JP5205109B2 - Magnesium alloy article and magnesium alloy member - Google Patents

Description

  The present invention relates to a magnesium alloy article in which a resin surrounding at least a part of the outer periphery is bonded, and a magnesium alloy member subjected to a surface treatment for bonding a resin surrounding a part of at least the outer periphery, and in particular, a magnesium alloy substrate and a resin The present invention relates to a magnesium alloy article and a magnesium alloy member that are excellent in adhesiveness and have little deformation.

  Magnesium and magnesium alloys are widely used in casings of mobile phones, cameras, personal computers and the like because they have high specific strength and specific rigidity and can be easily reduced in weight. A magnesium alloy article in which a resin covering at least a part of the surface such as the outer periphery of the magnesium alloy substrate is bonded is not obtained by a resin molded product alone by the magnesium alloy substrate, and has excellent rigidity, and the magnesium alloy by the resin. It is possible to obtain complex shapes and aesthetics that cannot be formed alone, and they are used in many fields including the above-mentioned applications.

  In order to use such a magnesium article in which a resin is bonded to a magnesium alloy substrate in a wide range of applications including a housing or the like, it is necessary to increase the bonding strength between the magnesium alloy and the resin.

  As a method for obtaining the bonding force between the resin and the substrate, a method using an adhesive such as an epoxy adhesive (Patent Document 1) has been proposed.

  In addition to this method, a porous layer having fine irregularities is formed on the surface, and an engineering resin is injection-molded and joined to a magnesium alloy substrate immersed in ammonia, hydrazine, a water-soluble amine compound and alcohol (patent) Documents 2 to 4) and a method of injection molding a PPS resin on a substrate having irregularities with an average inner diameter of 10 to 80 nm on the surface by immersion treatment or anodic oxidation with an erodible aqueous solution (Patent Document 5) have been proposed. Yes.

In addition, in order to obtain a stronger bonding force between a metal containing a magnesium alloy and a resin, a reactive functional group is introduced on the metal surface using an alkoxysilane-containing triazine thiol derivative, and a chemical reaction between the metal and the resin is performed. Are known (Patent Documents 6 and 7).
However, the joining force obtained by these methods is not sufficient.

  Therefore, as a result of various studies, the present inventors have formed a predetermined chemical conversion film and a dehydrated silanol-containing triazine thiol derivative coating on the surface of the magnesium alloy substrate, as will be described in detail later. It has been found that high bonding strength can be obtained with the alloy substrate.

  However, the magnesium article obtained by using this method may be deformed such as a curve.

  FIG. 15 is a perspective view showing a magnesium alloy article 200 shown as an example. FIG. 16 is a perspective view showing a magnesium alloy substrate 250 used in the magnesium alloy article 200.

  The magnesium alloy base body 250 has a structure in which the standing walls 211 to 214 surround the periphery of the top plate (or bottom surface) 235 so as to form a space in which an electronic component such as a printed circuit board can be accommodated.

  For example, a joining portion in which a predetermined chemical conversion film and a dehydrated silanol-containing triazine thiol derivative coating are formed is provided on a part of the outer surface of 211 to 214 on the standing wall of the surface of the base body 250, and the base body 250 is heated in a mold. The casing 200 is obtained by insert molding in which the molten resin 204 is injected into a mold. The resin 204 is bonded to the magnesium alloy substrate 250 at this bonded portion.

  However, in the cooling step after heating in insert molding or the like, the shrinkage amount of the resin is larger than the shrinkage amount of the magnesium alloy, and the resulting magnesium alloy article 200 is bent due to the stress caused by the difference in shrinkage amount. In some cases, such deformation occurs.

  In particular, the bonding method using the chemical conversion film and the dehydrated silanol-containing triazine thiol derivative coating found by the inventors has a strong bonding force, and even if such a stress occurs at the bonding interface, the resin 204 and the magnesium alloy substrate 250 However, the stress is not relieved because it does not peel off, and such deformation may be promoted.

  As a method for preventing deformation caused by the difference in shrinkage between the resin and the metal during cooling, for example, in Patent Document 8, a thin portion is formed in a plate-shaped resin molded portion close to a joint portion with a metal plate, A method of absorbing the deformation distortion with this thin portion is shown.

  In Patent Document 9, a groove is formed in the vicinity of the butt portion of the metal plate in the butt between the plate-shaped resin portion and the metal plate, the metal portion is deformed by the pressure when the resin is injected, and the resin contracts by cooling. In this case, a method for preventing a gap from being generated between the metal plate and the resin by returning the deformation to the original state is shown.

Further, Patent Document 10 discloses a method in which a fitting-shaped resin molded portion attached to a metal part gives a tightening force when the resin expands at a high temperature.
JP 2007-15337 A JP 2003-103563 A JP 2005-342895 A JP 2006-27018 A JP 2007-50630 A JP 2006-213677 A JP 2007-131580 A JP-A-9-147520 Japanese Patent Laid-Open No. 9-167461 JP 2007-64363 A

However, the methods described in Patent Documents 8 and 9 are intended for matching between a metal plate and a plate-like resin, and for joining a magnesium alloy substrate having a complicated shape having a standing wall as shown in FIG. Not applicable.
Moreover, the method of patent document 10 gives clamping force at the time of use at high temperature, and cannot be applied to the articles | goods used at normal temperature.

  Accordingly, an object of the present invention is to provide a magnesium alloy article in which a magnesium alloy substrate and a resin are strongly bonded and deformation is suppressed. Another object of the present invention is to provide a magnesium alloy member that is less deformed even when a resin is bonded to the surface.

  In the present invention, each of at least one pair of opposing sides on the outer periphery is located between the first joint portion located between the center and one end portion, and between the center portion and the other end portion. A magnesium article including a base made of magnesium or a magnesium alloy, wherein the first joint and the second joint include hydroxide, carboxylate, phosphorus A conversion film comprising at least one selected from the group consisting of acid salts, silicates, carbonates, sulfates, thiosulfates, nitrates, nitrites, permanganates, amino compounds and metal acetylacetonates, and dehydration A magnesium alloy article characterized by being bonded to a resin surrounding at least a part of the outer periphery of the substrate through a silanol-containing triazine thiol derivative coating.

  The present invention also provides that each of at least one pair of opposing sides on the outer periphery is between a first joint located between the center and one end, and between the center and the other end. A second joint located, wherein the first joint and the second joint are hydroxide, carboxylate, phosphate, silicate, carbonate, sulfate, It is coated with a dehydrated silanol-containing triazine thiol derivative via a chemical conversion film containing at least one selected from the group consisting of thiosulfate, nitrate, nitrite, permanganate, amino compound and metal acetylacetonate. It is the magnesium alloy member characterized.

  According to the present invention, a bonding portion appropriately disposed on a magnesium alloy substrate is formed, and a chemical conversion film and a dehydrated silanol-containing triazine thiol derivative coating are formed on the surface of the bonding portion, whereby the magnesium alloy substrate and the resin are formed. In addition, it is possible to provide a magnesium alloy article having a high bonding strength and suppressed deformation. In addition, it is possible to provide a magnesium alloy member that can firmly bond a resin to the surface and that is less deformed.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the following description, terms indicating a specific direction and position (for example, “up”, “down”, “right”, “left” and other terms including those terms) are used as necessary. These terms are used for easy understanding of the invention with reference to the drawings, and the technical scope of the present invention is not limited by the meaning of these terms. Moreover, the part of the same code | symbol which appears in several drawing shows the part or member which is the same or corresponds.

  As described above, the present inventor forms a predetermined chemical conversion coating on the surface of a magnesium or magnesium alloy substrate, and forms a dehydrated silanol-containing triazine thiol derivative coating on the chemical conversion coating using an alkoxysilane-containing triazine thiol derivative. I found a way to do it. By coating the resin on the dehydrated silanol-containing triazine thiol derivative coating, a high bonding strength can be obtained between the resin and the magnesium alloy substrate.

