JP2009107285A - Magnesium alloy sheet material, and its plastic deformation processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the plastic deformation processability of a magnesium alloy sheet material without using a surface protective sheet. <P>SOLUTION: First, the magnesium alloy sheet 1 is prepared (figure 1(a)). Then, the magnesium alloy sheet 1 is immersed in a chemical polishing treatment agent solution 3 which is housed in a chemical polishing treatment tank 2, and a chemical polishing treatment is performed (figure 1(b)). Then, the magnesium alloy sheet 1 is housed in a vapor deposition polymerizer 4 (figure 1(c)). On the surface of the magnesium alloy sheet 1, a high molecular polymer thin film 7 is formed by the vapor deposition polymerization of the first raw material monomer 5 and the second raw material monomer 6 (figure 2(d)). Then, the magnesium alloy sheet 1 on the surface of which the high molecular polymer thin film 7 has been formed is deep draw-processed by a deep drawing processing apparatus consisting of dies 8 and 9 (figure 2 (e)). In the last, the magnesium alloy sheet 1 after the deep drawing processing is taken out from the die 9 (figure 2 (f)). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a magnesium alloy sheet and a plastic deformation processing method thereof, and in particular, a magnesium alloy sheet whose plastic deformation workability is improved by forming a polymer thin film by vapor deposition polymerization of two or more kinds of raw material monomers, and the plasticity thereof. The present invention relates to a deformation processing method.

Conventionally, as a surface protection sheet for deep drawing processing of metal plate materials such as stainless steel plate and aluminum plate material, a base material film made of polyvinyl and a resin composition formed by blending liquid polyester oligomer in a specific ratio with polylactic acid are molded. The base film etc. which were obtained by this are known (for example, refer patent document 1). Such a surface protective sheet for deep drawing is adhered to the surface of a metal plate using an adhesive, and prevents the metal plate from cracking (breaking) by following the metal plate during deep drawing of the metal plate. Can do. The deep-drawing surface protective sheet is peeled off from the metal plate after the deep drawing and is subjected to disposal such as incineration.

On the other hand, a surface protective sheet is also known that gives decorativeness to the surface of a metal plate without being peeled off from the metal plate after deep drawing (see, for example, Patent Documents 2 and 3). Such a surface protective sheet can improve the followability with respect to deep drawing of a metal plate material, etc., and at the same time, can prevent distortion of decoration such as printing and cracking of the sheet.
Japanese Patent Application Laid-Open No. 7-100549 JP 2001-328216 A JP 2004-243565 A

However, in the above-described prior art, the surface protective sheet is attached to the surface of the metal plate with an adhesive, so that the surface protective sheet itself is easily peeled off due to the thickness of the surface protective sheet itself. There was a problem that the protection of the film was not achieved uniformly. Further, there is a problem that it is difficult to evenly attach the surface protective sheet to the metal plate material having a complicated surface shape.

Furthermore, the surface protective sheet peeled off from the metal plate after deep drawing has a problem in that it requires a disposal process such as an incineration process, which is troublesome to handle and has a large environmental load.

By the way, since magnesium is the lightest metal in industrial use, its alloy is used in various fields such as aircraft, automobile, precision machine, personal computer, mobile phone, etc. It has come to be widely used in place of conventional metal parts such as aluminum alloys.

For example, a typical AZ31B magnesium alloy is an alloy in which malleability is improved by adding about 3% aluminum and about 1% zinc as alloy elements to magnesium. Up to 3% of aluminum is added as an alloy for extension because no β phase (intermetallic compound of Mg17Al12) appears in the structure. However, at room temperature, the minimum bending radius of soft steel, brass, and pure aluminum is 0.5 μt (t is the plate thickness) or less, while the bending workability of magnesium alloy is higher than that of any other general-purpose metal. Inferior. For this reason, ductility at room temperature is only in the case of uniaxial tension, and ductility in other bending and drawing processes is extremely limited, and warm forming is required.

In particular, deep drawing is a processing method in which, for example, a cup-shaped cylindrical container with a bottom is formed by pressing a metal plate with a pair of male and female dies to cause plastic deformation. The deep drawing process is mainly a deformation of the flange part, and the limit is determined by the balance with the strength of the cup side wall part. In the deep drawing of a magnesium alloy plate material, it is known that a special forming defect such as a fracture from a die corner portion occurs and the forming limit is lowered.

An object of the present invention is to provide a magnesium alloy plate material that improves plastic deformation workability, particularly deep drawing workability, without using a surface protective sheet in view of the above points.

Another object of the present invention is to provide a plastic deformation processing method for a magnesium alloy sheet that can be carried out without using a surface protective sheet.

