JPS59226197A - Surface treatment of aluminum alloy for patterning - Google Patents

Abstract

PURPOSE:To pattern clearly the surface of an extruded Al alloy with high work efficiency by patterning the surface of the Al alloy by mechanical operation, subjecting the alloy to two-stage age hardening, and forming a colored film. CONSTITUTION:The surface of an extruded Al alloy is patterned by mechanical operation, and the alloy is subjected to primary incomplete age hardening and secondary incomplete age hardening or complete age hardening at a temp. above the primary hardening temp. The surface of the Al alloy is then degreased and washed, and after removing smut as required, a colored oxide film is formed by electrochemical operation.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention provides a surface treatment method that can clearly produce various decorative patterns such as wood grain and print patterns on the surface of aluminum alloys (excluding pure aluminum) that have age hardening properties. More specifically, by applying a skillful combination of mechanical manipulation, two-step age hardening treatment, and electrochemical manipulation to the surface of aluminum alloy, it is possible to create shading differences on the surface of aluminum alloy using an extremely simple method. Patterning of aluminum alloys, which can produce a beautiful colored pattern and a corrosion-resistant colored film, is related to a surface treatment method.

Conventional technology and its problems Conventionally, as a method of generating a colored pattern on the surface of an aluminum material using artificial age hardening treatment, there is a method described in Japanese Patent Application Laid-open No. 53
-83941 is known. This technology involves attaching a desired patterned p-sheet to the surface of an aluminum material, subjecting it to artificial age hardening under normal conditions, removing the patterned p-sheet before or after cooling, and then removing the patterned p-sheet from the aluminum material. In this method, a colored pattern is generated on the surface of an aluminum material by applying an electrolytic coloring treatment using aluminum as an anode. The generation mechanism of the colored pattern in this method is to bring about a difference in the crystal structure due to heating between the part where the pattern sheet is attached to the aluminum material and the part where it has been adhered during the age hardening treatment. This creates a pattern during electrolytic coloring.

However, this technique has the following drawbacks.

α) The temperature inside the age hardening furnace is not necessarily uniform between the left and right, top and bottom, front and rear ends and the center, and there are temperature differences, making it difficult to control the pattern of the resulting product.

b) Aluminum material has very good heat conduction, so
It is difficult to create a temperature difference between the attached part of the patterned sheet and the unattached part. Therefore, it is difficult to produce a colored pattern with a clear difference in shading, and it is also difficult to make small patterns such as a spotted pattern, a polka dot pattern, and a woodgrain pattern appear on an aluminum material.

C) A process of attaching and detaching the patterned sheet is required, and a patterned sheet must be prepared for each shape of the extruded shape, so the workability is extremely poor and the resulting product is expensive. Get high.

Furthermore, as another method for forming a patterned oxide film, the method described in Japanese Patent Publication No. 43-6365 is known. This technology uses a specially selected aluminum alloy for the entire composition of the AL-M-Mf alloy, expands the aluminum alloy, applies special heat treatment during or after the processing process, and then anodizes the aluminum alloy. This is a method of producing a contrasting black-and-white pattern on the surface of an aluminum alloy due to the precipitation of a μmMn binary compound.

The patterns obtained by this method are completely random in form, making it possible to obtain any pattern, and the patterns are limited to black and white contrast, so it is still possible to obtain decorative and beautiful colored patterns. The problem is that it cannot be used.

OBJECTS OF THE INVENTION Therefore, the first object of the present invention is to provide a surface treatment method for patterning aluminum alloy, which is easy to work with and can produce various desired colored patterns such as beautiful woodgrain or printed patterns on the surface of aluminum alloy. It's about doing.

The second object of the present invention is to improve corrosion resistance, in relation to the above object.
The patterning of aluminum alloys can be done on the surface by creating colored patterns with excellent weather resistance, abrasion resistance, etc., and imparting mechanical strength, especially hardness, to aluminum alloys in a series of processes with high productivity and energy efficiency. The purpose is to provide a processing method.

A third object of the present invention, in relation to the above object, is to provide a surface treatment method for patterning an aluminum alloy, which allows the colored pattern to be an extremely clear colored pattern with further differences in shading. .

