyl group (including all structural isomers), linear or branched butylphenyl group (including all structural isomers), linear or branched pentylphenyl group (all structures) Isomers), linear or branched hexylphenyl groups (including all structural isomers), linear or branched heptylphenyl groups (including all structural isomers), linear or branched Octylphenyl group (including all structural isomers), linear or branched nonylphenyl group (including all structural isomers), linear or branched decylphenyl group (including all structural isomers) , Straight or branched (Including all structural isomers) undecylphenyl (including all structural isomers) straight or branched dodecylphenyl group and the like.

  Examples of the arylalkyl group having 7 to 12 carbon atoms include benzyl group, phenylethyl group, phenylpropyl group (including isomer of propyl group), phenylbutyl group (including isomer of butyl group), phenylpentyl group ( Pentyl group isomers), phenylhexyl group (including hexyl group isomers), and the like.

  When the content of sodium dioctyl sulfosuccinate and the oxygen-containing compound having one or more quaternary carbons in the molecule is less than 0.1% by weight, the effect of suppressing the adhesion of aluminum wear powder May not be sufficiently obtained. On the other hand, when it exceeds 5.0% by weight or when the oxygen-containing compound does not contain quaternary carbon, there is a possibility of adversely affecting the lubricity. In this case, the residue after the volatilization of the base oil increases, which may deteriorate the quality of the molded aluminum product.

Further, in the production of the forming aluminum alloy plate, it is preferable to perform a heating step of heating the forming aluminum alloy plate at a temperature of 100 ° C. or more and less than 300 ° C. after the lubricating film forming step. .
In this case, the adsorption of the hydrated oxide film and the lubricating film can be further strengthened, and the boundary lubricity of the aluminum alloy plate can be further improved. In particular, when the lubricating film contains the oily agent or / and extreme pressure agent, the effect of improving the boundary lubricity described above can be exhibited more remarkably. When the heating temperature in the heating step is less than 100 ° C., the effect of improving the adsorptive power between the hydrated oxide film and the lubricating film may not be sufficiently obtained. On the other hand, when the heating temperature is 300 ° C. or higher, the oily agent or the like contained in the lubricating film may start to decompose.

Next, in the said 3rd invention, press molding is performed using the aluminum alloy plate for shaping | molding of the said 1st invention.
When press-molding the forming aluminum alloy plate, press forming can be performed while supplying lubricating oil to the forming aluminum alloy plate. When an alloy plate having the lubricating film on the hydrated oxide film is used as the forming aluminum alloy plate, press forming can be performed without supplying lubricating oil to the forming aluminum alloy plate. it can.

Example 1
Next, the manufacturing method of the aluminum alloy plate for shaping | molding of this invention is demonstrated using FIGS.
As shown in FIG. 1, the forming aluminum alloy plate 1 of this example has an aluminum alloy plate 2 and an Al hydrated oxide film 3 formed on the surface thereof. Hydrated oxide film 3, as shown in FIG. 2, shown in the Fourier transform infrared spectroscopy measurement (FT-IR), near the wave number 1100 cm ^-1 and near wavenumber 1350 cm ^-1 to the peak of the absorption spectrum. Further, the FT-IR of the hydrated oxide film 3, and the maximum value of the absorbance maximum of the absorbance at the peak of 1100 cm ^-1 vicinity of the peak of A1,1350cm ^-1 vicinity and A2, A2 / A1 ≧ 0. Satisfy the relationship of 1.

  In this example, the aluminum alloy plate 2 is made of a 5000 series (Al-Mg series) alloy containing aluminum as a main component and further containing Mg as an alloy element. The film thickness of the hydrated oxide film 3 is 2.0 μm.

  The forming aluminum alloy plate 1 of this example can be manufactured by performing the following alkali treatment step and hot water treatment step. In the alkali treatment step, the surface of the aluminum alloy plate 2 is brought into contact with an alkali treatment solution made of an alkaline aqueous solution to remove the natural oxide film and generate smut. Next, in the hydrothermal treatment step, a hydrothermal treatment liquid composed of water or an alkaline aqueous solution having a temperature of 50 ° C. or higher is applied to the aluminum alloy plate 2 without performing a desmut treatment for removing the smut generated on the surface of the aluminum alloy plate 2. By contact, a hydrated oxide film 3 is formed on the surface of the aluminum alloy plate 2.