Means for Solving the Problems and Effects of the Invention

The magnesium alloy sheet according to claim 1 is characterized by comprising a magnesium alloy sheet and a polymer polymer thin film formed by vapor deposition polymerization of two or more kinds of raw material monomers on the surface of the magnesium alloy sheet. Here, vapor deposition polymerization means that two or more types of monomers (monomer) are heated and evaporated at the same time in a vacuum, and the monomers are polymerized on the substrate to polymerize the polymer such as polyimide, polyamide, and polyurea. It means forming a thin film. The film thickness can be controlled from nano (nm) order to several hundred microns (μm) order. According to the magnesium alloy sheet of claim 1, the surface friction of the magnesium alloy sheet is greatly increased by providing a polymer polymer thin film formed by vapor deposition polymerization of two or more kinds of raw material monomers on the surface of the magnesium alloy sheet. This lowers the occurrence of breakage during plastic deformation of the magnesium alloy sheet, and the effect of improving the plastic deformation workability of the magnesium alloy sheet is obtained. In addition, the polymer polymer thin film is easy to handle because it does not need to be peeled off from the magnesium alloy sheet after plastic deformation processing, and it does not require disposal such as incineration, so the environmental load is small. There are advantages.

The magnesium alloy sheet according to claim 2 is the magnesium alloy sheet according to claim 1, wherein the polymer polymer thin film is formed by vapor deposition polymerization using the first raw material monomer as a diamine component and the second raw material monomer as a diisocyanate component. A polyurea thin film formed by the above method.

The magnesium alloy sheet according to claim 3 is the magnesium alloy sheet according to claim 2, wherein the diamine component includes one or both of 1,12-diaminododecane and 1,3-bis (aminomethyl) cyclohexane. It is characterized by the following.

The magnesium alloy sheet according to claim 4 is the magnesium alloy sheet according to claim 2, wherein the diisocyanate component is one or both of 1,3-bis (isocyanatomethyl) cyclohexane and hexamethylene diisocyanate. It is characterized by comprising.

The magnesium alloy sheet according to claim 5 is the magnesium alloy sheet according to claim 2, wherein the combination of the diamine component and the diisocyanate component is a combination of 1,12-diaminododecane and hexamethylene diisocyanate, It consists of a combination of 1,3-bis (aminomethyl) cyclohexane and 1,3-bis (isocyanatomethyl) cyclohexane, or a combination of 1,3-bis (aminomethyl) cyclohexane and hexamethylene diisocyanate. It is characterized by that.

A magnesium alloy sheet according to claim 6 is the magnesium alloy sheet according to claim 2, wherein the combination of the diamine component and the diisocyanate component is 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylmethane. It is a combination with diisocyanate.

The magnesium alloy sheet according to claim 7 is the magnesium alloy sheet according to claim 1, wherein the polymer polymer thin film is formed by vapor deposition polymerization of pyromethric anhydride and bis (4-aminophenyl) ether. It is a thin film.

The method of plastic deformation processing of a magnesium alloy sheet according to claim 8 includes a step of forming a polymer thin film on the surface of the magnesium alloy sheet by vapor deposition polymerization of two or more kinds of raw material monomers, and the polymer thin film on the surface. And a step of subjecting the formed magnesium alloy sheet material to plastic deformation. According to the plastic deformation processing method for a magnesium alloy sheet according to claim 8, the surface friction of the magnesium alloy sheet is significantly reduced by forming a polymer polymer thin film on the surface of the magnesium alloy sheet, and the magnesium alloy sheet The occurrence of breakage during plastic deformation is suppressed, and the effect of improving the plastic deformation workability of the magnesium alloy sheet can be obtained.

The method of plastic deformation processing of a magnesium alloy sheet according to claim 9 is a method of forming a polymer thin film by vapor deposition polymerization of the two or more kinds of raw material monomers in the method of plastic deformation processing of a magnesium alloy sheet according to claim 8. The preceding stage includes a step of immersing the magnesium alloy plate material in a chemical polishing treatment agent solution and subjecting it to a chemical polishing treatment.

The plastic deformation processing method for a magnesium alloy sheet according to claim 10 is the plastic deformation processing method for a magnesium alloy sheet according to claim 8 or 9, wherein the polymer thin film has a first raw material monomer as a diamine component, The film is formed by vapor deposition polymerization using 2 raw material monomers as a diisocyanate component.

The method for plastic deformation of a magnesium alloy sheet according to claim 11, wherein the diamine component is 1,12-diaminododecane, 1,3-bis (aminomethyl) in the method for plastic deformation of a magnesium alloy sheet according to claim 10. ) Characterized in that it comprises either or both of cyclohexane.