Still another object of the present invention, in connection with the above-mentioned object, is to provide a method of surface treatment for patterning an aluminum alloy, which provides a clearer contrast of the colored pattern and has extremely excellent colorability.

Structure of the Invention The present invention provides an incomplete age hardening treatment after applying a base pattern to an aluminum alloy after extrusion molding by mechanical manipulation, instead of the conventional complete age hardening treatment after extrusion molding. and by subjecting the aluminum alloy to the treatment in two stages: incomplete to complete age hardening treatment at a temperature higher than the set temperature for the hardening treatment, and further applying a colored film to the aluminum alloy by electrochemical operation. , due to the mutual effect of the formation of the base pattern by the mechanical operation, the two-step age hardening treatment, and the formation of the electrochemical colored film, there is a gap between the base pattern part and the background (non-patterned part). This is based on the knowledge that differences in coloring occur and the base pattern is extremely clearly exposed on the surface of the aluminum alloy.Furthermore, by adding an oxide film modification step to the colored film forming step, This method is also based on the knowledge that the colored pattern obtained by the basic method described above can be further improved into an extremely clear colored pattern with different shading.

That is, the first invention according to the present invention corresponds to the objects of the first and second inventions, and includes (A) applying a base pattern by mechanical operation to the aluminum alloy surface after extrusion molding; Next, the aluminum alloy is subjected to a first incomplete age hardening treatment, and then subjected to a second incomplete age hardening treatment or a complete age hardening treatment at a temperature higher than the set temperature of the above hardening treatment. The basic structure is to form a colored film on the surface of an aluminum alloy.

Further, a second invention according to the present invention corresponds to the object of the first to fourth inventions, and includes the steps (A to (C) in place of step (a) of the first invention). After each step of (Z)') (i) forming an oxide film on the aluminum alloy by a conventional method, (11) then performing AC electrolysis in an inorganic acid and/or organic acid bath to form the oxide film. This method adopts a configuration in which G11) is subjected to coloring treatment after being modified into a double film structure.

Furthermore, a third invention according to the present invention corresponds to the object of the first to fourth inventions, and in place of step (2) of the first invention, the After each process, an oxide film is formed on the glazed aluminum alloy using a conventional method, (11) the aluminum alloy is then connected to a cathode in an inorganic acid and/or organic acid bath, and subjected to direct current electrolysis. After modifying the oxide film, a coloring treatment is applied.

(The following is a blank space) Aspects of the Invention Next, each step of the present invention and its aspects will be explained in detail.

First, the aluminum alloy (hereinafter referred to as aluminum (hereinafter referred to as "alloy" for short) is subjected to a base pattern by mechanical manipulation.Mechanical manipulation includes all operations other than etching with acid or alkali and chemical treatment.

This base pattern can be created using, for example, the plasto method in which sand, iron powder, etc. are sprayed, the high-pressure injection method in which water or other liquid is injected at high pressure, the brush method in which the aluminum alloy surface is scratched with a brush, the laser beam method in which the surface is irradiated with a laser beam, or the embossed plate roll. It is applied to the surface of an aluminum alloy by various mechanical operation means such as a roller method using a mold press and a press method using a mold press.

To be more specific, 1. For example, aiming to improve workability,
Immediately after extruding the aluminum alloy, a zero clearance mold or metal frame (jig) that has the same shape as the extrusion mold and is spaced at regular intervals is provided with injection grooves (holes) for high-pressure injection at, for example, straight-grain pattern intervals, and Or continuously adjust the surface while spraying abrasives, etc.
By applying a base pattern (applying a base pattern), it is possible to apply a base pattern to even complex-shaped irregularities. In this case, a desired continuous pattern (for example, a long straight-grain interval as in printing, a pattern that changes into a blur, etc.) can be easily imparted. In addition, instead of the above-mentioned high-pressure injection, metal or ceramic claw-shaped jigs are arranged inside the mold or metal frame arranged after the extrusion mold, for example, at straight-grained intervals, and extrusion molding is performed with a constant pressure. The method of rubbing the later form can also be adopted.

