• 专利附录
  • 专利说明
  • 权利要求
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  • 同族专利
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    • 专利摘要:
    PURPOSE: To provide a method for removing a coating film of a coated magnesium alloy member including a method for adequately and quickly removing a coating film formed on a surface of the magnesium alloy member. CONSTITUTION: The method for removing the coating film on the coated magnesium alloy member comprises a partially removing step (S11) of physically and partially removing the coating film from the coated magnesium alloy member, and a chemical treating step (S12) to further remove the coating film by applying alkaline removing solution to the magnesium alloy member after passing through the partially removing step (S11).
    公开号:KR20040023507A
    申请号:KR1020030058120
    申请日:2003-08-22
    公开日:2004-03-18
    发明作者:기무라고오이찌；니시이고따
    申请人:후지쯔 가부시끼가이샤；
    IPC主号:
    专利说明:

    METHODS FOR REMOVING A COATING FILM OF A COATED MAGNESIUM ALLOY MATERIAL}
    [23] The present invention relates to a recycling technique of a coated magnesium alloy material. Specifically, the present invention relates to a method for removing a coating film from a coated magnesium alloy material, such as a magnesium alloy housing used for a personal notebook computer or a mobile phone, for producing a magnesium alloy reclaimed material.
    [24] The housings of mobile electronic devices such as personal notebook computers, cellular phones, PDAs, and the like are required to have high strength, efficiently dissipate heat generated from internal electronic components, and excellent recycling properties. In order to cope with these demands, as the housing of the mobile electronic device, a metal housing has been adopted instead of the conventional resin housing.
    [25] As a material which comprises the metal housing for electronic devices, the light alloy which has light metals, such as magnesium (Mg) and aluminum (Al) as a main component, attracts attention from the viewpoint of weight reduction of an apparatus. In particular, Mg is characterized by having the largest specific strength among the single-member metals that can be used as structural materials, high enough to be Al for heat dissipation, and small to about 70% of Al for specific gravity. Therefore, Mg alloy which has Mg as a main component is useful as a constituent material of an electronic device housing.
    [26] As the injection molding method for parts and products made of Mg alloy, a die casting method is common, but a thixomolding method may be employed in some cases. In the case of injection molding a personal notebook computer housing using, for example, a molten alloy of Mg alloy by die casting or thixomolding, the volume occupied by the site for forming is about 30 to 50% with respect to one molten injection amount. to be. The remaining 50 to 70% is occupied by the Mg alloy solidified by a part to be cut and removed after molding, that is, a spool or a runner in a mold. According to the die-casting method or thixomolding method, the material loss rate in one injection molding in this way is large. Therefore, in the field of injection molding of Mg alloy material, in view of the effective use of earth resources and cost reduction, the use of Mg alloy material obtained by the part cut and removed after injection molding and product recovery from the viewpoint of effective use of earth resources as a material which contributes to injection molding again There is a demand for the establishment of recycling technology.
    [27] As a method for producing the Mg alloy reclaimed material from the site which is cut and removed after the injection molding of the Mg alloy material, the site which is cut and removed after the injection molding of the Mg alloy material is melted again with a predetermined flux and cooled after the component adjustment is performed in the molten state. A method of solidifying and regenerating as an Mg alloy having a predetermined composition is disclosed (see Patent Document 1, for example).
    [28] On the other hand, parts and products made of Mg alloy which are shipped to the market are generally subjected to coating treatment, and a coating film is formed on the surface thereof. When the Mg alloy material having the coating film formed thereon is melted without removing the coating film in the above-described method, a large amount of organic gas is generated by the combustion of a resin material such as an acrylic resin or a urethane resin contained in the paint, which is not preferable. . In addition, the molten metal may be excessively contaminated by titanium or the like contained in the paint. Therefore, in manufacturing Mg alloy regeneration material from Mg alloy material obtained by product collection | recovery, it is necessary to remove the coating film formed in the surface of Mg alloy material before melting Mg alloy material.
    [29] As a technique for removing the coating film formed on the surface of Mg alloy material, the wet blast method is disclosed, for example (refer patent document 2). The wet blasting method is a method for physically removing a coating film by blowing water as a fluid to an Mg alloy material to be coated together with inorganic particles, such as alumina, for example. However, it is difficult to remove a coating film appropriately only by such a wet blast method when the coating surface of Mg alloy material has an uneven | corrugated shape. Specifically, since the inorganic particles tend to be less likely to collide in the recesses, the coating film may not be sufficiently removed. On the contrary, since the collision frequency of an inorganic particle tends to be excessive in a convex part, the Mg alloy of the surface of a member may also be cut | disconnected with a coating film.
    [30] As another technique for removing the coating film formed on the surface of an Mg alloy material, the method of using an alkali peeling liquid is known. This method is a method for removing a coating film by washing with water, etc., after immersing a to-be-coated Mg alloy material in alkali peeling liquid, and swelling a coating film by the action of the said alkali peeling liquid. However, in the conventional method of immersing in an alkali peeling liquid, one immersion process is performed until the whole coating film swells. Specifically, the Mg alloy material to be coated is continuously immersed in an alkali stripping solution until both layers of the coating film, which generally consists of a lower coating layer and an upper coating layer, swell. In such immersion treatment, immersion time may require a long time of about 2 hours.
    [31] [Patent Document 1]
    [32] Japanese Patent Laid-Open No. 2001-316739 (4 to 6 pages, Figs. 1 to 2)
    [33] [Patent Document 2]
    [34] Japanese Patent Laid-Open No. 2000-263443 (4 to 5 pages, Figs. 2 to 5)
    [35] The present invention has been devised based on such circumstances, and an object thereof is to provide a method for producing a magnesium alloy reclaimed material, including a method for appropriately removing a coating film formed on the surface of a magnesium alloy material in a short time.
    [1] BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flowchart showing a process from peeling of a coating according to a first embodiment of the present invention to production of a magnesium alloy reclaimed material.
    [2] 2 illustrates an example of a magnesium alloy housing of a personal notebook computer.
    [3] Fig. 3 is a flowchart showing a process from peeling of the coating according to the second embodiment of the present invention to production of the magnesium alloy reclaimed material.
    [4] Fig. 4 is a flowchart showing a process from peeling of the coating according to the third embodiment of the present invention to production of the magnesium alloy reclaimed material.