Hereafter, the manufacturing method of the aluminum alloy plate for shaping | molding of this example is demonstrated in detail.
First, as the aluminum alloy plate 2, an aluminum alloy plate GC55-O (JIS 5052, plate thickness 1.0 mm, φ120 mm) manufactured by Sumitomo Light Metal Industries, Ltd. was prepared. The aluminum alloy plate 2 was washed with a 10 wt% aqueous sodium hydroxide solution to remove the natural oxide film on the surface of the aluminum alloy plate 2 and to generate smut (alkali treatment step). Next, the aluminum alloy plate 2 was immersed in a triethanolamine aqueous solution having a concentration of 3 wt% at a temperature of 80 ° C. to form the hydrated oxide film 3 on the surface of the aluminum alloy plate 2 (hot water treatment step). In this way, a forming aluminum alloy plate 1 was obtained. This is designated as test material D1.

Next, Fourier transform infrared spectroscopic analysis (FT-IR) was performed on the hydrated oxide film formed on the specimen D1. FT-IR was performed using FREEXACT-III (registered trademark) and FT-720 manufactured by Horiba. The result is shown in FIG.
As can be understood from the figure, hydrated oxide film in sample material D1 showed a near wave number 1100 cm ^-1, the peak of each absorption spectrum in the vicinity of wave number 1350 cm ^-1. Further, when the maximum value of absorbance at the peak of the absorption spectrum in A1,1350cm ^-1 vicinity of the maximum value of absorbance at the peak of the absorption spectrum in 1100 cm ^-1 vicinity and A2, the absorbance ratio A2 / A1 was 2.8 .

Next, the hydrated oxide film 3 on the surface of the test material D1 was observed with a scanning electron microscope. The photograph is shown in FIG. As is known from the figure, a hydrated oxide film having μ-order irregularities was formed.
Further, the film thickness of the hydrated oxide film 3 on the surface of the test material D1 was measured using a Fischer permascope. As a result, the hydrated oxide was formed with a thickness of 2.0 μm in the test material D1.

Next, in this example, four types of forming aluminum alloy plates (sample B1, sample materials D2 to D4) were prepared for comparison with the sample material D1.
Sample B1 is a forming aluminum alloy plate in which a lubricating film is formed on the hydrated oxide film of the specimen D1.
In preparing the sample B1, first, a forming aluminum alloy plate in which a hydrated oxide film was formed on the surface of the aluminum alloy plate was prepared in the same manner as the test material D1. Next, lubricating oil B1 was prepared. Lubricating oil B1 is a lubricating oil obtained by adding 10 wt% of methyl laurate to paraffinic mineral oil having a viscosity of 2.1 mm ² / s at a temperature of 40 ° C. This lubricating oil B1 was applied onto the hydrated oxide film of the forming aluminum alloy plate so that the adhesion amount was 0.4 g / m ² to form a lubricating film (lubricating film forming step). In this manner, a forming aluminum alloy plate 1 (sample B1) in which the lubricating coating 4 was further formed on the surface of the hydrated oxide coating 3 formed on the surface of the aluminum alloy plate 2 was produced (FIG. 5). 5).

Further, the sample material D2 is obtained by forming a hydrated oxide film having an absorbance ratio A2 / A1 different from that of the sample material D1 on the surface of the aluminum alloy plate.
In preparing the test material D2, first, similarly to the test material D1, an aluminum alloy plate GC55-O (JIS 5052, plate thickness 1.0 mm, φ120 mm) manufactured by Sumitomo Light Metal Industry Co., Ltd. was prepared. The aluminum alloy plate was washed with a 10 wt% aqueous sodium hydroxide solution to remove the natural oxide film on the surface of the aluminum alloy plate 2. Next, the aluminum alloy plate was washed with an aqueous nitric acid solution having a temperature of 25 ° C. and a concentration of 30 wt% to remove the surface smut (desmut treatment). Thereafter, similarly to the test material D1, the aluminum alloy plate was immersed in a triethanolamine aqueous solution having a temperature of 80 ° C. and a concentration of 3 wt% to form a hydrated oxide film on the surface of the aluminum alloy plate. In this way, an aluminum alloy plate for forming was obtained (sample material D2).

Next, FT-IR was performed on the hydrated oxide film formed on the test material D2 in the same manner as the test material D1. The result is shown in FIG. As a result of the FT-IR measurement, the absorbance ratio A2 / A1 of the hydrated oxide film in the specimen D2 was 0.05 or less (below the detection limit).
Subsequently, the film thickness of the hydrated oxide film 3 of the sample material D2 was measured in the same manner as the sample material D1. As a result, the hydrated oxide was formed with a thickness of 2.0 μm in the specimen D2.