In addition, after the extruded aluminum is cooled, it can be processed to give scratches or distortions.
Desired patterns such as letters and pictures can be easily formed, and the decorativeness can be further enhanced. Furthermore, regarding panel relations.

It can also be stamped using a die press, allowing any complex pattern to be created.

In addition, as a mutual effect method with the shape of the shape, patterns can also be imparted by creating unevenness in the shape of a pattern on the shape itself, and then rubbing the surface with metal, ceramic, carbon, etc. immediately after extrusion or after cooling. can.

The means for forming the base pattern is not limited to the above methods, but any method may be used as long as it can form a decorative pattern on the surface of the aluminum alloy profile using a method with good workability.

The formation of this base pattern is caused by the interaction of the subsequent age hardening treatment (first incomplete age hardening treatment and second incomplete to complete age hardening treatment) and electrochemical coloring treatment, which forms the base for the colored pattern to appear. The depth of the concave part of the scratched part is not an essential element for surface adjustment (base pattern formation), but it is sufficient that it is within the die mark to pass the appearance.
Even after the oxide film was formed, no performance deterioration due to the scratches was observed even when observed under a microscope.

Also, the parts that were subjected to strain were bent in the same way, and there was no deterioration in performance at all.

(Towards: 1st Incomplete Age Hardening Treatment Step The 1st age hardening treatment is carried out under conditions where the aluminum alloy does not reach complete aging.

To explain age hardening treatment, for example, Alba alloy A
In the case of -60635 material, the influence of age hardening temperature and time on the hardness of the alloy is as shown in FIG. That is, the dust reaches its maximum value after a certain amount of time has elapsed at any temperature, and age hardening at this stage is defined as complete age hardening.

Therefore, incomplete age hardening means age hardening before reaching this stage.

Although FIG. 1 shows the state of high-temperature aging or artificial aging, incomplete aging here is not limited to this, but also includes room temperature aging or natural aging. Therefore, to put it in an extreme case, it may be left to stand for a long time to allow natural aging.

(02nd incomplete to complete age hardening treatment process This means that either incomplete age hardening or complete age hardening may be used. This secondary age hardening treatment is more effective than the previous 1-pi primary age hardening treatment. Perform at high temperature.

Regarding the effect of the two-stage age hardening treatment (first and second), for example, the first aging (
Figure 2 shows the combination of aging (160°C) and secondary aging (190°C) and the effects of the conditions.

As is clear from Figure 2, under all conditions,
The combination of primary aging and secondary aging is 190℃ x 6Ar
Stage complete age hardening treatment also has the effect of increasing the height of the sand layer. This effect is achieved by a combination of primary and secondary age hardening treatments.

The subsequent coloring treatments (D), (1)') and (D') will darken the areas where the surface has been adjusted, such as scratches or scratches (base pattern areas), making it possible to create a pattern with contrast in coloring. Another effect is that sufficient hardness can be imparted to the aluminum alloy before electrolytic treatments such as anodic oxidation, electrolytic coloring, oxide film modification, and electrolytic coloring.

Note that Figure 2 shows the results when cooling to room temperature between the primary and secondary age hardening treatments, but the effect described above will not occur unless a cooling process is included between the primary and secondary aging treatments. It becomes less. Therefore, it is preferable to include a cooling process between the primary and secondary age hardening treatments, so that the hardness is greater than that of a simple two-step age hardening process, and the subsequent coloring process makes it possible to harden the underlying pattern. The difference in color shading from the background (non-patterned area) becomes even larger.

In addition, the temperature of the (01st incomplete age hardening treatment) and (C)
It is preferable that the temperature difference from the temperature of the secondary incomplete age hardening treatment to the secondary complete age hardening treatment is set to 5°C to 60'C. The reason is that if the temperature is less than 5℃, 1 age hardening treatment is
This is because the effect of dividing into stages is not clearly visible, and sufficient hardness and sufficient difference in color shading cannot be obtained in the coloring treatment. In addition, the reason why the upper limit was set at 60℃ is that if the temperature difference is larger than this, the temperature of the primary incomplete age hardening treatment will be lower, which will increase the treatment time and reduce the efficiency of the manufacturing process, making it uneconomical. It is because it is.