The method for plastic deformation of a magnesium alloy sheet according to claim 12, wherein the diisocyanate component is 1,3-bis (isocyanatomethyl) cyclohexane, hexagonal in the method for plastic deformation of a magnesium alloy sheet according to claim 10. It is characterized by comprising either or both of methylene diisocyanate.

The plastic deformation processing method for a magnesium alloy sheet according to claim 13, wherein the combination of the diamine component and the diisocyanate component is 1,12-diaminododecane in the plastic deformation processing method for a magnesium alloy sheet according to claim 10. And hexamethylene diisocyanate, 1,3-bis (aminomethyl) cyclohexane and 1,3-bis (isocyanatomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane and hexamethylene di It is characterized by being in any combination with an isocyanate.

The plastic deformation processing method for a magnesium alloy sheet according to claim 14, wherein the combination of the diamine component and the diisocyanate component is 4,4'-diamino in the plastic deformation processing method for a magnesium alloy sheet according to claim 10. It is characterized by comprising a combination of diphenylmethane and 4,4′-diaminodiphenylmethane diisocyanate.

The plastic deformation processing method for a magnesium alloy sheet according to claim 15 is the plastic deformation processing method for a magnesium alloy sheet according to claim 8 or 9, wherein the polymer polymer thin film comprises pyromethric anhydride and bis (4-aminophenyl). ) A polyimide thin film formed by vapor deposition polymerization with ether.

The purpose of improving the plastic deformation workability of a magnesium alloy sheet without using a surface protective sheet is to form a polymer polymer thin film by vapor deposition polymerization of two or more kinds of raw material monomers on the surface of the magnesium alloy sheet. Achieved.

Next, the principle of the present invention will be described with reference to the drawings.

First, as shown in FIG. 1A, a magnesium alloy sheet 1 having a thickness capable of plastic deformation is prepared. The plastic deformation includes bending, drawing, deep drawing, and the like, and the thickness capable of plastic deformation is about 10 mm or less.

Next, as shown in FIG. 1 (b), the prepared magnesium alloy sheet 1 is immersed in a chemical polishing agent solution 3 accommodated in a chemical polishing tank 2 to perform chemical polishing. As the chemical polishing agent, an ethylene glycol hydrochloride solution or the like is used. The chemical polishing treatment removes dirt and the like adhering to the surface of the magnesium alloy plate 1 in advance and increases the adhesion of the polymer polymer thin film 7 formed in the subsequent vapor deposition polymerization process to the magnesium alloy plate 1. Done.

Subsequently, as shown in FIG. 1 (c), the magnesium alloy plate material 1 after the chemical polishing treatment is accommodated in the vapor deposition polymerization apparatus 4, and the first raw material monomer 5 and the second raw material monomer 6 are heated. By evaporating and evacuating the inside of the vapor deposition polymerization apparatus 4, as shown in FIG. 2 (d), the magnesium alloy sheet 1 is formed by vapor deposition polymerization of the first raw material monomer 5 and the second raw material monomer 6. A polymer thin film 7 is formed on the surface. The thickness of the polymer thin film 7 is determined in consideration of the material fluidity of the magnesium alloy sheet 1 in the subsequent plastic deformation process, but is preferably in the range of about 0.5 to 10 μm.

Next, as shown in FIG. 2 (e), the magnesium alloy plate 1 having a polymer polymer thin film 7 formed on the surface thereof by a deep drawing apparatus comprising a pair of male and female dies (die, punch) 8, 9. Deep drawing. Here, the deep drawing process is exemplified as the plastic deformation process, but any other plastic deformation process may be used.

Finally, as shown in FIG. 2 (f), the magnesium alloy sheet 1 having the polymer polymer thin film 7 formed on the surface thereof is removed from the deep drawing apparatus comprising a pair of male and female dies 8 and 9.

Hereinafter, specific embodiments to which the present invention is applied will be described in detail with reference to the drawings.

Embodiment 1

FIG. 3 is a diagram showing an example of a combination of two types of raw material monomers employed in the vapor deposition polymerization step in the plastic deformation processing method for a magnesium alloy sheet according to Embodiment 1 of the present invention. In this example, diamine monomer 1,12-diaminododecane (1,12-Diaminododecane) and isocyanate monomer 1,3-bis (isocyanatomethyl) cyclohexane (1,3-Bis (isocyanatomethyl)) cyclohexane) becomes polyurea by polyaddition reaction. By-products are not generated by the polyaddition reaction.