  And it discovered that a deformation | transformation of a magnesium article can be suppressed by arrange | positioning a 1st junction part and a 2nd junction part appropriately in the at least 1 set of opposing edge on the outer periphery of the base | substrate which consists of magnesium or a magnesium alloy. .

That is, in each side, the first joint portion is disposed between the center and one end portion, and the second joint portion is disposed between the center and the other end portion. Has been found to be imparted to both sides of the side in a well-balanced manner to suppress deformation.
Below, the detail of the above-mentioned joining method is demonstrated first, and the detail of the deformation | transformation suppression method is demonstrated subsequently.

1. Joining Method When joining a magnesium alloy substrate and a resin, the inventors of the present invention have examined the reason why a sufficiently high bonding force cannot be obtained even when an alkoxysilane-containing triazine thiol derivative is used. It has been found that there is a high possibility that it is caused by the oxide film on the surface of the substrate.

  When a metal and a resin are bonded using an alkoxysilane-containing triazine thiol derivative, the alkoxysilane part chemically bonds to the metal, and a reactive functional group composed of the triazine thiol derivative part is introduced onto the metal surface. This functional group (triazine thiol derivative part) is chemically bonded to the resin, so that the dehydrating silanol-containing triazine thiol derivative (the result of the above-mentioned alkoxysilane part being chemically bonded to the metal is the result of the alkoxysilane-containing triazine thiol). The product can be chemically bonded via a product generated from the derivative, thereby making it possible to obtain a strong bonding force.

  Usually, the bond between the alkoxysilane group of the alkoxysilane-containing triazine thiol derivative and the metal is prepared by preparing a solution of the alkoxysilane-containing triazine thiol derivative, and immersing the metal in this solution to form a hydroxyl group (OH group) on the metal surface. This is performed by reacting an alkoxysilane group. For this reason, a method of removing an oxide film on a metal surface by plasma treatment and introducing a hydroxyl group (OH group) on the metal surface is generally used.

  However, magnesium has a strong binding force with oxygen, and since the oxide film formed on the surface of the magnesium alloy is dense and strong, OH groups are not sufficiently introduced, and the magnesium alloy and the alkoxysilane group It can be presumed that a sufficient number of bonds (density) cannot be obtained. In addition, simply removing the magnesium oxide film will result in the formation of a new oxide film immediately after the magnesium is combined with oxygen, so that a high bonding strength cannot be obtained.

Therefore, the present inventors surface-treat the magnesium alloy substrate to react with and bond to the alkoxysilane group on the metal surface, hydroxide, carboxylate, phosphate, silicate, carbonate, After forming a chemical conversion film containing at least one of sulfate, thiosulfate, nitrate, nitrite, permanganate, amino compound, and metal acetylacetonate, magnesium alloy using triazinethiol containing alkoxysilane The inventors have arrived at the invention described in the present application that strongly bonds the substrate and the resin disposed on the surface thereof.
Details of the present invention will be described below.

FIG. 1 is a cross-sectional view schematically showing a part of a magnesium alloy article according to the present invention, the whole of which is represented by 100. A magnesium alloy substrate 1 made of magnesium or a magnesium alloy and a resin layer 4 are bonded together via a chemical conversion film 2 and a dehydrated silanol-containing triazine thiol derivative coating 3 which will be described in detail later.
FIG. 2 shows a cross section of a conventional magnesium alloy article 200 in which the magnesium alloy substrate 1 and the resin layer 4 are bonded using the dehydrated silanol-containing triazine thiol derivative 3. The conventional magnesium alloy article 200 does not have the chemical conversion film 2.

The chemical conversion film 2, which is a feature of the magnesium alloy article 100 according to the present invention, includes hydroxide, carboxylate, phosphate, silicate, carbonate, sulfate, thiosulfate, nitrate, nitrite, permanganese. At least one selected from the group consisting of acid salts, amino compounds and metal acetylacetonates.
A method for producing the magnesium alloy article 100 of the present invention in which the magnesium alloy substrate 1 and the resin 4 are strongly bonded by using the chemical conversion film 2 will be described in detail below.

1-1. Pretreatment Before forming a chemical conversion film by chemical conversion treatment, degreasing treatment and / or etching treatment is preferably performed as pretreatment for the purpose of degreasing and / or removing oxide film on the surface of the magnesium alloy substrate 1.

  The degreasing treatment may be a method usually used for degreasing the magnesium alloy substrate, for example, degreasing using a strong alkali such as sodium hydroxide. Preferred degreasing conditions are, for example, degreasing in sodium hydroxide at a concentration of 10 to 100 g / L and a temperature of 50C to 90C. More preferable conditions are that after preliminary degreasing in sodium hydroxide at a concentration of 10 to 100 g / L (most preferably 10 to 20 g / L) and a temperature of 50 ° C. to 90 ° C., a concentration of 10 to 100 g / L ( Most preferably, degreasing is performed in sodium hydroxide at a temperature of 50 ° C. to 90 ° C.

  In addition, sodium salts such as sodium carbonate, sodium bicarbonate, borax, silicates such as sodium orthosilicate, sodium silicate, primary sodium phosphate, secondary sodium phosphate, tertiary sodium phosphate Degreasing may be performed using various phosphates such as sodium phosphate, sodium pyrophosphate, and sodium hexametaphosphate.

  Etching treatment to remove the magnesium oxide film is performed in an inorganic acid such as phosphoric acid, silicohydrofluoric acid, sulfuric acid, nitric acid, hydrofluoric acid, or in an organic acid such as oxalic acid, acetic acid, citric acid, Thereafter, neutralization and desmutting treatment is performed in an alkali.

  Preferable etching conditions with an acid include a concentration of 1 to 10 g / L and a temperature of 30 to 70 ° C. for an inorganic acid, and a concentration of 10 to 50 g / L and a temperature of 20 to 70 ° C. for an organic acid. Is preferred.

  More preferably, the magnesium alloy substrate 1 is subjected to both degreasing and etching. This is to increase the bonding force between the chemical conversion coating produced by the chemical conversion treatment described in detail below and the magnesium alloy substrate.

  The magnesium alloy substrate 1 is made of magnesium or a magnesium alloy, and any magnesium alloy used in industry can be used as the magnesium alloy. Examples of preferred magnesium alloys are AZ-based alloys such as AZ21, AZ31, AZ61, AZ91, and AZ101 alloys, and AM-based alloys such as AM50 and AM60.

1-2. Chemical conversion treatment On the surface of the magnesium alloy substrate 1, hydroxide, carboxylate, phosphate, silicate, carbonate, sulfate, thiosulfate, nitrate, nitrite, permanganate, amino compound and metal In order to produce the chemical conversion film 2 containing at least one of acetylacetonate, chemical conversion treatment is performed by the following method. The chemical conversion film is formed using at least one of these methods.

(1) Hydroxide One method for obtaining a chemical conversion film 2 made of hydroxide is to apply an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide or ammonia water to treat the surface of the magnesium alloy substrate 1. In this method, a chemical conversion film mainly composed of hydroxide is formed on the surface.

  An example of a hydroxide formed as a chemical conversion film is a hydroxide mainly composed of magnesium hydroxide and / or aluminum hydroxide, which is formed as a result of bonding of a hydroxyl group and magnesium and / or aluminum in a magnesium alloy. .

  For example, when the chemical conversion treatment is performed using potassium hydroxide, the aqueous solution preferably has a concentration of 5 to 100 g / L and a temperature of 50 to 90 ° C. Moreover, when using alkaline aqueous solutions, such as sodium hydroxide and ammonia water other than this, it is preferable that they are a density | concentration: 10-150 g / L and temperature: 50-90 degreeC.