Moreover, the appropriate range of time and temperature for the first incomplete age hardening treatment in the two-stage age hardening treatment is shown in FIG.

The shaded areas indicate particularly preferred ranges.

Note that the secondary age hardening treatment requires at least 1 hour or more.

(Colored film treatment process) The Alba alloy that has gone through each of the above steps (4 to A colored oxide film is formed on the surface of the aluminum alloy by the method described above.

α) After subjecting the Alba alloy to 1-pole oxidation treatment using direct current, alternating current, or a current waveform similar to these in an electrolytic solution containing an inorganic acid and/or an organic acid, an electrolytic solution containing an inorganic metal salt is applied. A colored film is formed by AC electrolysis or DC cathode electrolysis.

A colored film is formed by so-called anodic oxidation-electrolytic coloring. The electrolyte used for anodization is a well-known inorganic acid and/or organic acid.

For example, well-known electrolytes such as sulfuric acid, chromic acid, phosphoric acid, or a mixed acid solution of these acids, oxalic acid, malonic acid, etc., or a mixed acid solution of these or inorganic acids can be used, and the applied voltage and application voltage for anodic oxidation can be The time etc. are also sufficient as usual.

Inorganic metal salts used for electrolytic coloring include sulfates, hydrochlorides, oxalates, tartrates, and chromium such as nickel, cobalt, chromium, copper, cadmium, titanium, manganese, molybdenum, tin, magnesium, silver, and lead. Various conventionally known salts such as acid salts and phosphates can be used, and the electrolysis can be carried out under conventional conditions.

b) A colored film is formed by an electrolytic coloring method in which an anodized film is formed on the aluminum alloy surface and colored at the same time in an electrolytic solution containing an inorganic acid and a metal salt, or an electrolytic solution containing an organic acid.

Various methods are known such as the ematal method and the Rα1calor method, and the organic acids that cause the anodic oxide film to develop color include oxalic acid, malonic acid, sulfosalicylic acid,
Various acids or mixed acids such as sulfophthalic acid, maleic acid, and tartaric acid are known.

C) In an electrolytic solution containing an inorganic acid, a colored film is formed by a natural coloring method in which an anodized film is formed on the surface of an aluminum alloy made of a naturally colored alloy and at the same time the color develops and fades.

Also known as the alloy coloring method, this method produces color when anodic oxidized due to the influence of metals added to aluminum, and exhibits a color unique to the alloy components. In general, when the contained component is Cr, it is yellowish-brown, and when it is Crt, it is yellowish-brown.
In the case of Si, it is blackish.

In the case of Mn, it is known that the color becomes pinkish.

Further, in the Δt-Mn-Cr alloy, the coloration varies depending on the heat treatment conditions, such as bronze color when Mn and Cr are in a solid solution state and black color when they are precipitated.

By p-electrochemically coloring using the various methods described above, a colored film with excellent corrosion resistance and weather resistance is formed, and the base pattern portion (scratches or distortions) is transformed into a background (non-patterned portion). The base pattern applied to the aluminum alloy surface by mechanical operation appears as a colored pattern.

The aluminum alloy thus treated with a colored film is sent to a painting process, if necessary, and subjected to painting and baking treatments using well-known methods.

The second and third inventions according to the present invention adopt the steps of anodic oxidation film treatment → oxide film modification treatment → coloring treatment instead of the colored film treatment step (1) of the first invention,
Depending on the difference in oxide film modification treatment, it can be divided into the following two methods.

That is, after each step of the above (4 to (0), (D') (i
) An oxide film is formed on the aluminum alloy by a conventional method.

(11) Subsequently, the oxide film is modified into a double film structure by alternating current electrolysis in an inorganic acid and/or organic acid bath.

A method of applying OIO coloring treatment (second invention), (D (1) forming an oxide film on the aluminum alloy by a conventional method; This is a method (third invention) of connecting the oxide film to a cathode and modifying the oxide film by direct current electrolysis, and then subjecting the oxide film to a coloring treatment (11D).

The oxide film modification treatments (D') (ii) and (D"Xti) are not necessarily essential as in the first invention, but are steps performed for the purpose of making the pattern contrast clearer That is, the colored film treatment (4)
Although there are cases where the @ body is sufficient, oxide film modification treatment is performed to improve workability and improve decorativeness.