    [5] <Explanation of symbols for the main parts of the drawings>
    [6] S11: Partial Removal Process
    [7] S12: first chemical liquid treatment step (first chemical liquid treatment step)
    [8] S13: water washing process
    [9] S14: Squeeze Treatment
    [10] S15: sorting process
    [11] S16, S16a-S16c: 2nd chemical liquid processing process (additional chemical liquid processing process)
    [12] S17, S17a to S17c: water washing process
    [13] S18, S18a to S18c: neutralization step
    [14] S19, S19a to S19c: water washing process
    [15] S20, S20a to S20c: removal process
    [16] S21: drying process
    [17] S22 dissolution process
    [18] S23 sludge separation process
    [19] S24: Cleansing Process
    [20] S25: Component Analysis Process
    [21] S26: Component Adjustment Process
    [22] S27: Casting Process
    [36] The coating film removal method of the coated magnesium alloy material provided by this invention is a partial removal process which physically and partially removes a coating film with respect to the magnesium alloy material to which the coating was given, and the magnesium alloy material via the said partial removal process. It is characterized by including the chemical | medical solution treatment process which makes an alkali peeling liquid act on, and peels a coating film further.
    [37] According to the coating film removal method including such a process, in a partial removal process, the contact area of a coating film and a processing liquid is enlarged, and an alkali peeling liquid is easy to permeate into the interface or coating film between a coating film and a magnesium alloy material. Part of the coating film is physically removed. Thereby, the time of the rice cleaning required in order to remove the whole coating film is shortened. In addition, since the coating film can be removed to some extent by physical action, the time required for removing the coating film is shortened as the amount of the coating film to be removed in the following processing step decreases.
    [38] In suitable embodiment of this invention, the said partial removal process is performed by incision formation or wet blast into the coating film by a cutter knife.
    [39] In the case of forming into the coating film by the cutter knife as described above, it is preferable that at least the cutting reaches the surface of the magnesium alloy material. As a result, in the subsequent chemical liquid treatment step, the alkali stripping liquid can penetrate into the interface between the magnesium alloy material and the coating film from the incision and cause the coating film to float, thereby promoting the peeling of the coating film.
    [40] The coating film in a magnesium alloy material to be coated generally consists of an upper coating layer for achieving a desired color tone and a lower coating layer for achieving a good coating adhesion state of the upper coating layer on the magnesium alloy surface. Generally, the lower coating layer is more difficult to remove than the upper coating layer. However, if the chemical liquid treatment step is carried out in the state where the upper coating layer is present, the alkaline coating liquid is deteriorated at the time when the upper coating layer can be peeled off and the lower coating layer is removed. There is a possibility that the ability to peel off remains. Therefore, when using a wet blast, it is preferable to partially remove a coating film at least to the level (for example, about 20 to 50% of the coating film whole quantity) from which an upper coating layer is removed. Thereby, since the upper coating layer is already removed, the alkaline peeling liquid of the processing process performed continuously by the partial removal process can act on the lower coating layer immediately. Therefore, since this alkali peeling liquid does not deteriorate due to peeling and dissolving an upper coating layer, since the lower coating layer can be reliably peeled off with the so-called "fresh" alkali peeling liquid, the whole coating film is removed. The net time required for it is shortened.
    [41] The coating film removal method of the present invention further includes an additional chemical liquid treatment step of further peeling the coating film by using a separation solution separate from the alkali stripping liquid, and the peeling area ratio of the coating film surface is 90 in the first chemical liquid treatment step. The magnesium alloy material which is% or more may be removed to perform the above additional chemical liquid treatment step only on the remaining magnesium alloy material.
    [42] When the proportion of the peeling area reaches 90% or more, the amount of organic gas generated by burning of resin materials such as acrylic resin and urethane resin contained in the paint is small even when the magnesium alloy is regenerated in the melting furnace at that time. The molten metal is not excessively contaminated by titanium or the like contained in the paint. Therefore, the thing which peeled 90% or more of peelings at this time is reduced, and the burden of the process required for peeling is further reduced. In addition, the ratio of a peeling area shows the ratio of the area of the part from which the coating film peeled with respect to the whole coating area by a percentage.
    [43] In a preferred embodiment of the present invention, the remaining magnesium alloy material via the first chemical liquid treatment step is classified into a plurality of groups according to the peeling area ratio of the coating film, and the additional chemical liquid treatment step is performed using a different peeling liquid for each group. To do it.
    [44] In addition, when performing an additional chemical | medical solution treatment process in this way, at least 1 of the peeling liquid used for the said further chemical liquid processing process is an alkaline peeling liquid separate from the alkaline peeling liquid used for the initial chemical liquid processing process, and the said further chemical liquid processing It is preferable that at least another one of peeling liquid used for a process is an acid peeling liquid.
    [45] According to the ratio of the peeling area, it is classified into a plurality of groups, and the peeling area is relatively large, and the alkaline peeling solution is applied to the group which can sufficiently peel off with the alkaline peeling solution without using an acid peeling solution. If the acid stripping solution is not used, the acid stripping solution is applied to the group that cannot be sufficiently peeled in the further treatment step. Thereby, since an acid peeling liquid is not used with respect to the magnesium alloy material which can be peeled sufficiently without using an acid peeling liquid with a comparatively large ratio of peeling area, it can suppress that a magnesium alloy material melt | dissolves. Moreover, even when using an alkali peeling liquid, the usage-amount of the concentrated alkali peeling liquid which requires attention at handling can be suppressed by changing the density | concentration of alkali peeling liquid appropriately for each group according to the ratio of the peeling area. In addition, the "separate alkali stripping liquid" as used herein means an alkali stripping liquid not used in the first chemical liquid treatment step, and may have the same composition as the alkaline stripping liquid used in the chemical liquid processing step, and has a different composition. It may be. In addition, it is preferable that the alkaline stripping liquid used for an initial chemical | medical solution treatment process and a further chemical | medical solution treatment process contains potassium hydroxide or sodium hydroxide as an alkaline main component, and it is preferable that an acid stripping liquid contains organic acid as an acid main component.
    [46] In a preferred embodiment of the present invention, an additional physical removal step may be performed in order to remove the coating film remaining in the magnesium alloy material even after performing the additional chemical liquid treatment step. Specifically, the remaining coating film portion is physically removed by a scraper or the like. Thereby, it becomes possible to remove coating films, such as the part which has a complicated shape of a housing | casing, such as the part which has a complicated shape of a housing which is difficult to remove in an initial chemical liquid processing process and an additional chemical liquid processing process.