FIG. 4 is a schematic diagram showing an outline of a vapor deposition polymerization apparatus 4 used in a vapor deposition polymerization step in the plastic deformation processing method for a magnesium alloy sheet according to Embodiment 1 of the present invention. FIG. 5 is a principle diagram of a vapor deposition polymerization process in the plastic deformation processing method for a magnesium alloy sheet according to Embodiment 1 of the present invention, and equivalently shows the operation of the vapor deposition polymerization apparatus 4 of FIG. .

In FIG. 4, the vapor deposition polymerization apparatus 4 is formed by connecting a vacuum chamber 102 to a vacuum exhaust system 103. The vacuum chamber 102 includes a vacuum processing chamber 104, raw material chambers 112 and 113, flow rate adjusting valves 110 and 111, and evaporation tubes 114a and 114b. The vacuum exhaust system 103 includes a vacuum pump 115, an exhaust valve 120, and an exhaust pipe 118a.

The two types of raw material monomers 5 and 6 can be stored in the raw material chambers 112 and 113 by applying a pressure slightly higher than the pressure in the vacuum processing chamber 104 as a film forming chamber, and are kept at a constant temperature by a heater (not shown). Can keep. Further, the wall 104 a of the vacuum processing chamber 104 can be heated to about the evaporation temperature of the two types of raw material monomers 5 and 6.

The inside of the vacuum processing chamber 104 is evacuated S by the evacuation system 103 and heated to a temperature at which the saturated vapor pressures of the two types of raw material monomers 5 and 6 are equal to each other. Then, the polymer thin film 7 can be formed on the surface of the magnesium alloy sheet 1 by vapor deposition polymerization of the raw monomers 5 and 6.

Next, a plastic deformation processing method for a magnesium alloy sheet according to Embodiment 1 of the present invention will be described.

(1) Chemical polishing process The magnesium alloy board | plate material 1 which consists of AZ31B magnesium alloy was immersed in the chemical polishing treatment agent solution 3 which consists of 3 wt% ethylene glycol solution for 10 minutes at room temperature, and the chemical polishing process was performed.

(2) Vapor deposition polymerization process Polymer polymer thin film using 1,12-diaminododecane and 1.3-bis (isocyanatomethyl) cyclohexane by vapor deposition polymerization apparatus 4 using magnesium alloy sheet 1 after chemical polishing treatment. 7 was formed, and magnesium alloy sheet 1 having a thickness of the polymer thin film 7 of 0.6, 1.5, and 3.0 μm was prepared, respectively.

Specifically, the magnesium alloy plate 1 attached to the base holder 109 is held in the vacuum processing chamber 104 with the flow rate adjusting valves 110 and 111 and the exhaust valve 120 closed. Note that the inside of the vacuum processing chamber 104 is maintained in a vacuum atmosphere (Pc) of, for example, 30 ° C. (Tc) and 6 × 10 ⁻² Pa (see FIG. 5).

An isocyanate monomer (hereinafter denoted by the same reference numeral 5 as the first raw material monomer) is used as the first raw material monomer 5 in the raw material chamber 112, and a diamine monomer (hereinafter referred to as the second raw material monomer 6) in the raw material chamber 113. And the same reference numeral 6 as that of the second raw material monomer). The isocyanate monomer 5 is kept at 91 ° C. (T ₁ ) and 5.2 Pa (P ₁ ), for example, in the raw material chamber 112. In addition, the diamine monomer 6 is maintained at, for example, 98 ° C. (T ₂ ) and 0.46 Pa (P ₂ ) in the raw material chamber 113.

Next, the exhaust valve 120 is opened, and the vacuum processing chamber 104 is evacuated S. At this time, the vacuum pump 115 of the vacuum exhaust system 103 is used. The inside of the vacuum processing chamber 104 is, for example, a vacuum atmosphere (Pc) of 1 × 10 ⁻³ Pa.

Subsequently, the flow control valves 110 and 111 are opened, and the isocyanate monomer 5 and the diamine monomer 6 are introduced into the vacuum processing chamber 104. At the same time or a little later, the exhaust valve 120 is closed and the vacuum exhaust S is stopped. At this time, the conductance C ₁ is applied to the isocyanate monomer 5 and the conductance C ₂ is applied to the diamine monomer 6 by the flow control valves 110 and 111, respectively. That is, the respective flow rates Q1 and Q2 are set so that a polyurea thin film (hereinafter denoted by the same reference numeral 7 as the high polymer thin film) which is the high polymer thin film 7 is formed stoichiometrically. The amount of evaporation is adjusted so that the molar ratio is 1: 1.