The test material D3 is an aluminum alloy plate that does not have a hydrated oxide film.
As the test material D3, an aluminum alloy plate GC55-O (JIS 5052, plate thickness 1.0 mm, φ120 mm) manufactured by Sumitomo Light Metal Industries, Ltd. was employed.

  The specimen D4 is a forming aluminum alloy plate similar to the specimen D1, except that the absorbance ratio A2 / A1 of the hydrated oxide film is 0.1. The specimen D4 was produced by a method substantially similar to the specimen D1.

Next, the surface slipperiness was evaluated as follows for each of the test materials (sample material D1, sample B1, sample material D2 to sample material D4) produced as described above.
"Slippery"
A 3/16 inch SUJ-2 steel ball was slid at a load of 3 kg and a sliding speed of 4 mm / sec. The coefficient of friction at that time was measured. The case where the friction coefficient exceeded 0.35 was evaluated as x, the case where it was 0.35 to 0.15 was evaluated as ◯, and the case where it was below 0.15 was evaluated as ◎. The results are shown in Table 1.

As is known from Table 1, it can be seen that the specimen D1 on which the hydrated oxide film having the absorbance ratio A2 / A1 of 2.8 is formed has good slipperiness. Therefore, the sample material D1 is excellent in moldability. Moreover, in sample B1 which formed the lubricous film on test material D1, the slipperiness improved further compared with test material D1. Further, the sample material D4 on which the hydrated oxide film having the absorbance ratio A2 / A1 of 0.1 was formed also had good slipperiness as the sample material D1.
On the other hand, the sample material D2 having an absorbance ratio A2 / A1 of 0.05 or less and the sample material D3 not forming the hydrated oxide film were poor in slipperiness and not suitable for molding.

(Example 2)
Next, in this example, similarly to the sample B1 prepared in Example 1, the hydrated oxide film formed on the surface of the aluminum alloy plate and the lubricity formed on the hydrated oxide film were further obtained. A forming aluminum alloy plate having a film is prepared, and its formability, adhesion of aluminum powder, detergency, etc. are evaluated. That is, this example is an example of evaluating characteristics such as formability when a lubricating film is formed on a forming aluminum alloy plate having a hydrated oxide film.

First, in this example, 24 types of forming aluminum alloy plates were obtained by changing the absorbance ratio of the hydrated oxide film, the film thickness, the type of lubricating oil used to form the lubricating film, the amount of lubricating oil to be adhered, and the like. (Sample B1 to Sample B24) were produced.
As shown in Tables 2 and 3, the forming aluminum alloy plates of the samples (Sample B1 to Sample B24) were hydrated with the test material D1, the test material D2, or the test material D4 as in Example 1. Various lubricating oils were applied on the oxide film to form a lubricating film. Sample B1 is the same as Sample B1 produced in Example 1. Sample B14, Sample B15, and Sample B16 were prepared by performing a heating step of heating at a temperature of 100 ° C. to 300 ° C. after the formation of the lubricating film.
The meanings of symbols in Tables 2 and 3 are as follows.

"FT-IR absorption spectrum of hydrated oxide"
A1: The maximum value of absorbance at the peak of the absorption spectrum appearing near 1100 cm ⁻¹ A2: The maximum value of absorbance at the peak of the absorption spectrum appearing near 1350 cm ⁻¹

"Lubricant"
B1: Lubricating oil obtained by adding 10 wt% of methyl laurate to paraffinic mineral oil having a viscosity of 2.1 mm ² / s at a temperature of 40 ° C. B2: 10 wt% of lauryl alcohol being added to a paraffinic mineral oil having a viscosity of 2.1 mm ² / s at a temperature of 40 ° C. B3: Lubricating oil with 10 wt% oleic acid added to paraffinic mineral oil with a viscosity of 2.1 mm ² / s at a temperature of 40 ° C.

"Additive"
The following various additives were added to the lubricating oil.
C1: di-2-ethylhexyl sulfosuccinate sodium C2: N-ethylisopropanolamine C3: 2-butyl-2-ethyl-1,3-propanediol ethylene oxide 2 mol adduct

`` Sample material ''
D1: Aluminum alloy plate for forming produced in Example 1 (sample D1) formed by forming a hydrated oxide film (A2 / A1 = 2.8) on an aluminum alloy plate
D2: Molding aluminum alloy plate produced in Example 1 (sample D2) formed by forming a hydrated oxide film (A2 / A1 = 0.05 or less) on an aluminum alloy plate
D4: Aluminum alloy plate for molding produced in Example 1 (sample D4) formed by forming a hydrated oxide film (A2 / A1 = 0.1) on an aluminum alloy plate