    [47] Preferably, the method further comprises a neutralization step of neutralizing the acid stripping solution adhering to the magnesium alloy material via the further processing step following the further processing step using the acid stripping solution.
    [48] Since the magnesium alloy material is dissolved in an acid, dissolution of the magnesium alloy material is suppressed by neutralizing the acid stripping solution adhering to the additional treatment step in the neutralization step. As a result, the recovery loss of the magnesium alloy material is reduced, and the magnesium alloy material can be regenerated without waste. In addition, it is preferable that neutralization in a neutralization process is performed by making sodium hydroxide act.
    [49] In this invention, you may repeat the cycle which consists of an initial chemical liquid processing process and an additional chemical liquid processing process. Thereby, it becomes possible to peel even the coating film which is hard to peel off in one cycle.
    [50] In a preferred embodiment of the present invention, a water washing step for water washing the magnesium alloy material is performed immediately after the first chemical solution treatment step and / or the additional chemical solution treatment step. By water washing the magnesium alloy material via the chemical liquid treatment step at a predetermined hydraulic pressure, it is possible to appropriately remove the coating film whose application adhesion to the magnesium alloy material surface is reduced due to swelling or the like from the magnesium alloy material surface.
    [51] EMBODIMENT OF THE INVENTION Next, preferred embodiment of this invention is described based on an accompanying drawing.
    [52] 1 is a flowchart from peeling of the coating according to the first embodiment of the present invention to production of a magnesium (Mg) alloy reclaimed material. By passing through each process, the coating film formed in the surface of Mg alloy material as shown in FIG. 2, for example is removed. The Mg alloy material of Fig. 2 is a personal notebook computer housing, and coating is applied to a predetermined portion of the surface thereof. The coating film is made up of, for example, an upper coating layer for achieving a desired color tone, and a lower coating layer for achieving a good coating adhesion state of the upper coating layer on the Mg alloy surface, and includes an epoxy resin coating, a urethane resin coating, and an acrylic. Resin paints and the like are used. Examples of the epoxy resin paints include epoxy amino resin paints, epoxy ester paints, epoxy dip cream primers, epoxy tar paints (tar epoxy paints), epoxy phenol resin paints, epoxy polyamide paints, and the like. As a urethane resin paint, a two-component urethane paint, a moisture hardening type urethane paint, an oxidative hardening type urethane paint, etc. are mentioned. Examples of the acrylic resin paint include paints containing acrylic monomers such as acrylic acid or methacrylic acid esters.
    [53] In partial removal process (S11), a part (especially upper coating layer) of the coating film of the to-be-coated Mg alloy material is removed physically. Specifically, it is performed by cutting into a coating film with the blade of a cutter knife, etc., or by wet blast (for example, blowing water as a fluid to a coating film with inorganic particles, such as alumina). . It is preferable that the cutting into the coating film by the blade cutter such as a cutter knife is performed to a depth reaching the interface between the lower coating layer and the substrate. In addition, it is preferable that the removal amount of the coating film removed by the wet blast is performed until at least the upper coating layer is removed (about 20 to 50% of the total coating film amount).
    [54] In 1st chemical liquid processing process S12, the to-be-coated Mg alloy material via the partial removal process S11 is immersed in 1st alkali peeling liquid. The first alkali stripping liquid used in the first chemical liquid treatment step (S12) is 10 to 20 times the volume of the Mg alloy material. The temperature of a 1st alkali stripping liquid shall be 50-90 degreeC, and immersion time shall be 5-30 minutes. It is preferable that the 1st alkali peeling liquid contains the hydroxide of an alkali metal or alkaline-earth metal as an alkali component. Especially as an alkaline component, potassium hydroxide is suitable. As for the density | concentration of potassium hydroxide in a 1st alkali peeling liquid, 2-40 weight% is preferable. A part of coating film is peeled off by such a 1st chemical liquid processing process (S12). In addition, part of the remaining coating film is also swollen, and the coating adhesion to the Mg alloy material is lowered.
    [55] Next, the Mg alloy material is pulled out of the first alkali stripping solution and water washed in the water washing step (S13). In this step, water is sprayed onto the Mg alloy material using a shower device. The water pressure at this time is made into 0.5-2 kgf / cm <2>. Alternatively, in this step, water washing may be performed by immersing the Mg alloy material in the washing water stored in a predetermined bath. By such a water washing step (S13), the coating film swelling on the surface of the Mg alloy material or the coating film member attached to the Mg alloy material surface is physically removed from the Mg alloy material.
    [56] Next, in scraping-out process (S14), it removes that the ratio of the peeling area of a coating film in the Mg alloy material via the water washing process (S13) is 90% or more. Here, after quenching, the Mg alloy material is dried and introduced into a dissolution step (S20) described later. In addition, before performing drying, you may make it pass through processes, such as a neutralization process (S17), a water washing process (S18), and a removal process (S19) mentioned later as needed. In addition, the ratio of peeling area shows the ratio of the area of the part to which the coating film peeled with respect to the whole coating film area in percentage.
    [57] Next, in the second chemical liquid treatment step (S16), the Mg alloy material which is not removed in the thinning step (S14) is immersed in the second alkali stripping liquid or the acid stripping liquid.
    [58] The second alkali stripping liquid used in the second chemical liquid treatment step (S16) is 10 to 20 times the volume of the Mg alloy material. The temperature of a 2nd alkali peeling liquid is 50-90 degreeC, and immersion time is 10-30 minutes. It is preferable that the 2nd alkali peeling liquid contains the hydroxide of an alkali metal or alkaline-earth metal as an alkali component. Especially as an alkaline component, potassium hydroxide is suitable. As for the density | concentration of the potassium hydroxide in a 2nd alkali peeling liquid, 2-40 weight% is preferable. You may use the thing of the same composition as a 1st alkali peeling liquid for a 2nd alkali peeling liquid. The coating film swells by such a 2nd chemical | medical solution process process S16, and the coating adhesive force with respect to Mg alloy material falls. In addition, a part of coating film is peeled from Mg alloy material.