Thereafter, the polyurea thin film 7 is autonomously formed on the surface of the magnesium alloy sheet 1 by polyaddition reaction. That is, the gas of the two kinds of raw material monomers of the isocyanate monomer 5 and the diamine monomer 6 becomes the polyurea thin film 7, but the volume becomes extremely small and there are no by-products, so the vacuum atmosphere in the vacuum processing chamber 104 is maintained. Will remain. Therefore, as long as two kinds of raw material monomer gases, isocyanate monomer 5 and diamine monomer 6, are supplied, the film forming reaction proceeds autonomously.

(3) Friction coefficient test The magnesium polymer plate 1 having a thickness of the polymer thin film 7 of 0.6, 1.5 and 3.0 μm was used as a test material, and a ball-on-disk friction tester was used. The friction coefficient was tested. Since the ball-on-disk friction tester is not directly related to the present invention, its details are omitted. Table 1 shows the friction test conditions. Specifically, the counterpart material is a high carbon chromium bearing steel SUJ2, each load is 1, 2, 5, 10 Newton, the diameter of the ball material is 4.73 mm, the friction speed is 10 mm / s, and the friction distance is 100 m. did. The number of trials was 3 times.

6 (a), (b), and (c) are graphs showing the friction coefficient test results of the magnesium alloy sheet 1 with the polyurea thin film 7 having a thickness of 0.6, 1.5, and 3.0 μm, respectively. is there. While the untreated material has a coefficient of friction of about 0.3, the polyurea (PU) thin film 7 has a thickness of 0.6, 1.5 and 3.0 μm, and the magnesium alloy sheet 1 (hereinafter referred to as appropriate). , Abbreviated as PU vapor deposition material 1) shows a value of about 0.1, and it can be seen that the friction coefficient has been greatly reduced.

(4) Deep drawing workability test As a deep drawing workability test, a cylindrical deep drawing test was performed using a tensile tester. The tensile tester is not directly related to the present invention, and the details are omitted. In the same test, after annealing at 250 ° C. for 30 minutes, the magnesium polymer sheet 1 having a thickness of the polymer thin film 7 of 0.6, 1.5, and 3.0 μm was used as a test material. Deep drawing was performed until it occurred, and the drawing depth was compared with the untreated material. Table 2 shows the cylindrical deep drawing test conditions. Specifically, the material is AZ31B magnesium alloy, and the specimen size is 50 mm in width, 50 mm in length, and 0.7 mm in thickness. The PU film thickness value is 3.0 μm, the punch dimension is 21.4 mm in diameter and the radius of curvature is 8 mm, and the die dimension is 24.7 mm in diameter and the radius of curvature is 8 mm. The molding temperature was 250 ° C., and the molding speed was 5.0 mm / min.

FIG. 7 is a graph showing punch stroke results until the untreated material and the PU vapor deposition material 1 are broken. In the PU vapor deposition material 1, the molding load required to obtain the same punch stroke was drastically reduced as compared with the untreated material. As revealed by the friction test, since the friction coefficient of the PU vapor deposition material 1 shows a low value, it can be considered that the resistance of the blank contact portion is reduced and the load applied to the PU vapor deposition material 1 is reduced.

FIGS. 8A and 8B are drawing-substituting photographs showing the appearance of the untreated material and the PU vapor-deposited material 1 after deep drawing. As is clear from FIGS. 8A and 8B, a PU vapor deposition material (AZ31B magnesium alloy plate material having a polyurea thin film 7 formed on the surface) 1 having a polyurea thin film 7 formed on the surface by vapor deposition polymerization 1 It can be seen that the deep drawability is greatly improved compared to the untreated material.

According to the first embodiment, the surface friction of the magnesium alloy sheet 1 is greatly increased by forming the polymer polymer thin film 7 on the surface of the magnesium alloy sheet 1 by vapor deposition polymerization of two kinds of raw material monomers 5 and 6. The occurrence of breakage during plastic deformation of the magnesium alloy sheet 1 is suppressed, and the effect of improving the plastic deformation workability of the magnesium alloy sheet 1 is obtained. In addition, the polymer thin film 7 is easy to handle because it does not need to be peeled off from the magnesium alloy sheet 1 after plastic deformation as compared with the surface protection sheet, and has no environmental impact because it does not require disposal such as incineration. There is an advantage of being small.

Embodiment 2

FIG. 9 is a schematic diagram showing an outline of a vapor deposition polymerization apparatus 4 ′ used in the plastic deformation processing method for a magnesium alloy sheet according to Embodiment 2 of the present invention. FIG. 10 is a principle diagram of a vapor deposition polymerization process in the plastic deformation processing method for a magnesium alloy sheet according to Embodiment 2 of the present invention, and equivalently shows the operation of the vapor deposition polymerization apparatus 4 ′ of FIG. is there.