  By the way, it is known that a film mainly composed of magnesium hydroxide can be formed on the surface of the magnesium alloy by selecting an appropriate electrolytic solution in the anodic oxidation method (for example, JP-A-2006-322044). However, since the coating film produced by the anodic oxidation method is porous and thick, it is fragile and may not always have a sufficient bonding strength, and it is preferable to perform the chemical conversion treatment using the above-described alkaline solution.

  Similarly, it is known that an aluminum alloy is covered with a coating of AlOOH using an aqueous hydrazine solution (for example, Patent Document 6). However, when hydrazine is used for a magnesium alloy, the resulting coating is brittle, so that the alkali described above is used. It is preferable to perform chemical conversion treatment using a solution.

(2) Carboxylic acid, carboxylate salt A magnesium alloy substrate 1 is subjected to chemical conversion treatment using an aqueous carboxylic acid solution such as tannic acid. As a result, on the surface of the magnesium alloy substrate 1, these carboxylic acid and magnesium and / or aluminum in the magnesium alloy are bonded to each other, and a chemical conversion film containing the magnesium salt and / or aluminum salt of the carboxylic acid as a main component is generated.

  Further, the chemical conversion treatment may be performed using an aqueous solution of an alkali metal salt such as a sodium salt or a potassium salt of a carboxylic acid such as lauric acid, palmitic acid or stearic acid. In this case, a chemical conversion film 2 mainly composed of alkali metal salts of these carboxylic acids is formed on the surface of the magnesium alloy substrate 1. This chemical conversion film 2 may contain the magnesium salt and / or aluminum salt of the said carboxylic acid.

  Chemical conversion treatment may be performed using an aqueous solution of an aluminum salt of formic acid, acetic acid, oxalic acid, or succinic acid. In this case, a chemical conversion film 2 mainly composed of an aluminum salt of these carboxylic acids is formed on the surface of the magnesium alloy substrate 1. This chemical conversion film 2 may contain the magnesium salt of the said carboxylic acid. For example, when the chemical conversion treatment is performed using an aluminum oxalate aqueous solution, the aqueous solution preferably has a concentration of 0.5 to 30 g / L and a temperature of 30 to 70 ° C.

(3) Phosphoric acid, phosphate Phosphoric acid, manganese phosphate, manganese hydrogen phosphate, aluminum hydrogen phosphate, aluminum dihydrogen phosphate, aluminum phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate, calcium phosphate Chemical conversion treatment is performed using a solution of phosphoric acid and phosphate containing —H ₂ PO ₄ , —HPO ₄ or —PO ₄ , such as sodium and zirconium phosphate. The phosphoric acid referred to in this specification is phosphoric acid in a broad sense including orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and the like, and phosphate refers to orthophosphoric acid, metaphosphoric acid, pyrolinic acid. It is a concept including a compound of phosphoric acid in a broad sense such as acid, triphosphoric acid, and tetraphosphoric acid.

  By using phosphoric acid, the chemical conversion film 2 containing magnesium phosphate and / or aluminum phosphate as a main component is formed on the surface of the magnesium alloy substrate 1.

  Meanwhile, phosphoric acid such as manganese phosphate, manganese hydrogen phosphate, aluminum hydrogen phosphate, aluminum dihydrogen phosphate, aluminum phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate, sodium calcium phosphate and zirconium phosphate By performing a chemical conversion treatment using an aqueous solution of a salt (a metal salt of phosphoric acid), the chemical conversion film 2 containing these phosphates as a main component can be formed on the surface of the magnesium alloy substrate 1. These phosphate chemical conversion films 2 may contain magnesium phosphate and / or aluminum phosphate. Further, for example, a plurality of phosphates other than magnesium phosphate and aluminum phosphate may be included by performing chemical conversion treatment in a solution in which different types of metal phosphates are mixed.

  For example, when the chemical conversion treatment is performed using an aqueous solution of zirconium phosphate, the aqueous solution preferably has a concentration of 1 to 100 g / L and a temperature of 20 to 90 ° C. Other than this, such as phosphoric acid, manganese phosphate, manganese hydrogen phosphate, aluminum hydrogen phosphate, aluminum dihydrogen phosphate, aluminum phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate, calcium phosphate sodium When using an aqueous solution of phosphoric acid and phosphate, the aqueous solution preferably has a concentration of 5 to 30 g / L and a temperature of 20 to 90 ° C, and more preferably a temperature of 25 to 75 ° C. .

(4) Silicate Chemical conversion treatment is performed using an aqueous solution of silicate or metasilicate such as sodium metasilicate, sodium orthosilicate, or potassium metasilicate. As a result, a chemical conversion film 2 mainly composed of silicate or metasilicate such as sodium metasilicate, sodium orthosilicate, or potassium metasilicate is obtained on the surface of the magnesium alloy substrate 1. The obtained chemical conversion film 2 may contain magnesium silicate (magnesium metasilicate) and / or aluminum silicate (aluminum metasilicate).

  On the other hand, by performing a chemical conversion treatment using an aqueous solution of a silicate (metal salt of silicate) such as aluminum silicate or zirconium silicate, the surface of the magnesium alloy substrate 1 has these silicates as main components. The chemical conversion film 2 to be formed can be formed. For example, when the chemical conversion treatment is performed using an aqueous solution of aluminum silicate, the aqueous solution preferably has a concentration of 0.5 to 30 g / L and a temperature of 30 to 70 ° C.

  Moreover, the chemical conversion film 2 of these silicate metal salts may contain magnesium silicate and / or aluminum silicate. Furthermore, a plurality of silicates other than magnesium silicate and aluminum silicate may be included, for example, by performing a chemical conversion treatment in a solution in which different types of metal silicates are mixed.

(5) Carbonic acid, carbonate Chemical conversion treatment is performed using carbonic acid or an aqueous solution of carbonate such as sodium carbonate, potassium carbonate, sodium bicarbonate, manganese carbonate, aluminum carbonate, calcium carbonate, strontium carbonate, zirconium carbonate. When carbonic acid is used, it binds to magnesium and / or aluminum in the magnesium alloy, and a chemical conversion film 2 of magnesium carbonate and / or aluminum carbonate is formed on the surface of the magnesium alloy substrate 1. On the other hand, when carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, manganese carbonate, aluminum carbonate, calcium carbonate, strontium carbonate, and zirconium carbonate are used, a chemical conversion film mainly composed of these carbonates is formed. The obtained chemical conversion film may contain magnesium carbonate and / or aluminum carbonate.
For example, when the chemical conversion treatment is performed using an aqueous solution of aluminum carbonate, the aqueous solution preferably has a concentration of 1 to 50 g / L and a temperature of 50 to 90 ° C.

(6) Sulfuric acid, sulfate salt Chemical conversion treatment is performed using sulfuric acid or an aqueous solution of sulfate such as sodium sulfate, manganese sulfate, aluminum sulfate, calcium sulfate, titanyl sulfate, zirconium sulfate, potassium aluminum sulfate, sodium aluminum sulfate. When sulfuric acid is used, a chemical conversion film 2 containing magnesium sulfate and / or aluminum sulfate as a main component is formed on the surface of the magnesium alloy substrate 1. On the other hand, when a metal salt of sulfuric acid such as sodium sulfate, manganese sulfate, aluminum sulfate, calcium sulfate, titanyl sulfate, zirconium sulfate, potassium aluminum sulfate, or sodium aluminum sulfate is used, the chemical conversion film 2 containing these metal salts as a main component is obtained. It is formed. The obtained chemical conversion film 2 may contain magnesium sulfate and / or aluminum sulfate.
For example, when the chemical conversion treatment is performed using an aqueous solution of potassium aluminum sulfate, the aqueous solution preferably has a concentration of 0.5 to 30 g / L and a temperature of 30 to 60 ° C.