    [59] The acid stripping solution used in the second chemical liquid treatment step (S16) is 10 to 20 times the volume of the Mg alloy material. The temperature of the acid stripping liquid is set to 20 to 70 ° C, and the immersion time is set to 5 to 30 minutes. It is preferable that an acid stripping liquid contains organic acid as an acid component. Examples of the organic acid include formic acid, acetic acid and benzoic acid. When formic acid is employed as the organic acid, the concentration of formic acid in the acid stripping liquid is preferably 2 to 20% by weight. In such a second chemical liquid treatment step (S16), the coating film is subjected to a decomposition action or a dissolving action to be dissolved or swelled and peeled off from the Mg alloy material.
    [60] Next, the Mg alloy material is pulled out of the second alkali stripping solution or the acid stripping solution and water washed in the water washing step (S17). Also in this process, the water pressure sprayed to Mg alloy material using a shower device is made into 0.5-2 kgf / cm <2>. Alternatively, in this step, water washing may be performed by immersing the Mg alloy material in the washing water stored in a predetermined bath. By such a water washing step (S17), the coating film swelling on the surface of the Mg alloy material or the coating film member attached to the Mg alloy material surface is physically removed from the Mg alloy material.
    [61] Next, in the neutralization step (S18), the second alkali stripping solution or acid stripping solution remaining in the Mg alloy material via the water washing step (S17) is neutralized. At this time, the alkaline solution used to neutralize the remaining acid stripping solution is made into a volume of 10 to 20 times the amount of the Mg alloy material. What is necessary is just to arbitrarily determine the temperature of an alkali solution in 10-30 degreeC, and the immersion time and concentration of an alkaline solution in the range which can achieve neutralization according to the grade of the acid stripping liquid which remains. As an alkaline solution, sodium hydroxide etc. are mentioned, for example. In addition, the acid solution used for neutralizing the residual 2nd alkali peeling liquid is made into the volume of 10-20 times of Mg alloy material. The temperature of the acid solution may be 10 to 30 ° C., and the immersion time and the concentration of the acid solution may be arbitrarily determined within a range in which neutralization can be achieved according to the degree of the remaining second alkali stripping solution. As an acid solution, formic acid etc. are mentioned, for example.
    [62] Next, in the water washing step (S19), water washing of the Mg alloy material via the neutralization step (S18) is performed under the same conditions as the water washing step (S17). However, when 2nd chemical liquid processing process S16 is performed using a 2nd alkali peeling liquid, neutralization process (S18) and washing process (S19) may be abbreviate | omitted. In addition, when the removal of the coating film is insufficient at this stage, the steps from the first chemical liquid treatment step S12 to the water washing step S19 may be repeated in sequence.
    [63] Next, in the further physical removal step (S20), via the water washing step (S19) (when the neutralization step (S18) and the water washing step (S19) were omitted), the water washing step (S17) was passed. ] Since the shape is complicated by Mg alloy material, the coating film of the part which is hard to peel off in immersion by each peeling liquid is removed physically. Specifically, the coating film is removed using a scraper or the like. In addition, the additional physical removal step (S20) may be selectively performed only for those requiring physical removal of the coating film.
    [64] Next, in the drying step (S21), the Mg alloy material from which the coating film has been sufficiently removed is dried. For example, in a dryer, Mg alloy material is dried by leaving it to stand for 30 minutes-1 hour at the temperature of 50-80 degreeC.
    [65] Next, Mg alloy reclaimed material is manufactured using the Mg alloy material from which the coating film was fully removed by passing through each said process. In addition, it is known that Fe contained in the alloy tends to increase and Mn tends to decrease as the Mg alloy passes through the recycling process. Then, in this embodiment, the case where the forging Mg alloy equivalent to JISMD1D or AZ91D is manufactured as a regeneration material by adjusting the content rate of both the Fe component and Mn component contained in Mg alloy is described.
    [66] In the melting step (S22), the Mg alloy material from which the coating film has been removed is dissolved in the melting furnace together with the first flux. Specifically, a fragmented or once ingot-made Mg alloy material and powdery first flux are introduced into a melting furnace heated to about 680 ° C in advance, and after the addition, the temperature is raised to about 720 ° C to dissolve them. At this time, in order to ensure the homogeneity of the molten Mg alloy, ie, the molten metal, the molten metal in the melting furnace is stirred by rotating a mechanical blade. The first flux is added with the main purpose of reducing oxides generated during dissolution and sedimentation of impurities such as oil in the molten metal as sludge in the following steps, for example, halides of alkali metals or alkaline earth metals. This is used. More specifically, as the first flux, a powder mixture containing 40 to 60 wt% of MgCl 2 , 15 to 35 wt% of KCl, 1 to 10 wt% of CaF 2 , and 10 to 30 wt% of BaCl 2 can be used. have. When ignition occurs on the surface of the molten metal, the first flux is appropriately added in accordance with the ignition state.
    [67] Next, in the sludge separation step (S23), impurities in the molten metal are separated as sludge by continuously stirring the molten metal. In this step, when the sludge is separated in the molten metal, the sludge is promoted by adding a powdery second flux to the molten metal. As the second flux, substantially the same one as the first flux is used. However, unlike the first flux, it is preferable to reduce the proportion of BaCl 2 having a large specific gravity, unlike the first flux. More specifically, as the second flux, for example, a powder containing 60 to 75 wt% of MgCl 2 , 20 to 35 wt% of KCl, 0.1 to 5 wt% of CaF 2 , and 1 to 10 wt% of BaCl 2 . Mixtures can be used. When ignition occurs on the surface of the molten metal, the second flux is appropriately added in accordance with the ignition state.
    [68] Next, the molten metal is cleaned in the cleaning step (S24). Specifically, after stopping the stirring of the molten metal, the molten metal is allowed to settle for 10 to 30 minutes to settle the sludge at the bottom of the melting furnace. At this time, an antioxidant gas layer covering the surface of the molten metal is formed. Specifically, a powdery third flux is added to the molten metal. The third flux is decomposed by the heat of the molten metal to generate a gas for preventing oxidation of the molten metal. An anti-oxidation gas layer covering the surface of the molten metal is formed by filling the gas into the melting furnace. As the third flux, for example, a powder mixture containing 60 to 90% by weight of sulfur (S) and 10 to 40% by weight of MgF 2 can be used.