The vapor deposition polymerization apparatus 4 ′ shown in FIG. 9 is an apparatus devised to form a high-quality polymer polymer thin film 7 than the vapor deposition polymerization apparatus 4 shown in FIG. 4. Differences from the vapor deposition polymerization apparatus 4 shown in FIG. 4 will be briefly described.

First, the vapor deposition polymerization apparatus 4 ′ mixes two kinds of raw material monomers 5 and 6 in the mixing chamber 107 and rectifies them by the shower plate 107a, thereby spraying uniformly on the magnesium alloy plate 1 to produce magnesium. The quality of the polymer thin film 7 formed on the surface of the alloy plate 1 is improved.

Secondly, the vapor deposition polymerization apparatus 4 ′ also takes into consideration the gas component (released amount) coming out from the wall surface 104 a of the vacuum processing chamber 104. In other words, the inside of the vacuum processing chamber 104 may be made atmospheric to carry in the magnesium alloy sheet 1 or carry out the finished product. At this time, gas components in the atmosphere are stored on the wall surface 104 a of the vacuum processing chamber 104. This gas component comes out in a high vacuum atmosphere. In order to perform exhaust according to the amount of discharge, the vacuum exhaust system 103 ′ has an exhaust adjustment valve 122 capable of adjusting conductance in addition to the exhaust valve 120, and an exhaust valve 121 for switching to the piping 118b. Is provided. Further, in order to increase the efficiency of restoration of the vacuum atmosphere after being brought into the atmosphere for carrying in the magnesium alloy sheet 1 and carrying out the finished product, a roughing pipe 118c, an exhaust valve 124, and a roughing vacuum pump 116 are provided. Have.

Next, regarding the vapor deposition polymerization step in the plastic deformation processing method of the magnesium alloy sheet according to Embodiment 2 of the present invention, the difference from the vapor deposition polymerization step in the plastic deformation processing method of the magnesium alloy sheet according to Embodiment 1 is mainly described. Explained.

First, the magnesium alloy plate 1 attached to the substrate holder 109 is held in the vacuum processing chamber 104 with the flow rate adjusting valves 110 and 111, the exhaust valves 120, 121, 123, and 124, and the exhaust control valve 122 closed. Note that the inside of the vacuum processing chamber 104 is maintained in a vacuum atmosphere (Pc ′) of 30 ° C. (Tc ′) and 6 × 10 ⁻² Pa, for example (see FIG. 10).

The raw material chamber 112 is filled with the isocyanate monomer 5 as the raw material monomer 5, and the raw material chamber 113 is filled with the diamine monomer 6 as the raw material monomer 6. The isocyanate monomer 5 is kept at 91 ° C. (T ₁ ) and 5.2 Pa (P ₁ ), for example, in the raw material chamber 112. In addition, the diamine monomer 6 is maintained at, for example, 98 ° C. (T ₂ ) and 0.46 Pa (P ₂ ) in the raw material chamber 113.

Next, the exhaust valve 124 is opened, and the vacuum processing chamber 104 is evacuated S ′. At this time, the vacuum pump 116 for roughing of the evacuation system 103 ′ is used. Then, the vacuum exhaust S ′ = the vacuum exhaust Seff, and the vacuum processing chamber 104 is exhausted rapidly. The inside of the vacuum processing chamber 104 is, for example, a vacuum atmosphere of 1.3 × 10 ^{−1 to} 1.3 × 10 ⁻² .

Subsequently, the exhaust valve 124 is closed. At the same time or a little later, the exhaust valves 120 and 123 are opened and the vacuum pump 115 is driven. The inside of the vacuum processing chamber 104 is, for example, a vacuum atmosphere (Pc ′) of 1 × 10 ⁻³ Pa.

Next, the flow rate adjusting valves 110 and 111 are opened, and two kinds of raw material monomers 5 and 6 are introduced into the vacuum processing chamber 104. At the same time or a little later, the exhaust valve 120 is closed and the exhaust valve 121 and the exhaust adjustment valve 122 are opened. The exhaust adjustment valve 122 adjusts the conductance C ₀ in accordance with the amount of gas discharged from the wall 104 a in the vacuum processing chamber 104. As a result, the vacuum exhaust Seff is adjusted to a slight flow rate corresponding to the gas discharge amount. At this time, the relationship of l / Seff = 1 / S ′ + l / C ₀ is established.

Thereafter, film formation on the surface of the magnesium alloy sheet 1 proceeds autonomously by the polyaddition reaction.