The conditions include the above-mentioned colored film treatment (1 electrolyte, which is the same as the electrolyte solution, or one in which additives such as metal salts are added to it,
Alternatively, a different electrolyte may be used, but cathodic electrolysis is performed in this electrolytic solution, or electrolytic treatment is performed using alternating current or a waveform having an equivalent effect.

For example, a standard combination is to perform anodization in a sulfuric acid bath, followed by alternating current electrolysis using the same electrolyte and carbon as a counter electrode. Note that the same effect can be obtained by performing anodization and oxide film modification by changing the concentration, temperature, etc. using the same electrolyte as the colored film treatment (gradient), and by adding additives.

Each step will be explained below.

(D') (i), (D'Xl) Oxide film formation step As explained above (gradient (α)), in an electrolyte of inorganic acid and/or organic acid, direct current or alternating current or similar A current waveform is used to anodize an aluminum alloy to form an oxide film.

The electrolytic conditions such as applied voltage and bath temperature are sufficient as usual.

(D') (11), (D"Xti) Oxide film modification step The oxide film on the surface of the aluminum alloy obtained as described above is modified by one of the following methods.

(D') (Ii) Alternating current electrolytic reforming An electric current having alternating current or equivalent properties to an aluminum alloy in an electrolytic solution consisting of an inorganic acid such as sulfuric acid, phosphoric acid, or chromic acid or an organic acid such as oxalic acid. By applying a waveform current, the oxide film is modified into a double film structure. The electrolytic conditions are as usual and are sufficient, but preferably 5 to 30V, 1
The test is carried out for ~30 minutes.

This secondary anodic oxidation treatment by AC electrolysis is not intended to produce a two-colored film, but in conjunction with the oxide film treatment described above, is to produce an oxide film with a double film structure.

Due to the formation of this double film structure, in the colored pattern formed by the subsequent coloring process, the difference in color shading between the base pattern portion and the background becomes remarkable, and the contrast of the single colored pattern becomes clearer.

(D (11) Cathode Direct Current Electrolytic Reforming The aluminum alloy on which the oxide film has been formed is connected to the cathode in an electrolytic solution consisting of an inorganic acid such as sulfuric acid or phosphoric acid, and a direct current of t
or a current waveform having properties equivalent to this, the aluminum alloy is energized.

This current treatment causes a dissolution effect on the oxide film on the aluminum alloy surface, but at this time, because the amount of current flowing is different between the base pattern and other parts (background), there is a difference in the quality of the film between the two. Get out. As a result, the contrast of the colored pattern becomes more noticeable through the subsequent coloring process.

The concentration of the electrolytic solution, the applied voltage for 1 hour, etc. are sufficient as usual, but preferably the conditions are 13 to 20 V and 20 seconds to 10 minutes.

(DsuGij), CDsu011) Coloring treatment step The oxide film modified in the above step is colored by the method described in (gradient (α)) above. That is, alternating current in an electrolytic solution containing an inorganic metal salt. A colored film is formed by electrolysis or direct current cathode electrolysis.

As a result, an extremely clear colored pattern with varying shading is formed on the aluminum alloy surface.

Material Although pure aluminum is excluded in the present invention, various aluminum alloys can be used. Aluminum alloys are alloys that increase strength by quenching and tempering, i.e. Ctb, AIr + S' + Zn + J as the main additives.
(Although a preferable example is one to which f or the like is added, it is not limited to this only.

Furthermore, the color tone of a single colored pattern and the contrast of the pattern can be adjusted by combining additive elements, work hardening, heat treatment conditions, etc. Further, in order to enhance the heat treatment effect and shorten the treatment time, the amount of added elements can be changed. For example, Al-M
In the W-5i alloy, or Aff -Si -
/'g alloy, age hardening can be promoted by combining the amounts of addition, for example by adding excess Si.

Therefore, for the purpose of improving color tone, pattern contrast, workability of processing steps, etc., it is possible to use an aluminum alloy with an alloy component suitable for the processing steps and conditions.