    [69] Next, in the component analysis process (S25), the component contained in the clarified molten metal is analyzed. Specifically, first, a part of the molten metal is extracted from the melting furnace, and a cylindrical sample having a diameter of 5 cm and a length of 10 cm is cast from the molten metal, for example. And the content rate of the Fe component and Mn component in a molten metal is specified by performing component analysis with respect to this sample. As the analysis method, for example, arc emission spectroscopy can be adopted.
    [70] Next, in the component adjustment step (S26), the content of the Fe component and the Mn component is adjusted within a desired range based on the measurement result obtained in the previous step. For example, when manufacturing the forging Mg alloy corresponding to AZ91D, the desired range of Fe component is 40 ppm (0.004 weight%) or less, and the desired range of Mn component is 0.17-0.4 weight%.
    [71] When the Mg alloy passes through the recycling process, it is known that Fe contained in the alloy increases. Therefore, in order to adjust the Fe component, an appropriate amount of Fe precipitation agent in accordance with the excess amount is added to the molten metal. As the Fe precipitater, for example, an Al-Mn intermetallic compound can be used. On the other hand, when the Mg alloy passes through the recycling process, it is known that the Mn contained in the alloy decreases. Therefore, in order to adjust the Mn component, an appropriate amount of Mn feed agent is added to the molten metal in accordance with the shortage thereof. As the Mn feed agent, a single member Mn or a compound containing Mn can be used. For example, the Al-Mn intermetallic compound can also be used as the Mn feeder. If the content of the Fe component and the Mn component is already within the desired range, the Fe precipitater and the Mn feed agent are not added.
    [72] After determining the type and amount as appropriate, the Fe precipitater and the Mn feeder are added to the molten metal, the molten metal is stirred and subsequently cleaned, and the component analysis step (S25) is performed again. Such component adjustment step (S26) and subsequent component analysis step (S25) are repeatedly performed until the content rate of Fe component and Mn component is suppressed in a desired range.
    [73] Next, in the casting step (S27), an ingot of a predetermined size is cast from the molten metal having a desired component composition as the casting material. In this way, an Mg alloy reclaimed material is produced.
    [74] By the above process, for example, the coating film is applied not only to the flat portion 1 of the personal notebook computer housing shown in FIG. 2 but also to the housing side wall 2, the retreat portion 3, and the minute uneven portion 4. It can be removed well. In the partial removal step (S11), the incision is easily infiltrated by forming an incision in the coating film by the cutter knife or by removing a part of the coating film by the wet blast and forming irregularities on the coating film surface. Thereby, the infiltration of the peeling liquid with respect to a coating film is accelerated | stimulated, and the time of the netting required for removing the whole coating film is shortened. In the thinning treatment (S14), by removing 90% or more of the coating film at this point, the next second chemical treatment step (S16), water washing step (S17), and the like can be omitted, and the overall coating film The removal time can be shortened and the cost can be reduced. Therefore, Mg alloy regeneration material can be manufactured efficiently.
    [75] 3 is a flowchart from peeling of the coating according to the second embodiment of the present invention to production of the Mg alloy reclaimed material. In this figure, the same process as the above-mentioned 1st Embodiment is attached | subjected with the same code | symbol, and the overlapping description is abbreviate | omitted.
    [76] The Mg alloy material via the partial removal step (S11), the first chemical liquid treatment step (S12), and the water washing step (S13) is classified into a plurality of groups according to the peeling area ratio of the coating film in the classification S15. As an example, it classifies into three groups of the group A whose peeling area ratio is more than 80%, the group B whose peeling area ratio is 40 to 80%, and the group C whose peeling area ratio is less than 40%. The grouping of this group may be classified into four or more as needed, and may classify only two. In addition, since the range of the peeling area ratio used as the reference | standard at the time of sorting changes with materials, thickness, and other conditions of a coating material, what is necessary is just to determine arbitrarily as needed.
    [77] Next, in the second chemical liquid treatment steps (S16a to S16c), the Mg alloy material classified into the groups A to C in the classification S15 is immersed in an alkali stripping liquid or an acid stripping liquid for each group. As an example, group A is immersed in the second alkali stripping liquid, group B in the third alkali stripping liquid, and group C in the acid stripping liquid. Moreover, it is preferable that the content of an alkali component is smaller in a 2nd alkali peeling liquid rather than a 3rd alkali peeling liquid. Moreover, you may use the thing of the same composition as a 1st alkali peeling liquid for either of a 2nd and 3rd alkali peeling liquid.
    [78] Then, water washing steps (S17a to S17c) such as the water washing step (S17), neutralization steps (S18a to S18c) such as the neutralization step (S18), water washing steps (S19a to S19c) such as the water washing step (S19) , Additional physical removal processes (S20a to S20c) such as additional physical removal process (S20), drying processes (S21a to S21c) such as drying process (S21), dissolution process (S22), sludge separation process (S23), A cleaning process (S24), a component analysis process (S25), a component adjustment process (S26), and a casting process (S27) are performed in order.
    [79] By passing through the above process, the ratio of the peeling area is relatively large in the second chemical liquid treatment steps (S16a to S16c), and the magnesium alloy material (for example, Groups A and B) that can be sufficiently peeled without using an acid stripping solution is used. Since no acid stripping solution is used, the magnesium alloy material can be prevented from being dissolved. In addition, even when using an alkali stripping solution, by appropriately changing the alkaline stripping solution for each group according to the ratio of the stripping area, the amount of the alkaline stripping solution having a high concentration of the alkaline component which is dangerous and requires attention in handling may be used. It can suppress and it becomes possible to remove paint more safely.
    [80] 4 is a flowchart from peeling of the coating according to the third embodiment of the present invention to production of the magnesium alloy reclaimed material. In this figure, the same process as the above-mentioned 1st and 2nd embodiment is attached | subjected with the same code | symbol, and the overlapping description is abbreviate | omitted.
    [81] By passing through the above process, the characteristic in 1st Embodiment and the characteristic in 2nd Embodiment can be combined.
    [82] EXAMPLE
    [83] Next, the Example of this invention is described.