(7) Thiosulfate Chemical conversion treatment is performed using an aqueous solution of thiosulfate such as sodium thiosulfate and calcium thiosulfate. A chemical conversion film 2 mainly composed of these thiosulfates is formed on the surface of the magnesium substrate 1. In addition, the obtained chemical film 2 may contain magnesium thiosulfate and / or aluminum thiosulfate.
For example, when the chemical conversion treatment is performed using an aqueous solution of calcium thiosulfate, the aqueous solution preferably has a concentration of 20 to 50 g / L and a temperature of 40 to 60 ° C.

(8) Nitric acid, nitrate, nitrite Nitric acid or sodium nitrate, ammonium nitrate, manganese nitrate, calcium nitrate, calcium nitrite, aluminum nitrate, solution of nitrite (metal salt) such as strontium nitrate (for example, aqueous solution) Use chemical conversion treatment. When nitric acid or ammonium nitrate is used, a chemical conversion film 2 mainly composed of magnesium nitrate and / or aluminum nitrate is formed on the surface of the magnesium alloy substrate 1. On the other hand, when a metal salt of nitric acid or nitrous acid such as sodium nitrate, manganese nitrate, calcium nitrate, calcium nitrite, aluminum nitrate, or strontium nitrate is used, the chemical conversion film 2 containing these metal salts as a main component is formed. In this case, the obtained chemical conversion film may contain magnesium nitrate and / or aluminum nitrate.
For example, when the chemical conversion treatment is performed using an aqueous solution of aluminum nitrate, the aqueous solution preferably has a concentration of 0.5 to 50 g / L and a temperature of 30 to 60 ° C.

(9) Permanganate A chemical conversion treatment is performed using an aqueous solution of permanganate such as a solution of potassium permanganate. A chemical conversion film 2 mainly composed of these permanganates is formed on the surface of the magnesium substrate 1. The obtained chemical conversion film 2 may contain magnesium permanganate and / or aluminum permanganate.
For example, when the chemical conversion treatment is performed using an aqueous solution of potassium permanganate, the aqueous solution preferably has a concentration of 1 to 10 g / L and a temperature of 30 to 70 ° C.

(10) Amino compound Chemical conversion treatment is performed using an amino compound containing an amino group such as ethylamine, isopropylamine, diethylamine, triazole, aniline, or a solution of these amino compounds (for example, an aqueous solution, or an alcohol or benzene solution). A chemical conversion film 2 mainly composed of these amino compounds is formed on the surface of the magnesium substrate 1.
For example, when the chemical conversion treatment is performed using an aqueous solution of ethylamine, the aqueous solution preferably has a concentration of 5 to 100 g / L and a temperature of 30 to 70 ° C.

(11) Metal acetylacetonate A chemical conversion treatment is performed using a metal acetylacetonate solution such as Zn (COCH ₂ COOCH ₃ ) ₂ (for example, an aqueous solution). A chemical conversion film 2 containing metal acetylacetonate as a main component is formed. For example, when the chemical conversion treatment is performed using an aqueous solution of Zn (COCH ₂ COOCH ₃ ) ₂ , the aqueous solution preferably has a concentration of 0.1 to 30 g / L and a temperature of 20 to 70 ° C.

  Among the chemical conversion treatments described above, a method using hydroxide is preferable, and a method using phosphoric acid and phosphate is more preferable.

  In the method using hydroxide, the formed chemical conversion film 2 is dense, and the bonding strength with the magnesium alloy substrate 1 is strong. If the concentration and temperature of the aqueous solution of hydroxide are within the above-mentioned preferred ranges, it is possible to obtain a dense chemical conversion film 2 in a relatively short time.

In the method using phosphoric acid and phosphate, it is possible to form a relatively uniform chemical coating 2 having a thickness of preferably 0.05 to 5 μm, more preferably 0.05 to 2 μm. .
For this reason, the alkoxysilane-containing triazine thiol derivative penetrates into the chemical conversion film 2 and there are more sites that react with the chemical conversion film 2, and silanol formed by hydrolysis of the alkoxysilane of the triazine thiol derivative and phosphoric acid of the chemical conversion film component The group undergoes a dehydration reaction by heat treatment and is chemically bonded. In this way, a stronger bond can be obtained between the dehydrated silanol-containing triazine thiol derivative coating 3 and the chemical conversion film 2 to be produced.

  Further, when the resin 4 is cooled and contracted after bonding, the chemical conversion film 2 disperses and absorbs the stress generated between the resin 4 and the chemical conversion film 2, and the resin 4 is peeled off and the chemical conversion film 2 is cracked. Has the effect of preventing. If the concentration and temperature of phosphoric acid or phosphate are within the above-mentioned preferred ranges, it is possible to obtain a dense chemical conversion film 2 in a relatively short time.

  In addition, the chemical conversion treatment using the above solution is not limited to immersing all or part of the magnesium alloy substrate 1 in the solution (chemical conversion solution), but also spraying all or part of the surface of the magnesium alloy substrate 2. Coating the solution by application or the like, or contacting with the solution.

  Therefore, as apparent from the above, the chemical conversion film 2 does not necessarily have to be formed on the entire surface of the magnesium alloy substrate 2, and may be formed only on necessary portions as appropriate.

1-3. Coating of Alkoxysilane-Containing Triazine Thiol Derivative After forming the chemical conversion film 2 on the surface of the magnesium alloy substrate 1 by the method described above, the chemical conversion film 2 is coated with the alkoxysilane-containing triazine thiol derivative.
The alkoxysilane-containing triazine thiol derivative to be used may be a known one such as an alkoxysilane-containing triazine thiol metal salt disclosed in Patent Document 6, for example.
That is, it is represented by the general formula shown in the following (Formula 1) or (Formula 2).

R ¹ in the formula is, for example, any one of H—, CH ₃ —, C ₂ H ₅ —, CH ₂ ═CHCH ₂ —, C ₄ H ₉ —, C ₆ H ₅ —, C ₆ H ₁₃ —. is there. R ² is, for example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ SCH ₂ CH ₂ —, —CH. ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ —. R ³ is, for example, — (CH ₂ CH ₂ ) ₂ CHOCONHCH ₂ CH ₂ CH ₂ — or — (CH ₂ CH ₂ ) ₂ N—CH ₂ CH ₂ CH ₂ —, in which case N and R ³ is a ring structure.

X in the formula _{is, CH 3 -, C 2 H} 5 -, n-C 3 H 7 -, i-C 3 H 7 -, n-C 4 H 9 -, i-C 4 H 9 -, t- One of C ₄ H ₉ —. Y _{is, CH 3 O-, C 2 H} 5 O-, n-C 3 H 7 O-, i-C 3 H 7 O-, n-C 4 H 9 O-, i-C 4 H 9 O- a _{t-C 4 H} 9 O- and alkoxy groups. N in a formula is either 1, 2, or 3 numbers. M is an alkali metal, preferably Li, Na, K or Ce.

  A solution of an alkoxysilane-containing triazine thiol derivative that covers the chemical conversion film 2 is prepared. The solvent to be used is not particularly limited as long as the alkoxysilane-containing triazine dithiol derivative can be dissolved, and water and alcohol solvents correspond to this. For example, water, methanol, ethanol, propanol, carbitol, ethylene glycol, polyethylene glycol, and a mixed solvent thereof can be used. A preferable concentration of the alkoxysilane-containing triazine dithiol derivative is 0.001 g to 20 g / L, and a more preferable concentration is 0.01 g to 10 g / L.

  In the obtained alkoxysilane-containing triazine dithiol derivative solution, the magnesium alloy substrate 1 provided with the chemical conversion film 2 is immersed. The preferable temperature range of a solution and the more preferable temperature range are 0 degreeC-100 degreeC, and 20 degreeC-80 degreeC, respectively. On the other hand, the immersion time is preferably 1 minute to 200 minutes, more preferably 3 minutes to 120 minutes.