Effects of the Invention As described above, the patterning of the aluminum alloy according to the present invention can be achieved by a surface treatment method, which includes one step of forming a base pattern by mechanical operation and two steps of age hardening treatment.

Due to the mutual effects of the steps of forming the electrochemically colored film and the electrochemically colored film formation, a difference in color shading occurs between the base pattern portion and the background, and the surface of the aluminum alloy is affected.

In addition to being excellent in various performances such as corrosion resistance, weather resistance, and abrasion resistance,
Various desired beautiful colored patterns such as woodgrain, print, etc. can be created. Furthermore, by adding the oxide film modification step, the difference in color shading is further increased, and a colored pattern with sharper contrast and extremely excellent coloring properties can be obtained.

Furthermore, since a two-step age hardening process is adopted, mechanical strength, especially hardness, can be imparted to the aluminum alloy in a series of steps before anodizing or forming a colored film, and furthermore, immediately after extrusion, it is possible to impart mechanical strength, especially hardness, to the aluminum alloy. Since patterns can be formed, surface treatment of aluminum pentalloys can be performed with good workability, productivity, and energy efficiency. In addition, since the underlying pattern is exposed as a colored contrast pattern, the racking form in the first surface treatment process can be either horizontally hung or vertically hung, and there is no need to add any new technology, which is currently standardized. This method has the advantage of being sufficient to deal with the problem.

In addition, the aluminum alloy shapes treated according to the present invention showed no deterioration in performance even after being given a base pattern, no defects were observed when observing the oxide film or colored film under a microscope, and various tests showed that the aluminum alloy shapes were not colored by electrolytic coloring. It is no different from shaped materials and can be used freely for the same purpose, without any restrictions on interior or exterior use.

Examples Example 1 Aluminum alloy (-60635) immediately after extrusion molding
After pressing uneven carbon onto the surface of the shape to form a base pattern and subjecting it to a first incomplete age hardening treatment at 160°C for 3 hours, the aluminum alloy shape was once cooled to room temperature, and then 190℃.

A secondary age hardening treatment was performed for 3 hours.

After that, the aluminum alloy shape is degreased, etched,
After removing the smut, the profile was prepared using a conventional method.
The current density was 1. I, 4/
dm2 (voltage approximately 12F), liquid temperature 20℃.

The anodic oxidation treatment was carried out for 30 minutes to form an anodic oxide film of about 10 μm on the surface.

After washing with water, as a coloring process, the length is 200mb and the width is 150mm.
A container with a height of 150 m and a carbon counter electrode placed at one end is used as an electrolytic coloring device, and the length is 150 W + m.
, the aluminum alloy shape having a width of 70 wn and a thickness of 1.3 wn was set to a carbon counter electrode with a distance of 180 m, and sulfuric acid hot 7 t, sodium trithionate + t 7 t, sulfuric acid 1
When immersed in an electrolytic solution having a composition of 4 f/l tin and having a temperature of 16°C, AC electrolysis was performed for 5 minutes and 30 seconds at an initial current density of 1 A/dm2 and an applied voltage of +oV. A beautiful ocher decorative pattern, which is darker than the original, was revealed.

Example 2 Aluminum alloy (, (-6
0635) Water is applied to the surface of the profile using a high-pressure injection device.
A base pattern was formed by spraying 100 OKP/- from a 2 mφ nozzle, and then heated at 160°C.

Immediately after the first incomplete age hardening treatment was carried out under the conditions of 2 hours, the secondary age hardening treatment was carried out under the conditions of 190° C. and 4 hours.

After that, the aluminum alloy shape is degreased, etched,
After removing the smut, the profile was immersed in a 1 gW/V% sulfuric acid aqueous solution, and the current density was 1. l A/dm2 (voltage approx. 12
V) An anodizing treatment was performed at a liquid temperature of 20° C. for 1 hour and 30 minutes to form an anodic oxide film of about 10 μm. Subsequently, as an oxide film modification treatment, a current density of 3 A / 2 was applied to a carbon counter electrode at the same concentration and temperature as in the anodic oxidation treatment bath.
AC electrolysis was carried out at dm2 (voltage approximately gV) for 8 minutes, and then the aluminum alloy shape was subjected to AC electrolysis coloring using the same equipment as in Example 1 and under the same conditions. The patterned area was colored much darker ocher than the background, revealing a clear decorative pattern.