In the second embodiment, the shower plate 107a is used as a means for rectifying the mixed gas of the two kinds of raw material monomers 5 and 6. For example, a louver structure in which metal thin plates are arranged in parallel, or a metal thin plate is used. A honeycomb structure assembled in a lattice shape, a hexagonal shape, or the like may be used.

Although the exhaust control valve 122 of Katachikuma second embodiment is adjusted to the conductance C ₀ commensurate with the emission of gas from the wall 104a of vacuum processing chamber 104, two or more of the raw material monomer that is slightly byproducts You may adjust according to the combination of. Any discharge amount that does not hinder autonomous film formation by polyaddition reaction can be handled.

Furthermore, there are various types (types) of vacuum pumps 115 and 116 used in the vacuum exhaust systems 103 and 103 ′ of the first and second embodiments, and these can be appropriately selected or combined. Pumps are, for example, turbo molecular pumps, cryopumps, sorption pumps, sputter pumps, getter pumps, oil diffusion pumps, oil diffusion ejectors, oil rotary pumps, dry pumps, mechanical booster pumps, water seal pumps, reciprocating pumps, steam ejectors Etc.

The embodiments of the present invention have been described above. However, these are merely examples, and the present invention is not limited to them, and the knowledge of those skilled in the art without departing from the scope of the claims. Various modifications based on the above are possible.

For example, in Embodiments 1 and 2, the combination of raw material monomers 5 and 6 is a combination of 1,12-diaminododecane and 1,3-bis (isocyanatomethyl) cyclohexane. There may be. Furthermore, two or more kinds of raw material monomers may be used in combination as long as the combination causes a polyaddition reaction. In these cases, the present invention can be similarly applied.

For example, any one or both of 1,12-diaminododecane and 1,3-bis (aminomethyl) cyclohexane can be mixed and used as the diamine component.

Further, as the diisocyanate component, any one or both of 1,3-bis (isocyanatomethyl) cyclohexane and hexamethylene diisocyanate can be mixed and used.

Furthermore, as a combination of a preferred diamine component and diisocyanate component, in addition to the embodiment, a combination of 1,12-diaminododecane and hexamethylene diisocyanate, 1,3-bis (aminomethyl) cyclohexane and 1 , 3-bis (isocyanatomethyl) cyclohexane, and 1,3-bis (aminomethyl) cyclohexane and hexamethylene diisocyanate.

Furthermore, as a combination of two kinds of raw material monomers used for vapor deposition polymerization of the polyurea thin film 7, for example, 4,4′-diaminodiphenylmethane (MDA) and 4,4′-diaminodiphenylmethane diisocyanate (MDI) A combination of can be used. Also in this example, no by-product is generated because of the polyaddition reaction.

In addition, the polymer polymer thin film to be formed is not limited to a polyurea thin film, and a polyimide thin film, a polyamide thin film, or the like can also be used. For example, a polyimide thin film formed by vapor deposition polymerization of pyromethric anhydride (PMDA) and bis (4-aminophenyl) ether (ODA) can be used. In this example, since it is a polycondensation reaction, water (H ₂ O) is generated as a by-product. However, a magnesium alloy plate material with a polyurea thin film formed on a magnesium alloy plate material with a polyimide thin film formed on the surface and Needless to say, the same plastic deformation workability can be obtained.

(A)-(c) is the first half process figure in the plastic deformation processing method of the magnesium alloy board | plate material of this invention. (D)-(f) is the latter-half process drawing in the plastic deformation processing method of the magnesium alloy board | plate material of this invention. The figure which shows an example of the combination of two types of raw material monomers employ | adopted at the vapor deposition polymerization process in the plastic deformation processing method of the magnesium alloy board | plate material which concerns on Embodiment 1 of this invention. The schematic diagram which shows the outline of the vapor deposition polymerization apparatus used at the vapor deposition polymerization process in the plastic deformation processing method of the magnesium alloy board | plate material which concerns on this Embodiment 1. FIG. The principle figure of the vapor deposition polymerization process in the plastic deformation processing method of the magnesium alloy board | plate material which concerns on Embodiment 1 of this invention. (A), (b), (c) is a graph which respectively shows the test result of the friction coefficient of the magnesium alloy board | plate material whose thickness of a polyurea thin film is 0.6, 1.5, and 3.0 micrometers. The graph which shows the punch stroke result to the fracture | rupture of an untreated material and PU vapor deposition material, respectively. (A), (b) is drawing substitute photograph which shows the external appearance of the untreated material and PU vapor deposition material after a shaping | molding process. The schematic diagram which shows the outline of the vapor deposition polymerization apparatus used for the plastic deformation processing method of the magnesium alloy board | plate material which concerns on Embodiment 2 of this invention. The principle figure of the vapor deposition polymerization process in the plastic deformation processing method of the magnesium alloy board | plate material which concerns on Embodiment 2 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Magnesium alloy board | plate material 2 Chemical polishing processing tank 3 Chemical polishing processing agent solution 4, 4 'Deposition polymerization apparatus 5, 6 Raw material monomer 7 Polymer polymer thin film 8, 9 Mold 102, 102' Vacuum tank 103, 103 'Exhaust system 104 Vacuum processing chamber 104a Wall (wall surface)
107 Mixing chamber 107a Shower plate 109 Base holder 110, 111 Flow rate adjusting valve 112, 113 Raw material chamber 114a, 114b Evaporating pipe 115, 116 Vacuum pump 118a, 118b, 118c Exhaust pipe 119a, 119b Branch 120, 121 Exhaust valve 122 Exhaust adjustment Valve 123, 124 Exhaust valve