Various evaluations were performed as follows.
"Formability"
After subjecting each sample to heat treatment according to the conditions, each sample was stretched and molded at a molding speed of 2.0 mm / s using a ball head punch having a diameter of 50 mm and R = 25. At this time, the height at which each sample was cracked was defined as “molding height”. The moldability is evaluated by the size of the molding height. The case where the molding height is less than 18 mm is set as “X”, the case where it is 18.0 mm to 18.5 mm is set as “Δ”, and the case where it is 18.5 mm to 19 mm. The case of “◯” was evaluated, and the case of exceeding 19 mm was evaluated as “◎”. The results are shown in Tables 2 and 3.

"Amount of adhesion"
Each sample was subjected to an overmolding process under the same conditions as in the above-described moldability evaluation test. The overhang forming process was performed 100 sheets for each sample. Thereafter, the aluminum wear powder adhered to the punch surface was dissolved using a 10 wt% aqueous sodium hydroxide solution and quantified by atomic absorption spectrometry. Adhesion amount is a case of less than 5mg / m ² as a "◎", to evaluate the case of 5~20mg / m ² as "○", was to evaluate the case of more than 20mg / m ² as "×". The results are shown in Tables 2 and 3.

"Cleanability"
Each sample was immersed in a degreasing solution composed of an alkaline aqueous solution having a pH of 10.5 and a temperature of 40 ° C., and it was visually confirmed whether the entire surface of each sample was wetted with pure water every 10 seconds after the immersion. The time when the entire surface was wet with pure water was defined as the degreasing completion time, and the cleanability was evaluated by the size. The case where the degreasing time was 120 seconds or less was evaluated as “◯”, and the case where it exceeded 120 seconds was evaluated as “x”. The results are shown in Tables 2 and 3.

As is known from Tables 2 and 3, it can be seen that the test material D1 can exhibit more excellent moldability by forming a lubricating film.
In addition, when Sample B1 and Sample B24, which are formed with a lubricating film under the same conditions except for the type of the test material, are compared, Sample B24 is characterized in terms of formability and the amount of adhesion of aluminum wear powder. It was inferior to sample B1. This is considered to be attributable to the use of the specimen D1 in the sample B1 and the specimen D2 in the sample B24. The specimen material D1 and the specimen material D2 have different absorbance ratios A2 / A1 in FT-IR. In addition, the sample B23 using the test material D4 in which the absorbance ratio A2 / A1 of the hydrated oxide film was 0.1 also improved the moldability and reduced the amount of adhesion compared to the sample B24.
Therefore, the formability can be improved by using aluminum alloy plates for forming (sample D1 and sample D4) having a hydrated oxide film satisfying A2 / A1 ≧ 0.1 in FT-IR. It is thought that the amount of wearing can be reduced.

Also, from Table 2 and Table 3, it can be seen that the thickness of the hydrated oxide film is preferably 0.6 to 10 μm. Moreover, it turns out that 0.1-10 g / m < ² > is preferable for the adhesion amount of a lubricous film. Furthermore, when the additives (C1 to C3) are added, the amount of adhesion can be reduced, but it can be seen that if the amount added is increased, the moldability may be adversely affected.
Moreover, it can be seen that the heat treatment is performed after the formation of the lubricating film to improve the moldability, but the temperature is preferably 100 ° C. or higher and lower than 300 ° C.

Explanatory drawing which shows the cross section of the aluminum alloy plate for shaping | molding (Example D1) concerning Example 1. FIG. Explanatory drawing which shows the result of the FT-IR measurement of the hydrated oxide membrane | film | coat of the aluminum alloy plate for shaping | molding (test material D1) concerning Example 1. FIG. Explanatory drawing which shows the result of the FT-IR measurement of the hydrated oxide membrane | film | coat of the aluminum alloy plate for shaping | molding (sample D2) concerning Example 1. FIG. The electron micrograph figure showing the surface of the hydrated oxide membrane | film | coat of the aluminum alloy plate for shaping | molding (sample D1) concerning Example 1. FIG. Explanatory drawing which shows the cross section of the aluminum alloy plate for shaping | molding (Example B1) concerning Example 1. FIG.