Example 3 The oxide film modification treatment of Example 2 was carried out at a current density IA/
When the aluminum alloy profile was treated in exactly the same manner as in Example 2, except that the aluminum alloy profile was connected to the cathode and subjected to direct current electrolysis at dm2 (voltage approximately 5F) for 2 minutes, the surface of the profile was A beautiful decorative pattern with a difference in shading between the base pattern and the background appeared.

Example 4 Aluminum alloy (Δ-60
635) A laser beam with a frequency of 3.0 KB and I 6 A was irradiated onto the surface of the pattern at a speed of 10 degrees/sec to form a base pattern. Then, 170℃×2hr
After the first incomplete age hardening treatment was carried out under the following conditions, the sample was once cooled to room temperature, and then the second age hardening treatment was carried out under the conditions of 190°C x 3hγ.

After that, the aluminum alloy shape is degreased, etched,
After removing the smut, the profile was immersed in a sulfuric acid aqueous solution of 'i I 8 W/l'%, and the current density was 1. l A/dm2(
Anodizing was carried out under the conditions of 12 V)% solution temperature and 30 minutes to form an anodic oxide film of about 10 μm. Next, as a first coloring treatment, using the same apparatus as in Example 1, the shape was immersed in an electrolytic solution having the following composition at a temperature of 20°C, and the initial current density was 1 A / dm2, IIV.
When alternating current electrolysis was carried out for 5 minutes and 30 seconds at an applied voltage of O, the underlying pattern was colored much darker than the background, resulting in a clear decorative pattern.

Electrolyte composition: sulfuric acid 204 and nickel sulfate
309/1 Stannous sulfate 5 f/l cresol sulfonic acid 10 Gua was extruded into an argonium alloy (A-60) which was naturally cooled after extrusion molding.
63S) After contacting the surface of the profile with uneven carbon to form a base pattern, and then subjecting it to a primary incomplete age hardening treatment under the conditions of 160°C and 4Ar, the aluminum alloy profile was directly treated with l90'CX3Ar. Secondary age hardening treatment was performed under the following conditions.

After that, the aluminum alloy profile is degreased, etched, and smut removed, and then anodized to a length of 2.
A container with a width of 150 mm, a width of 150 wn, and a height of 150 points and a carbon counter electrode placed at one end of the container was used as an anodizing treatment device, and was immersed in an electrolytic solution having the following composition and a bath temperature of 20 ° C. When AC electrolysis was carried out for 45 minutes at an applied voltage of a current density of 2 A/dm2.7, the underlying pattern was colored much darker than the background, resulting in a clear decorative pattern.

Electrolyte composition: Sulfuric acid + BW/V% 2 t/s of tinned sulfate Example 6 The base pattern forming treatment of Example 2 was performed by etching a stainless steel plate with a thickness of approximately 0.1 μm to form irregularities of approximately 30 μm. The method was exactly the same as in Example 2, except that a patterned embossing plate was made, placed on an aluminum alloy profile, and then stamped with a roller to form a pattern on the aluminum alloy surface. The aluminum alloy profile was processed using

Example 7 Aluminum alloy immediately after extrusion molding (-6063,5
) A base pattern was formed on the surface of the profile by injecting silica sand (particle size: 00) from a nozzle of 6.4 φ at an air pressure of 2 Kp/crA.

Next, after first incomplete age hardening treatment under the conditions of 160°C x 4 hr, once cooled to room temperature, 200°C) <
A secondary age hardening treatment was performed under the conditions of 2Ar, and then degreased, etched, and smut removed in the same manner as in Example 3, and the shape was immersed in a 17 W/V% sulfuric acid aqueous solution at a current density of 1. 2 A/dm2 (voltage 12.5 V),
Anodized at a liquid temperature of 20°C for 35 minutes, approximately 105
A μm thick anodic oxide film was formed. Next, as an oxide film modification treatment, a current density of 1.2 A/dm2 (voltage: 6 J) was applied.
') for 1 minute and 30 seconds.