  By this immersion, the alkoxysilane part of the alkoxysilane-containing triazine thiol derivative becomes silanol, and the hydroxide, carboxylate, phosphate, silicate, carbonate, sulfate, thiosulfuric acid contained in the chemical conversion film 2 described above. A hydrogen-bonded loose bond is formed between at least one of a salt, nitrate, nitrite, oxo compound, permanganate, amino compound and metal acetylacetonate.

  And this magnesium alloy member is heated to 100 to 450 degreeC for the purpose of drying and dehydration reaction promotion. This heating causes a dehydration bond reaction in the silanol portion of the silanol-containing triazine thiol derivative. Therefore, the silanol-containing triazine thiol derivative is changed to a dehydrated silanol-containing triazine thiol derivative and chemically bonded to the chemical conversion film 2. .

  Therefore, this makes it possible to obtain a magnesium alloy member used for bonding a resin to the surface, which comprises the magnesium alloy substrate 1, the chemical conversion film 2, and the dehydrated silanol-containing triazine thiol derivative coating 3.

  Next, in order to further strengthen the bonding force between the dehydrated silanol-containing triazine thiol derivative and the resin, the dehydrated silanol-containing triazine thiol derivative formed on the chemical conversion film 2 is appropriately used as a bonding aid, for example, as necessary. N, N'-m-phenylene dimaleimide, which is a dimaleimide, N, N'-hexameethylene dimaleimide, and compounds such as dicurmyl peroxide, benzoyl peroxide and the like. Immerse in a solution containing an oxide or other radical initiator. After immersion, the magnesium alloy member is dried and heat-treated at 30 ° C. to 270 ° C. for 1 minute to 600 minutes.

  As a result, the dehydrated silanol-containing triazine thiol derivative removes the metal ion of the triazine thiol metal salt (triazine thiol derivative) portion, and the sulfur becomes a mercapto group, and this mercapto group becomes N, N′-m-phenylenedimaleimide. It reacts with one of the two double bonds of maleic acid to form a dehydrated silanol-containing triazine thiol derivative bonded with N, N′-m-phenylene dimaleimide.

  Furthermore, if necessary, a solution obtained by dissolving a radical initiator such as a peroxide or a redox catalyst in an organic solvent such as benzene or ethanol is attached to the surface of the magnesium alloy member by spraying by dipping or spraying, etc. Air dry.

  The radical initiator generates radicals by thermal decomposition such as heating performed when molding the resin, opens the other bond of the two double bonds by the maleic acid, or forms a metal salt part of the triazine thiol derivative. It works to react and bond with the resin.

1-4. Bonding with Resin A magnesium alloy member 100 having a chemical conversion coating 2 and a dehydrated silanol-containing triazine thiol derivative layer 3 and a resin 4 are bonded (composite integrated) to the surface of the magnesium metal substrate 1 to obtain a magnesium article 100. The resin 4 is disposed so as to be in contact with the dehydrated silanol-containing triazine thiol derivative layer 3 in a heated state. As a result, the resin 4 and the triazine thiol derivative part of the dehydrated silanol-containing triazine thiol derivative 3 (triazine thiol metal salt part or triazine thiol derivative combined with bismaleimides) react with the radical of the radical initiator as a chemical, Create a bond.
The resin may be disposed only on a part of the dehydrated silanol-containing triazine thiol derivative coating 3.

  As a method for disposing the heated resin 4 on the dehydrated silanol-containing triazine thiol derivative coating 3, for example, a magnesium alloy member (including the metal substrate 1, the chemical conversion film 2, and the dehydrated silanol-containing triazine thiol derivative coating 3) is placed on the mold. When placing and injecting molten resin into a mold to obtain an insert molded article or an outsert molded article, the radical initiator is decomposed by the heat of the mold and the resin, and the triazine thiol derivative coating and the resin are separated by a radical reaction. An injection molding method in which the magnesium alloy member and the resin 4 are bonded by chemical bonding, or after the resin molding, the injection molded product is heated on an oven or a hot plate to decompose the radical initiator and chemically bond by radical reaction. Thus, a welding method for joining the magnesium member and the resin can be used.

  In the case of injection molding, the mold temperature is 20 to 220 ° C., 5 seconds to 10 minutes, and in the case of the welding method, the oven or hot plate temperature is maintained at 30 to 430 ° C. for 1 minute to 10 hours. The temperature needs to be equal to or higher than the decomposition temperature of the radical initiator, and the holding time needs a sufficient time for the radical to form a chemical bond between the triazine thiol derivative and the resin.

  As the resin to be joined, any industrially usable resin can be used, but a resin having an element that reacts with a radical or a functional group is preferable. Examples of such preferred resins are phenol resin, hydroquinone resin, cresol resin, polyvinyl phenol resin, resorcin resin, melamine resin, glyphtal resin, epoxy resin, modified epoxy resin, polyvinyl formal resin, polyhydroxymethyl methacrylate and its co-polymer. Polymer, polyhydroxyethyl acrylate and copolymer, acrylic resin, polyvinyl alcohol and copolymer, polyvinyl acetate, polyethylene terephthalate resin, polyimide resin, polyetherimide resin, polyketoneimide resin, polybutylene terephthalate resin, unsaturated Polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polystyrene resin, ABS resin, 6-nylon resin, 66-nylon resin, 610-na Ron resins, aromatic polyamide resins, urea resins, and composite resins were combined two or more kinds selected from these resins, and glass fibers of these resins, reinforced resin reinforced carbon fibers, ceramics or the like.

  As described above, the magnesium alloy article 100 in which the magnesium alloy substrate 1 and the resin 4 are bonded via the chemical conversion film 2 and the dehydrated silanol-containing triazine thiol derivative coating 3 can be manufactured.

  The magnesium alloy article obtained by this method does not require any special machining on the surface of the magnesium article in addition to the advantage that the bonding strength between the magnesium alloy substrate and the resin is high. Since the resin can be joined without using a relaxation elastic resin or the like, there are advantages in that the number of processing steps is small, the joint is finished cleanly, and can be finished with high dimensional accuracy.

  Furthermore, by covering a portion of the magnesium base that is difficult to be molded with poor molding accuracy with a resin, the article is finished with the resin molding accuracy, and the yield of the product can be increased.

1-5. Evaluation Example A die-cast plate of AZ91 magnesium alloy having a length of 80 mm, a width of 20 mm, and a thickness of 1.5 mm was pretreated.

  The pretreatment was pre-degreasing in a sodium hydroxide aqueous solution having a concentration of 15.0 g / L and a temperature of 60 ° C., and then degreasing in a sodium hydroxide aqueous solution having a concentration of 75.0 g / L and a temperature of 70 ° C. . Etching is performed in a strong acid mainly composed of sulfuric acid having a temperature of 60 ° C. and a concentration of 1 to 3 g / L for 60 seconds, followed by a strong alkali treatment for 120 seconds in sodium hydroxide having a concentration of 60.0 g / L and a temperature of 70 ° C. Washed with water.

  In order to obtain the samples of Examples 1 to 3, following the pretreatment, the magnesium alloy sheet was subjected to the following chemical conversion treatment.

  The sample of Evaluation Example 1 was immersed in a sodium hydroxide solution having a concentration of 60 g / L and a temperature of 70 ° C. for 180 seconds to obtain a chemical conversion film containing magnesium hydroxide and aluminum hydroxide as main components on the surface of the magnesium alloy plate. .

  In the sample of Evaluation Example 2, the sample was immersed in an aqueous manganese phosphate solution having a concentration of 7.5 to 10.0 g / L and a temperature of 35 ° C. for 30 seconds, containing manganese phosphate as a main component, and containing magnesium phosphate and aluminum hydroxide. A chemical conversion film having a thickness of 0.5 to 1 μm was obtained on the surface of the magnesium alloy plate.