    [84] [First Embodiment]
    [85] As the Mg alloy material to be coated, 210 pieces of personal notebook computer housings as shown in Fig. 2, which were surface-coated with Mg alloy, were prepared. The details of this 210 personal notebook computer housing are epoxy series whose surface coating is epoxy magne EP1000 (made by Nippon Paint), and the lower layer coated by epoxy mag powder # 1000 (made by Dainippon paint). 70 housings with a coating film, the upper coating layer is urethane-based NC-7 (manufactured by Yukosha), 70 housings with a urethane-based coating film of which the lower coating layer is an acrylic silicone UB primer (manufactured by Micasa Paint), and an upper coating layer The housing | casing which has this acryl urethane type PS high coat B (made by Micasa paint) and the acrylic coating film whose lower coating layer is an acryl silicone type UB primer (made by Micassa paint) is 70 sheets. First, the incision is cut into the coating film of the housing in which these coatings are completed. The spacing of these incisions was 50 mm. Next, in a state in which 210 sheets of cut housings were accommodated in a jig, firstly, the first alkaline stripping solution of 800 d 3 prepared in a stainless steel treatment bath (1 m 3) was immersed. The first alkaline stripping solution contained 3.5% by weight of potassium hydroxide, 2.5% by weight of sodium hydroxide, 20% by weight of anionic surfactant, and 40% by weight of diethylene glycol monoethyl ether. The temperature of the 1st alkali peeling liquid was kept at 70 degreeC, and immersion time was made into 10 minutes. By this first chemical liquid treatment, the coating film was swollen and a part thereof was peeled off. Next, the jig containing the housing was lifted from the first alkali peeling liquid, and then the housing was immersed in 800 dm3 of first washing water prepared in a stainless steel treatment bath (1m3) to wash the water. Thereby, about 90% of the housing | casing which has an epoxy type coating film removed these since the peeling area ratio of the coating film surface reached 90% or more. In addition, the housing | casing which has a urethane type coating film and an acryl type coating film peeled the upper coating layer part in this step.
    [86] Next, in the state which accommodated the housing which was not removed, it was immersed in the 800 dm <3> acid stripping liquid prepared in the stainless steel process bath (1m <3>). This acid stripper contains 5% by weight of formic acid which is an organic acid, 30% by weight of aromatic alcohol and 30% by weight of ethylene glycol monobutyl ether. The temperature of the acid stripping solution was maintained at 60 ° C, and the immersion time was 10 minutes. By the second chemical liquid treatment, a part of the coating film was subjected to a decomposition action or a dissolution action, and was peeled from the Mg alloy material by melting or swelling. Next, the jig containing the housing was lifted from the acid stripping liquid, and then the housing was immersed in 800 dm3 of second washing water prepared in a stainless steel treatment bath (1m3), followed by water washing. Subsequently, the water-washed housing was immersed in an 800 dm3 alkaline solution prepared in a stainless steel treatment bath (1m3). This alkaline solution contains 5 weight% of sodium hydroxide. The temperature of the alkaline solution was kept at room temperature, and the immersion time was 5 minutes. This neutralized the acid stripping solution remaining in the housing. Next, after the housing was pulled out of the alkaline solution, the housing was immersed in 800 dm3 of third washing water prepared in a stainless steel treatment bath (1m3), followed by water washing. The coating film peeled completely in 50% of housing | casings which were not scraped off by each of these processes. In addition, the remaining 50% of the housing also has a coating film remaining in the housing side walls, recesses, uneven portions, etc., which are difficult to peel off, and the coating film remaining on these portions is physically removed by a scraper. Next, the housing from which the coating film was removed was dried by a dryer. Thus, in the personal notebook computer housing made of Mg alloy, the coating film formed on the flat part 1, the housing side wall 2, the retreat part 3, and the fine uneven part 4 shown in FIG. Could be removed.
    [87] Next, 30 kg of the Mg alloy housing from which the coating film was removed as described above with respect to the melting furnace (60 dm3) preheated to about 680 ° C, and 1 kg of the first flux were put therein, and the melting furnace was then heated to 720 ° C. To dissolve them. The first flux is a powder mixture comprising 50% by weight of MgCl 2 , 25% by weight of KCl, 5% by weight of CaF 2 , and 20% by weight of BaCl 2 . In order to obtain homogeneity of the molten Mg alloy, that is, the molten metal, the molten metal was stirred by a mechanical blade. The rotation speed of the blade was 100 rpm.
    [88] The stirring was continued and 0.2 kg of the second flux was added to the molten metal when the sludge began to separate from the molten metal. The second flux is a powder mixture comprising 67.5 wt% MgCl 2 , 27.5 wt% KCl, 1 wt% CaF 2 , and 4.5 wt% BaCl 2 . And the second flux was suitably added by 0.1 kg according to the ignition state of the molten metal surface. The addition of this second flux promoted the separation of sludge from the melt.
    [89] Next, the stirring was stopped and the molten metal was allowed to settle for 20 minutes to settle the sludge in the molten metal to clean the molten metal. At that time, 0.2 kg of 3rd flux was thrown into the molten metal immediately after stirring was stopped. The third flux is a powder mixture containing 80% by weight of S and 20% by weight of MgF 2 . SF 6 was generated by the introduction of the third flux, filled the furnace, and an antioxidant gas layer covering the molten metal surface was formed by SF 6 . In this way, the sludge was sufficiently settled while the oxidation of the molten metal was suppressed.
    [90] Next, 0.2 kg was extracted as a sample from the cleaned molten metal, and the cylindrical sample (5 cm in diameter, 10 cm in length) was cast from this molten metal. Next, the component analysis was performed about this sample using the arc luminescence spectroscopy apparatus (PDA-5500II, the Shimadzu Corporation). As a result, the Fe content was 0.0058% by weight and the Mn content was 0.120% by weight.
    [91] Next, in order to lower the Fe content and increase the Mn content, an Al-Mn intermetallic compound having both a function of a Fe precipitater and a Mn feeder was added to the melting furnace. In order to obtain the forging Mg alloy (Fe: 0.004 wt% or less, Mn: 0.17 to 0.4 wt%) corresponding to AZ91D, the dose of Al-Mn intermetallic compound was 4 kg. Next, after stirring the molten metal in which the component adjustment was performed in this way, the molten metal was cleaned by cooling for 10 minutes.
    [92] Next, 0.2 kg was extracted as a sample from the cleaned molten metal, and the cylindrical sample (5 cm in diameter, 10 cm in length) was cast from this molten metal. Next, component analysis was performed on the sample using an arc emission spectrophotometer (PDA-5500II, manufactured by Shimadzu Corporation), whereby the Fe content was lowered to 0.0015% by weight and the Mn content was 0.210% by weight. Was rising. Next, five ingots (5 kg) were cast from the molten metal in which the component adjustment was performed to the desired composition in this way. In this way, an Mg alloy reclaimed material could be produced from the Mg alloy personal notebook computer housing to be coated.