The aluminum alloy profile was connected to the cathode and subjected to direct current electrolysis. Next, as a coloring treatment, in the same container as in Example 1,
Immersed in an electrolytic solution with a bath temperature of 28 ° C. having the following composition,
AC electrolysis was performed for 3 minutes at an applied voltage of initial current density +/IALm2°11F.

Only the side that was sandblasted became a black striped color, while the side that was not sandblasted was a dark brown, resulting in a beautiful shape with different colors depending on the side of the shape.

Electrolyte composition: Nickel sulfate 25t/Magnesium sulfate +5t/Ammonium sulfate 30μ Boric acid 20f/l Ammonium thiosulfate I f/1 PR5,5 Comparative example 1 In Example 1, age hardening treatment was performed by primary incomplete aging +6
When the same treatment as in Example 1 was carried out except that only the conditions were 0'C/3hr, the result was a light yellowish color, and the base pattern was colored slightly darker than the background, but it was less clear than in Example 1. The hardness and Vickers hardness were also low.

Vickers hardness: Example 1 80.9 Comparative example 1 66.5 Comparative example 2 In Example 1, the age hardening treatment was performed at 190°C.

When the same treatment as in Example 1 was carried out except that Ohr's complete age hardening treatment was carried out, the entire surface was colored ocher, and there was no difference in coloring between the underlying pattern and the background, and no pattern was exhibited.

Furthermore, the Vickers hardness was low.

Vickers hardness: Example 1 80.9 Comparative example 2 74.5

[Brief explanation of drawings]

Figure 2 is a graph showing the influence of age hardening temperature and treatment time on the hardness of aluminum alloy (A 6063S).
60℃) and secondary aging (190℃) and the effects of these conditions on the hardness of aluminum alloy (Δ-6063.5). Figure 3 shows the time of the primary incomplete age hardening treatment. It is a graph showing the appropriate range of temperature. Applicant Yoshida Kogyo Co., Ltd. Representative Patent Attorney Masaaki Yonehara Patent Attorney Flood Tadashi Procedural Amendment July 5, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1. Indication of Case Patent Application No. 100321 No. 1988 2. Invention Name: Aluminum alloy patterning is surface treatment method 3, relationship with the amended case Patent applicant address: Ichibanchi, Kanda Izumi-cho, Chiyoda-ku, Tokyo Name (6)
82) Yoshida Kogyo Co., Ltd. Representative Director Yoshi 1) Tadao 4, Representative 5-16-5 Toranomon-chome, Minato-ku, Tokyo
, Date of amendment order Voluntary amendment 6, Subject of amendment

Claims (1)

[Scope of claims] A secondary incomplete age hardening treatment or a complete age hardening treatment is performed at a temperature higher than the set temperature for the treatment, and then a colored film is formed on the aluminum alloy surface to make the base pattern clear on the aluminum alloy surface. The patterning of aluminum alloy, which is characterized by exposing it, is a surface treatment method. After age hardening treatment at 1!fAL, 7'C, (0) perform secondary incomplete age hardening treatment or complete age hardening treatment at a temperature higher than the set temperature of the above hardening treatment, (D') L. An oxide film is formed on an aluminum alloy by a conventional method, (11) followed by alternating current electrolysis in an inorganic acid and/or organic acid bath to modify the oxide film into a double film structure, and then 611) coloring. A surface treatment method for patterning an aluminum alloy, characterized in that the underlying pattern is clearly exposed on the surface of the aluminum alloy by the treatment. 3 (a) Mechanical manipulation on the aluminum alloy surface after extrusion molding. (h) Next, the aluminum alloy is subjected to a first incomplete age hardening treatment, and (C) a second incomplete age hardening treatment or a complete aging treatment is performed at a temperature higher than the set temperature of the above hardening treatment. (y) After that, forming an oxide film on the aluminum alloy by a conventional method (1, (11) followed by connecting the aluminum alloy to a cathode in an inorganic acid and/or organic acid bath. A surface treatment method for patterning an aluminum alloy, characterized in that after the oxide film is modified by direct current electrolysis, the base pattern is clearly exposed on the surface of the aluminum alloy by (iii) coloring treatment. .