  The thickness of the chemical conversion film containing manganese phosphate as a main component is measured by measuring the cross section with a scanning electron microscope after embedding and polishing a magnesium metal alloy plate having the chemical conversion film in a resin. It was obtained from the average.

  In the sample of Evaluation Example 3, compared with the sample of Evaluation Example 2, the treatment time for forming the conversion coating was 75 seconds for the purpose of obtaining a thicker conversion coating. The thickness of the obtained film was 1 to 2 μm, and was composed mainly of manganese phosphate as in Evaluation Example 2, and contained magnesium phosphate and aluminum hydroxide.

  As a comparative example, the magnesium alloy plate that has been subjected to the above-described pretreatment is referred to as comparative example 1, and a magnesium alloy plate that has been pretreated is subjected to a corona discharge surface treatment apparatus at an output of 0.37 kW and 2 m / min. A sample that was subjected to the plasma treatment once at a moving speed of was designated as Comparative Example 2. This plasma treatment is a method used as a surface treatment when, for example, a metal such as an aluminum alloy is joined to a resin using an alkoxysilane-containing triazine thiol.

Next, the samples of Evaluation Examples 1 to 3 and Comparative Examples 1 and 2 were immersed in an alkoxysilane-containing triazine thiol solution.
The alkoxysilane-containing triazine thiol derivative used was triethoxysilylpropylaminotriazine thiol monosodium, dissolved in a solvent of ethanol 95: water 5 (volume ratio) so that the concentration was 0.7 g / L, and the solution was dissolved. Obtained. This triethoxysilylpropylaminotriazine thiol monosodium solution was immersed for 30 minutes at room temperature.

  Thereafter, these samples were heat-treated in an oven at 160 ° C. for 10 minutes to complete the reaction and dry. Then, an acetone solution containing N, N′-m-phenylene dimaleimide (N, N′-1,3-phenylene dimaleimide) having a concentration of 1.0 g / L and dicumyl peroxide having a concentration of 2 g / L was added to room temperature. And then heat-treated in an oven at 150 ° C. for 10 minutes. Thereafter, an ethanol solution of dicumyl peroxide having a concentration of 2 g / L was sprayed on the entire surface of the sample at room temperature and air-dried.

Next, these samples were placed in a mold heated to 120 ° C., and ABS resin (Stylac (R) -ABS General Purpose 026) manufactured by Asahi Kasei Chemicals Co., Ltd. was 220 ° C. so that a part of the surface was bonded to the resin. Was injection molded to obtain a magnesium article sample.
The resin is molded in a mold so as to be a plate having a length of 80 mm, a width of 20 mm, and a thickness of 3 mm, and the end portion of one surface having a length of 12 mm and a width of 20 mm is subjected to the above treatment. It arrange | positions on the terminal part of an alloy plate sample, and this part is contacting. The magnesium alloy article obtained after the mold was cooled to 80 ° C. or lower was taken out.

The obtained magnesium alloy article samples of Evaluation Examples 1 to 3 and Comparative Examples 1 and 2 were used as tensile test pieces, and the joint strength was evaluated by a tensile test.
Using an autograph AG-10TD tester manufactured by Shimadzu Corporation, the magnesium plate part of the magnesium article sample and the terminal part of the resin plate part (terminal part on the side opposite to the joint part) were each gripped with a flat chuck, and the tensile speed was 5 mm / min. It pulled until it fractured at a pulling speed. The stress obtained by dividing the maximum ultimate load up to breakage by the joining area (length 12 mm × width 20 mm) was defined as joining strength (shear strength). Three tests were performed for each sample.
Table 1 shows the obtained bonding strength.

  In Comparative Examples 1 and 2, the fracture occurred at the joint surface, and the magnesium alloy plate and the resin were completely separated. On the other hand, in Evaluation Examples 1 to 3, the fracture was confirmed at the joint surface or the resin part. Further, regarding the fracture surface (magnesium alloy plate side) at the joint surface, adhesion of the resin was observed, and it was confirmed that a part of the fracture occurred in the resin.

2. Next, the detail of the deformation | transformation suppression method is shown below.
As described above, in each of at least one pair of opposing sides on the outer periphery of the base made of magnesium or a magnesium alloy, the first joint located between the center and one end, and the other from the center It has been found that by arranging the second bonding portion positioned between the end portions of the first and second end portions, stress is applied to the entire magnesium alloy substrate in a well-balanced manner and deformation is suppressed.

  For example, in the magnesium alloy substrate of FIG. 16, the chemical conversion film 2 and the dehydrated silanol-containing triazine thiol derivative coating 3 are formed over the entire length of two opposing sides (standing walls 211 and 213 and standing walls 212 and 214) of the substrate 250. Thus, a joint is formed on the entire outer periphery of the base body 250. That is, the first joint and the second joint (in this embodiment, the first and second joints are connected) are formed on all sides.

  Thereby, since the stress due to the shrinkage of the resin is uniformly applied to the entire base body 250, the deformation is suppressed. In this embodiment, the thickness of the resin to be joined is, for example, 50% or more of the thickness of the side on the outer periphery of the magnesium alloy substrate having a thickness of about 0.5 mm (the height of the standing walls 211 to 214 in FIG. 15). This is an effective method for joining thick resins.

  However, in the case of joining a thin resin such as less than 50% of the height of the standing wall (the thickness of the side on the outer periphery) because of the desire to reduce the thickness of the resin used for reasons such as weight reduction. The area of the joint is not sufficient, and there is a possibility that stress is not uniformly applied to the entire base body 250.

  Therefore, a more preferred embodiment that can more effectively suppress deformation of the magnesium alloy substrate even when the thickness of the resin to be joined is thin will be described below.

FIG. 3 is a perspective view showing the magnesium alloy article 110 according to the embodiment of the present invention.
FIG. 4 is a perspective view showing the magnesium alloy substrate 50 of the magnesium alloy article 110.

  The magnesium alloy article 110 can be used as a housing of various devices including electronic devices such as mobile phones. The magnesium alloy substrate 50 (the material and the like is the same as the magnesium alloy substrate 1 described above) includes a top plate (or bottom surface) 35 and the periphery of the top plate 35 (that is, so that various members such as electronic components can be accommodated therein). It has the standing walls 11-14 arrange | positioned on the outer periphery of the magnesium alloy base | substrate 50).

  In the standing walls 11 to 14, the standing wall 11 and the standing wall 13 face each other, and the standing wall 12 and the standing wall 14 face each other. Of the two sets of standing walls facing each other, at least one set of standing walls (in FIG. 4, standing walls 11 and 13) each have a joint protruding outward. The standing wall 11 has a joint portion 21 whose thickness is lower than the height of the standing wall 11 over the entire length in the outer peripheral direction (x direction in FIG. 4). Half of the joint 21 (for example, the length (the length along the outer circumference, the length in the x direction) to the −x direction) corresponds to the first joint, and the other half (the center of the length). To + x direction) corresponds to the second joint. That is, the joining part 21 has a form in which the first joining part and the second joining part are in contact with each other.

  On the other hand, the standing wall 13 has joint portions 31 and 32. The joint portions (fastening portions) 31 and 32 can be used as fastening portions for screwing the magnesium alloy article 110 to other parts. Thus, the joint portions have other functions. You may have. As can be seen from FIG. 4, the joint portion 31 is located in the x direction from the center of the length of the standing wall 13, and the joint portion 32 is located in the −x direction from the center of the length of the standing wall 13. 1 corresponds to a joint portion, and the other corresponds to a second joint portion. That is, the standing wall 13 has the 1st junction part and the 2nd junction part which were arrange | positioned apart.

  Of the magnesium alloy substrate 50, the above-described chemical conversion film 2 and dehydrated silanol-containing triazine thiol derivative film 3 are formed (not shown in FIG. 3) on at least the joining portions 21, 31, and 32 to obtain a magnesium alloy member. Then, the resin, the magnesium alloy substrate 50 and the resin 4 are bonded to each other on the surfaces of the bonding portions 21, 31 and 32 via the chemical conversion film 2 and the dehydrated silanol-containing triazine thiol derivative film 3.