    [93] <Bending Strength Measurement>
    [94] Five JIS Z22041 test members (10 mm x 50 mm x 3.2 mm) were produced from die-cast molding of the Mg alloy reclaimed material obtained as described above, and the bending strength was measured for these test members. Specifically, a three-point bending test was performed on each test member in accordance with JIS K7055 using a universal testing machine (trade name: INSTORON5581, manufactured by Instron Japan). The test conditions made the distance (span) between two points of support 40 mm, and made the load speed of the load with respect to the substantially center between the said two points of support 2 mm / min. In addition, five JIS Z 22041 test members were similarly produced from the virgin material AZ91D, and the 3-point bending test was done on these test members on the same conditions. As a result, the test member made of the Mg alloy recycled material of the present example had substantially the same strength as the test member made from the virgin material, exhibited an average bending strength of about 400 MPa, and the difference between the maximum value and the minimum value was about 12%.
    [95] Corrosion test
    [96] Five JIS Z 22041 test members (10 mm x 50 mm x 3.2 mm) were made from die-cast molding from the Mg alloy reclaimed material obtained as described above, and the salt spray according to JIS Z 2371 was applied to these test members. Corrosion resistance was evaluated by the test. In addition, five JIS Z 22041 test members were similarly produced from virgin material, and these test members were evaluated for corrosion resistance on the same conditions. As a result, the amount of corrosion of the test member of this example was about the same as the amount of corrosion of the test member made of a virgin material.
    [97] <Formulation Evaluation>
    [98] 50 pieces of personal notebook computer housings (320 mm x 240 mm x 1.2 mm) as shown in Fig. 2 were molded from die-cast Mg alloy recycled materials obtained as described above. On the other hand, 50 personal notebook computer housings were similarly formed from virgin materials. As a result, the Mg alloy reclaimed material of this example showed the same formability as that of the virgin material. For example, the quality ratio of products was about 83% as in the case of using the virgin material. Here, the quality ratio of the product refers to the ratio of the molded product that satisfies the appearance standard as the product without short shot of the molten metal or shrinkage and distortion in the molded product.
    [99] Second Embodiment
    [100] As the Mg alloy material to be coated, 210 pieces of personal notebook computer housings as shown in Fig. 2, which were surface-coated with Mg alloy, were prepared. The 210 personal notebook computer housing is a housing having an acrylic coating film whose upper coating layer is an acrylic urethane PS high coat B (manufactured by Micasa Paint) and whose lower coating layer is an acrylic silicone UB primer (manufactured by Micasa Paint). First, the wet blasting process was performed with respect to the coating film of the housing in which these coating was completed. This wet blasting process was performed by blowing a polishing liquid to a coating film on the conditions that a processing speed (moving speed of a spray nozzle) is 10 mm / sec, and injection pressure is 0.27 Mpa. The polishing liquid contained 20% by weight of alumina particles having an average particle diameter of about 130 µm, and the temperature was maintained at room temperature. A portion of the coating film was removed by this wet blast treatment, and fine irregularities were formed on the coating film surface. Next, the first chemical liquid treatment with the first alkali peeling liquid and subsequent water washing were performed in the same manner as in the first embodiment in a state where 210 housings in which a part of the coating film was shaved by the wet blast treatment were accommodated in a jig. . Thereby, a part of coating film is removed and the peeling area ratio of the coating film in a housing is more than 80%, about 15% of the whole (group A), and the peeling area ratio of 40 to 80% is about 50% of the whole ( It was about 35% of the whole (group C) that group B) and peeling area ratio were less than 40%. The 2nd chemical | medical solution process was performed by immersing the group A thru | or C classified according to the peeling area ratio of this coating film in each processing tank which starts below. The housing classified into group A was immersed in a first alkaline peeling solution of 800 dm3 prepared in a stainless steel treatment bath (1m3) while housed in a jig. The first alkaline stripping solution contained 3.5% by weight of potassium hydroxide, 2.5% by weight of sodium hydroxide, 20% by weight of anionic surfactant, and 40% by weight of diethylene glycol monoethyl ether. The temperature of the 1st alkali peeling liquid was kept at 70 degreeC, and immersion time was made into 20 minutes. The housings classified in the group B were immersed in a second alkaline peeling solution of 800 d 3 prepared in a stainless steel treatment bath (1 m 3) in a state of being accommodated in a jig. The 2nd alkali stripping liquid contains 35 weight% of potassium hydroxide, 14 weight% of monoethanolamine, and 10 weight% of diethylene glycol monoethyl ether. The temperature of the 2nd alkali peeling liquid was kept at 80 degreeC, and immersion time was made into 20 minutes. The housings classified in the group C were immersed in an acid stripping solution of 800 dm3 prepared in a stainless steel treatment bath (1m3) while housed in a jig. The acid stripping solution contains 5% by weight of formic acid, which is an organic acid, 30% by weight of aromatic alcohol, and 30% by weight of ethylene glycol monobutyl ether. The temperature of the acid stripping solution was maintained at 60 ° C, and the immersion time was 20 minutes. Thereby, the coating film of any housing also peeled completely.
    [101] Thus, using the Mg alloy housing from which the coating film was removed, the Mg alloy regeneration material was produced like Example 1 from melt | dissolution in a melting furnace to casting of a 5 kg ingot via component analysis and component adjustment. Bg strength measurement, corrosion resistance test, and moldability evaluation were carried out on the Mg alloy regenerated material in the same manner as in the first example. The Mg alloy regenerated material of this example also exhibited the same properties and physical properties as those of the virgin material.
    [102] As mentioned above, the structure of this invention and its change are listed as appendix below.
    [103] (Appendix 1) A partial removal step of physically and partially removing the coating film from the magnesium alloy material to which the coating is applied,
    [104] And a chemical liquid treatment step of further exfoliating the coating film by applying an alkali stripper to the magnesium alloy material via the partial removal step.
    [105] (Supplementary Note 2) The method of removing the coated film of the coated magnesium alloy material according to Supplementary Note 1, wherein the partial removing step is performed by incision formation or wet blasting into the coating film by a cutter knife.