Explanation of symbols

1 Aluminum alloy plate for forming 2 Aluminum alloy plate 3 Hydrated oxide film 4 Lubricant film

Claims (16)

An aluminum alloy plate for molding having an aluminum alloy plate and an Al hydrated oxide film formed on the surface of the aluminum alloy plate,
The hydrous oxide film is in the Fourier transform infrared spectroscopy measurement (FT-IR), a peak of the absorption spectrum in the vicinity of wave number 1100 cm ^-1 and near the wave number 1350 cm ^-1, the absorption spectrum in 1100 cm ^-1 vicinity The forming aluminum alloy satisfying the relationship of A2 / A1 ≧ 0.1, where A1 is the maximum absorbance at the peak and A2 is the maximum absorbance at the peak of the absorption spectrum in the vicinity of 1350 cm ^−1. Board.   2. The forming aluminum alloy sheet according to claim 1, wherein the hydrated oxide film has a thickness of 0.6 to 10 [mu] m. 3. The forming aluminum alloy plate according to claim 1, wherein the forming aluminum alloy plate has a lubricating film made of at least one selected from a lubricating oil, a solid lubricant, and a wax on the hydrated oxide film, The aluminum alloy plate for shaping | molding characterized by the adhesion amount of a conductive film being 0.1-10 g / m < ² >.   4. The aluminum alloy sheet for molding according to claim 3, wherein the lubricating oil contains at least one selected from esters, fatty acids, alcohols and fats and oils as an oily agent.   5. The forming aluminum alloy plate according to claim 3, wherein the lubricating oil contains a sulfur compound or / and a phosphorus compound as an extreme pressure agent.   The lubricating oil according to any one of claims 3 to 5, wherein the lubricating oil is selected from amines, alkanolamines, aliphatic polyamines, aromatic amines, alicyclic amines, heterocyclic amines, and alkylene oxide adducts thereof. An aluminum alloy sheet for molding, characterized by containing 0.01 to 2.0% by weight of at least one amine derivative.   The lubricating oil according to any one of claims 3 to 6, wherein the lubricating oil contains 0.1 to 5.0% by weight of sodium dioctylsulfosuccinate or / and an oxygen-containing compound having at least one quaternary carbon in the molecule. An aluminum alloy sheet for molding characterized by the above. A method for producing a forming aluminum alloy plate comprising an aluminum alloy plate and an Al hydrated oxide film formed on the surface of the aluminum alloy plate,
An alkali treatment step of contacting the alkali treatment liquid made of an alkaline aqueous solution on the surface of the aluminum alloy plate to remove the natural oxide film and generating smut;
In the alkali treatment step, without performing desmut treatment for removing the smut generated on the surface of the aluminum alloy plate, the aluminum alloy plate is contacted with water having a temperature of 50 ° C. or higher or a hydrothermal treatment solution made of an alkaline aqueous solution. And a hot water treatment step of forming the hydrated oxide film on the surface of the aluminum alloy plate.   9. The method for producing a forming aluminum alloy sheet according to claim 8, wherein, in the hydrothermal treatment step, the hydrated oxide film is formed with a thickness of 0.6 to 10 [mu] m. In Claim 8 or 9, the lubricating film forming agent which consists of 1 or more types chosen from lubricating oil, a solid lubricant, and wax is apply | coated on the said hydrated oxide film | membrane, and 0.1-10 g / m < ² >. The manufacturing method of the aluminum alloy plate for shaping | molding characterized by having the lubricating film formation process of forming the lubricating film of this.   11. The method for producing an aluminum alloy sheet for forming according to claim 10, wherein the lubricating oil contains at least one selected from esters, fatty acids, alcohols and fats and oils as an oily agent.   12. The method for producing a forming aluminum alloy sheet according to claim 10, wherein the lubricating oil contains a sulfur compound or / and a phosphorus compound as an extreme pressure agent.   The lubricant according to any one of claims 10 to 12, wherein the lubricating oil is selected from amines, alkanolamines, aliphatic polyamines, aromatic amines, alicyclic amines, heterocyclic amines, and alkylene oxide adducts thereof. A method for producing an aluminum alloy sheet for molding, comprising 0.01 to 2.0% by weight of at least one kind of amine derivative.   14. The lubricant according to claim 10, wherein the lubricating oil contains 0.1 to 5.0% by weight of sodium dioctylsulfosuccinate or / and an oxygen-containing compound having one or more quaternary carbons in the molecule. A method for producing a forming aluminum alloy sheet.   The forming aluminum alloy according to any one of claims 10 to 14, wherein a heating step of heating the forming aluminum alloy plate at a temperature of 100 ° C or higher and lower than 300 ° C is performed after the lubricating film forming step. A manufacturing method of a board.   A method for processing a forming aluminum alloy plate, comprising subjecting the forming aluminum alloy plate according to claim 1 to press forming.

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