  The joining with the resin 4 at the joining portions 21, 31 and 32 may be performed only on one surface of the joining portion. Preferably, the bonding portions 21, 31, and 32 are bonded to the resin on both surfaces of the bonding portion, for example, by completely covering the bonding portions 21, 31, and 32 with the resin 4 so as to increase the bonding area.

  Since the deformation can be suppressed more easily by increasing the number of joints between the resin 4 and the magnesium alloy base 50, the joint between the magnesium alloy base 50 and the resin 4 can be performed at portions other than the joints 21, 31, 32. Preferably it is done. For example, in the embodiment shown in FIG. 3, the chemical conversion film 2 and the dehydrated silanol-containing triazine thiol derivative film 3 are formed on the outer surfaces of the standing walls 11 to 14 (for example, the chemical conversion film on the entire surface of the magnesium alloy substrate 50). 2 and the dehydrated silanol-containing triazine thiol derivative coating 3 may be formed), and the outer surface of the standing walls 11 to 14 and the resin 4 are in contact via the chemical conversion coating 2 and the dehydrated silanol-containing triazine thiol derivative coating 3 Can be joined.

  A mechanism that can suppress the deformation of the magnesium alloy base 50 by providing such joints 21, 31, and 32 is estimated as follows.

  The stress applied to the standing wall 11 and the standing wall 13 due to the difference in shrinkage amount occurs inward of the magnesium alloy substrate 50 because the shrinkage amount of the resin is larger than the shrinkage amount of the magnesium alloy. Since the first joint portion and the second joint portion are formed on opposite sides of the center of the length of the standing wall 11 or 13, the stress is uniformly applied to the standing walls 11 and 13 and the deformation is suppressed. Can be obtained.

  Furthermore, since the joints 21, 31, and 32 protrude outward, even if the thickness of the resin 4 (z direction in FIG. 3) is thin, these joints should be joined to the resin 4 over a wide area. It is possible to avoid applying a strong stress locally.

Below, it demonstrates in detail about a standing wall and a junction part.
In the embodiment shown in FIGS. 3 and 4, the standing walls 11 to 14 have the entire outer periphery of the top plate 35 surrounded by the standing walls 11 to 14. One set may be provided. Further, the standing walls 11 to 14 may be disposed not only at the end of the top plate 35 but also between the top plate 35 as shown in FIG. 4 (for example, the standing wall 11). Furthermore, you may arrange | position not only in the edge part of the top plate 35 but in the position which entered a little into the inside from the edge part of the top plate 35.

  The standing walls 11 to 14 preferably have a height of 1 mm or more in order to secure a space for storing the members therein. Moreover, it is preferable that the thickness of the standing walls 11 to 14 is 0.5 mm or more so that the magnesium alloy article 110 can secure sufficient rigidity and can realize weight reduction even if the above-described stress occurs.

  In the embodiment shown in FIGS. 3 and 4, the top plate has a substantially rectangular shape, but may have various shapes such as a circle and a polygon other than this. When the top plate is circular, the facing vertical walls mean vertical walls or portions of the vertical walls whose arc-shaped positions are separated by 120 ° or more, and when the top plate is substantially triangular, it is located on two adjacent sides. Means standing walls.

Various arrangements are possible for the joint.
5-8 is a figure which shows roughly embodiment of the various arrangement | positioning of a junction part.
In the magnesium alloy base 51 shown in FIG. 5, as with the magnesium alloy base 50 shown in FIG. 4, one set of standing walls 11 ′ and 13 ′ out of a plurality of sets of opposing standing walls (two sets in the embodiment of FIG. 5). The joints 21 and 23 are attached so as to protrude outward from the standing wall. In the magnesium alloy base 51, the lengths of the standing walls 11 ′ and 13 ′ (length along the outer peripheral direction of the base 51, the x direction in FIG. 5) and the lengths of the joint portions 21 and 23 (along the outer peripheral direction of the base 51). The length (the x direction in FIG. 5) is the same, and both the standing wall 11 ′ and the standing wall 13 ′ are arranged so that the first joint portion and the second joint portion are in contact (integrated). .

  In addition, when selecting the set of the standing wall which provides the junction part 21 and the junction part 23 from a plurality of sets of the standing wall as shown in FIG. 5, it is more preferable to select the pair having a long distance between the opposing standing walls. Although it is preferable because the deformation can be suppressed, even if a pair having a short distance is selected, a certain deformation suppressing effect can be obtained.

The required bonding force between the magnesium alloy substrate and the resin differs depending on the part. In addition, since the chemical bonding force per unit area differs depending on the resin, the area of the bonding portion that can ensure the bonding force according to the component and the selected resin is required. In general, the joint portions 21 and 23 preferably have an area of 0.5 mm ² or more, and more preferably 1.0 mm ² or more.

9 is a top view of the magnesium alloy substrate 50 shown in FIG. 4 as viewed from the back side, which is the same embodiment as the magnesium alloy substrate 51 shown in FIG.
FIG. 10 is a top view showing a magnesium alloy substrate 55 which is a modification of the magnesium alloy substrate 50 shown in FIG. In the magnesium alloy base 55, the fastening portions 31 and 32 function as the first and second joints of the standing wall 13 as in the case of the magnesium alloy base 50, and the first wall and the second joint that are in contact with each other on the standing wall 11. A joining portion 21 ′ that functions as a joining portion is provided.

As for the width (y direction in FIG. 10) of the joining portion 21 ', the end portion (direction away from the center of the length) is wider than the central portion. As a result, the stress due to resin shrinkage (stress in the y-axis direction toward the inside of the base 55) can be increased at the end portion close to the standing wall 12 or 14, and can be decreased at the central portion where no support is provided by the standing wall.

  In the magnesium alloy base 52 shown in FIG. 6, two sets of opposed standing walls (standing walls 11 ′ and 13 ′ and standing walls 12 ′ and 14 ′) also have joint portions (joint portions 21 to 24). In the embodiment shown in FIG. 6, the joint portions 21 to 24 are arranged so as to surround the entire outer periphery of the standing wall. All of the upright walls 21 to 24 have a joint portion in which the first joint portion and the second joint portion are integrated.

  The plurality of sets of standing walls facing each other as described above has the first and second joint portions because deformation due to stress in a plurality of directions such as the x-direction stress and the y-direction stress in FIG. 6 can be suppressed. preferable.

FIG. 11 shows a magnesium alloy substrate 56 that is an example in which the embodiment shown in FIG. 6 is applied to a substrate similar to the magnesium alloy substrate 50 shown in FIG.
The magnesium alloy base 56 does not have a fastening portion, and the outer circumferences of the standing walls 11 to 14 are surrounded by the joint portions 21 to 24.

  FIG. 7 shows a magnesium alloy substrate 53 which is a modification of the magnesium alloy substrate 52 shown in FIG. The magnesium alloy base 53 also has two sets of opposed standing walls each having a joint. Each joint portion covers only a part of the periphery of the standing wall (the length of the standing wall 11 ′ (the length along the outer circumferential direction of the base 53, the length in the x direction in FIG. 7) is the same as the joining portion 21a. The length of 21b (the length along the outer circumferential direction of the base 53, the length in the x direction in FIG. 7) is longer, and the length of the standing wall 13 ′ is the sum of the lengths in the x direction of the joint portions 23a and 23b. Similarly, the length of the standing wall 12 '(the length along the outer circumferential direction of the base 53, the length in the direction of FIG. 7y) is the same as the length of the joining portions 22a and 22b (the length along the outer peripheral direction of the base 53). The length of the standing wall 14 'is longer than the sum of the lengths of the joint portions 24a and 24b.