Claims (15)

Magnesium alloy sheet,
A polymer thin film formed by vapor deposition polymerization of two or more kinds of raw material monomers on the surface of the magnesium alloy sheet;
A magnesium alloy sheet characterized by comprising: The magnesium alloy sheet according to claim 1, wherein the polymer polymer thin film is a polyurea thin film formed by vapor deposition polymerization using the first raw material monomer as a diamine component and the second raw material monomer as a diisocyanate component. The magnesium alloy sheet according to claim 2, wherein the diamine component comprises one or both of 1,12-diaminododecane and 1,3-bis (aminomethyl) cyclohexane. The magnesium alloy sheet according to claim 2, wherein the diisocyanate component comprises one or both of 1,3-bis (isocyanatomethyl) cyclohexane and hexamethylene diisocyanate. The combination of the diamine component and the diisocyanate component is a combination of 1,12-diaminododecane and hexamethylene diisocyanate, 1,3-bis (aminomethyl) cyclohexane and 1,3-bis (isocyanatomethyl). 3. The magnesium alloy sheet according to claim 2, which is one of a combination of cyclohexane and a combination of 1,3-bis (aminomethyl) cyclohexane and hexamethylene diisocyanate. The magnesium alloy sheet according to claim 2, wherein the combination of the diamine component and the diisocyanate component is a combination of 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylmethane diisocyanate. The magnesium alloy plate material according to claim 1, wherein the polymer polymer thin film is a polyimide thin film formed by vapor deposition polymerization of pyromethric anhydride and bis (4-aminophenyl) ether. Forming a polymer thin film by vapor deposition polymerization of two or more kinds of raw material monomers on the surface of the magnesium alloy sheet;
Applying a plastic deformation process to the magnesium alloy sheet having the polymer polymer thin film formed thereon;
A method of plastic deformation processing of a magnesium alloy sheet characterized by comprising. The process according to claim 8, further comprising a step of immersing the magnesium alloy plate material in a chemical polishing treatment solution and subjecting it to chemical polishing treatment before the step of forming a polymer thin film by vapor deposition polymerization of the two or more kinds of raw material monomers. Plastic deformation processing method of magnesium alloy sheet. The magnesium alloy sheet according to claim 8 or 9, wherein the polymer thin film is a polyurea thin film formed by vapor deposition polymerization using the first raw material monomer as a diamine component and the second raw material monomer as a diisocyanate component. Plastic deformation processing method. The method of plastic deformation of a magnesium alloy sheet according to claim 10, wherein the diamine component comprises one or both of 1,12-diaminododecane and 1,3-bis (aminomethyl) cyclohexane. The method for plastic deformation of a magnesium alloy sheet according to claim 10, wherein the diisocyanate component comprises one or both of 1,3-bis (isocyanatomethyl) cyclohexane and hexamethylene diisocyanate. The combination of the diamine component and the diisocyanate component is a combination of 1,12-diaminododecane and hexamethylene diisocyanate, 1,3-bis (aminomethyl) cyclohexane and 1,3-bis (isocyanatomethyl). The method for plastic deformation processing of a magnesium alloy sheet according to claim 10, which is any one of a combination of cyclohexane and 1,3-bis (aminomethyl) cyclohexane and hexamethylene diisocyanate. The plastic deformation processing of a magnesium alloy sheet according to claim 10, wherein the combination of the diamine component and the diisocyanate component is a combination of 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylmethane diisocyanate. Method. The method for plastic deformation processing of a magnesium alloy sheet according to claim 8 or 9, wherein the polymer polymer thin film is a polyimide thin film formed by vapor deposition polymerization of pyromethric anhydride and bis (4-aminophenyl) ether.