    [106] (Supplementary Note 3) The coating film removing method of the coated magnesium alloy material according to Supplementary Note 1 or Supplementary Note 2, in which 20% to 50% of the total amount of the coating film is removed in the partial removing step.
    [107] (Supplementary Note 4) Magnesium alloy further comprising an additional chemical liquid treatment step of further peeling the coating film by using a separation solution separate from the alkali stripping liquid, wherein the peeling area ratio of the coating film surface is 90% or more in the first chemical liquid treatment step. The coating film removal method of the to-be-coated magnesium alloy material in any one of notes 1-3 which perform the said further chemical-processing process only about the magnesium alloy material from which the ash was scraped off.
    [108] (Supplementary Note 5) Supplementary note 4 in which the remaining magnesium alloy material via the first chemical liquid treatment step is classified into a plurality of groups according to the peeling area ratio of the coating film, and the additional chemical liquid treatment step is performed using a different stripping solution for each group. The coating film removal method of the to-be-coated magnesium alloy material of description.
    [109] (Supplementary Note 6) At least one of the stripping liquids used in the additional chemical liquid treatment step is an alkaline stripping liquid separate from the alkaline stripping liquid used in the first chemical liquid processing step, and at least another one of the stripping liquids used in the additional chemical liquid processing step is The coating film removal method of the to-be-coated magnesium alloy material of Appendix 5 which is an acid peeling liquid.
    [110] (Supplementary Note 7) The coating film removal method of the coated magnesium alloy material according to any one of Supplementary Notes 1 to 6, wherein the alkali stripping liquid contains potassium hydroxide as an alkaline main component.
    [111] (Supplementary Note 8) The coating film removal method of the coated magnesium alloy material described in Supplementary Note 6, wherein the acid stripping liquid contains an organic acid as an acid main component.
    [112] (Supplementary Note 9) Supplementary Note 6 to Supplementary Note further comprising a neutralizing step of neutralizing the acid stripping solution adhering to the magnesium alloy material via the further chemical processing step following the additional chemical processing step using the acid stripping solution. The coating film removal method of the to-be-coated magnesium alloy material in any one of 8.
    [113] (Supplementary Note 10) The method for removing the coated film of the coated magnesium alloy material according to Supplementary Note 9, wherein the neutralization in the neutralizing step is performed by reacting sodium hydroxide.
    [114] (Supplementary Note 11) The coating film removing method of the coated magnesium alloy material according to any one of Supplementary Notes 4 to Supplementary Note 10 further comprising an additional physical removing step of removing the coating film remaining in the magnesium alloy material via the additional chemical liquid treatment step.
    [115] (Supplementary note 12) The coating film removal method of the coated magnesium alloy material according to any one of supplementary notes 1 to 11 including a water washing step for washing the magnesium alloy material immediately after the chemical liquid treatment step.
    [116] (Supplementary Note 13) The coating film removing method of the magnesium alloy material to be coated in any one of Supplementary Notes 4 to Supplementary Note 12, wherein the cycle including the first chemical liquid treatment step and the additional chemical liquid treatment step is repeated.
    [117] (Supplementary note 14) Magnesium alloy manufactured by using at least a magnesium alloy material and a magnesium alloy virgin material from which the coating film has been removed by the coating film removing method of the coated magnesium alloy material according to any one of Supplementary Notes 1 to 13. Reclaimed materials.
    [118] According to the present invention, the coating film formed on the surface of magnesium or alloy material can be appropriately removed in a short time. Therefore, it becomes possible to efficiently manufacture the magnesium alloy reclaimed material which can exhibit the characteristics equivalent to a virgin material from the to-be-coated magnesium alloy material.
    权利要求:
    Claims (5)
    [1" claim-type="Currently amended] A partial removal step of physically and partially removing the coating film from the magnesium alloy material to which the coating is applied;
    And a chemical liquid treatment step of further exfoliating the coating film by applying an alkali stripper to the magnesium alloy material via the partial removal step.
    [2" claim-type="Currently amended] The method for removing a coating film of a coated magnesium alloy material according to claim 1, wherein the partial removing step is performed by cutting or wet blasting into the coating film by a cutter knife.
    [3" claim-type="Currently amended] The method according to claim 1 or 2, further comprising an additional chemical liquid treatment step of further peeling the coating film by using a separation liquid separate from the alkali stripping liquid, and the peeling area ratio of the coating film surface in the first chemical liquid treatment step. A method for removing a coating film of a coated magnesium alloy material, wherein the additional chemical liquid treatment step is performed only on the magnesium alloy material obtained by thinning out the 90% or more magnesium alloy material.
    [4" claim-type="Currently amended] The method according to claim 3, wherein the remaining magnesium alloy material, which has passed through the first chemical liquid treatment step, is classified into a plurality of groups according to the peeling area ratio of the coating film, and the additional chemical liquid treatment step is performed using a different peeling liquid for each group. The coating film removal method of the to-be-coated magnesium alloy material characterized by the above-mentioned.
    [5" claim-type="Currently amended] The method according to claim 4, wherein at least one of the stripping liquids used in the additional chemical liquid processing step is an alkaline stripping liquid separate from the alkaline stripping liquid used in the first chemical liquid processing step, and is at least different from the stripping liquids used in the additional chemical liquid processing step. One is an acid peeling liquid, The coating film removal method of the to-be-coated magnesium alloy material characterized by the above-mentioned.
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    同族专利:
    公开号 | 公开日
    US7056445B2|2006-06-06|
    TWI248989B|2006-02-11|
    CN100343401C|2007-10-17|
    US20040045590A1|2004-03-11|
    TW200407464A|2004-05-16|
    KR100980182B1|2010-09-03|
    CN1495279A|2004-05-12|
    JP2004099993A|2004-04-02|
    JP4146198B2|2008-09-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2002-09-11|Priority to JPJP-P-2002-00264903
    2002-09-11|Priority to JP2002264903A
    2003-08-22|Application filed by 후지쯔 가부시끼가이샤
    2004-03-18|Publication of KR20040023507A
    2010-09-03|Application granted
    2010-09-03|Publication of KR100980182B1
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP-P-2002-00264903|2002-09-11|
    JP2002264903A|JP4146198B2|2002-09-11|2002-09-11|Method of removing coated magnesium alloy film for recycling magnesium alloy material|
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