  For example, in the standing wall 11 ′ shown in FIG. 7, all of the standing walls 11 ′ to 14 ′ are such that one of the joint portions 21 a and 21 b corresponds to the first joint portion and the other corresponds to the second joint portion. It has the 1st junction part and the 2nd junction part which were separated from each other.

In the magnesium alloy substrate 57 of the embodiment shown in FIG. 12, the standing wall 11 and the standing wall 13 are each provided with a joint portion 21 and a joint portion 23, respectively. On the other hand, the standing wall 12 includes two joint portions 22a and 22b, and the standing wall 14 also includes two joint portions 24a and 24b.
Thus, for example, depending on the length of the standing wall, a part of the standing walls 11 to 14 includes one joining portion in which the first joining portion and the second joining portion are integrated, and the remaining standing walls are the first. A plurality of joint portions may be provided so that the joint portion and the second joint portion are separated from each other.

  FIG. 13 shows the magnesium alloy article 120 in which the magnesium alloy substrate 57 and the resin 4 are joined at the joints 21, 22a, 22b, 23, 24a, and 24b.

  In the magnesium alloy base body 58 shown in FIG. 14, the standing walls 12 and 14 each have three joints, while the standing walls 11 and 13 each have two joints. Thus, for example, the number of joints may be changed according to the length of the standing wall. In the standing wall 12 of the embodiment shown in FIG. 14, the joint portions 22a and 22b correspond to one of the first or second joint portions, and the joint portion 22c corresponds to the other of the first or second joint portions. As described above, a plurality of first joint portions and / or a plurality of second joint portions may be provided on one standing wall.

  FIG. 8 shows a magnesium alloy base 54 which is another modification of the magnesium alloy base 52 shown in FIG. In the embodiment shown so far, the joint portion is provided at the upper portion or the lower portion of the standing wall. However, in the magnesium alloy base 54, the joint portions 21 to 24 are provided at the intermediate portion in the height direction of the standing wall (z direction in FIG. 8). Is provided. In addition, in the magnesium alloy base | substrate 54, although the junction part surrounds the whole circumference | surroundings of a standing wall, you may surround only a part of circumference | surroundings of a standing wall (namely, 1st and 2nd junction part may isolate | separate).

  The stress generated by providing a joint at the intermediate portion in the height direction of the standing wall is preferentially applied to the intermediate portion in the height direction of the base body, and a better deformation suppressing effect than when applied to the end portion can be obtained. There is a case.

  A method for producing a magnesium alloy article using the magnesium alloy substrate shown in the above embodiment (the surface is formed with the chemical conversion coating 2 and the dehydrated silanol-containing triazine thiol derivative coating 3 to become a magnesium alloy member) will be described below.

  A magnesium alloy substrate having a predetermined shape having a joint portion such as the magnesium alloy substrate 50 is obtained by, for example, die casting, thixo molding, press molding, or the like. Then, the conversion coating 2 and the dehydrated silanol-containing triazine thiol derivative coating 3 are formed on the surface of the magnesium alloy substrate, at least on the surface of the joint, using the method described in “1. obtain.

  Then, as shown in “1. Joining method”, the obtained magnesium alloy member is placed in a mold, heated to a predetermined mold temperature, and a predetermined molten resin is injected into the mold to perform insert molding. An article or an outsert molded article is obtained.

  Furthermore, after holding | maintaining predetermined temperature and time (for example, mold temperature 60-120 degreeC, 5 second-10 minutes), the magnesium alloy article | item obtained by cooling is taken out.

  At this time, it is preferable to cool to room temperature in order to prevent deformation of the resin 4. However, when the magnesium alloy article is taken out from the mold at a temperature higher than room temperature because the cooling time cannot be secured, for example, the extrusion pin for releasing the magnesium article from the mold avoids the resin 4 from being deformed. In this way, the push pin may be applied to the joint protruding outward from the standing wall.

  In the above-described embodiment, a magnesium alloy substrate having a standing wall has been described. However, the present invention describes a magnesium substrate (having a standing wall having a thickness corresponding to the standing wall (that is, a thickness capable of forming a joint protruding outward). And a magnesium alloy member in which the above-mentioned joint portion is provided on such a magnesium alloy substrate and the chemical conversion coating 2 and the water silanol-containing triazine thiol derivative coating 3 are formed, and the magnesium alloy member Magnesium alloy articles obtained by joining the resin 4 at the joint are also included in the technical scope of the present invention.

  In addition, the bonding method described above forms the chemical conversion film 2 and the dehydrated silanol-containing triazine thiol derivative coating 3 to obtain a strong bonding force between the magnesium alloy substrate and the resin. Magnesium alloy articles joined by the method described in “2. Joining method” using the means to obtain are also included in the technical scope of the present invention.

1 is a cross-sectional view of a magnesium alloy article 100 according to the present invention. It is sectional drawing of the conventional magnesium alloy article 200. FIG. It is a perspective view which shows the magnesium alloy article 110 concerning embodiment of this invention. 2 is a perspective view showing a magnesium alloy substrate 50 of a magnesium alloy article 110. FIG. It is the schematic which shows the magnesium alloy base | substrate 51 concerning embodiment of this invention. It is the schematic which shows the magnesium alloy base | substrate 52 concerning embodiment of this invention. It is the schematic which shows the magnesium alloy base | substrate 53 concerning embodiment of this invention. It is the schematic which shows the magnesium alloy base | substrate 54 concerning embodiment of this invention. It is the top view which looked at the magnesium alloy base | substrate 50 shown in FIG. 4 from the back side. It is a top view which shows the magnesium alloy base | substrate 55 concerning embodiment of this invention. It is a top view which shows the magnesium alloy base | substrate 56 concerning embodiment of this invention. It is a top view which shows the magnesium alloy base | substrate 57 concerning embodiment of this invention. It is a top view which shows the magnesium alloy article 120 concerning embodiment of this invention. It is a top view which shows the magnesium alloy base | substrate 58 concerning embodiment of this invention. It is a perspective view which shows the conventional magnesium alloy article 210. FIG. It is a perspective view which shows the conventional magnesium alloy base | substrate 250. FIG.

Explanation of symbols

  1,50-58,250 Magnesium alloy substrate, 2 conversion coating, 3 dehydrated silanol-containing triazine thiol derivative coating, 4,204 resin, 11, 11 ', 12, 12', 13, 13 ', 14, 14', 211 -214 Standing wall, 21, 21 ', 21a, 21b, 22, 22a, 22b, 22c, 23, 23a, 23b, 24a, 24b, 24c, 31, 32 Joint part, 231, 232 Fastening part, 35, 235 Top plate , 100, 110, 120 Magnesium alloy articles

Claims (12)

A bottom surface, at least one pair of opposing standing walls disposed around the bottom surface and projecting upward from the bottom surface, and a first joint disposed on each of the standing walls and projecting outward from the standing wall and a second joint portion, a second junction located between the center and the other end of the first joint and the standing wall which is located between the center and one end of the upstanding wall A magnesium article comprising a substrate made of magnesium or a magnesium alloy,
The first joint and the second joint include hydroxide, carboxylate, phosphate, silicate, carbonate, sulfate, thiosulfate, nitrate, nitrite, permanganate Bonding with a resin surrounding at least a part of the outer periphery of the substrate via a chemical conversion film containing at least one selected from the group consisting of a salt, an amino compound and a metal acetylacetonate and a dehydrated silanol-containing triazine thiol derivative coating A magnesium alloy article characterized by comprising:   The magnesium alloy article according to claim 1, wherein the first joint portion and the second joint portion are separated from each other.   The magnesium alloy article according to claim 1, wherein the first joint portion and the second joint portion are in contact with each other. The thickness of the said 1st junction part and the said 2nd junction part is smaller than the height of the at least 1 set of standing wall which opposes, The Claim 1 characterized by the above-mentioned. Magnesium alloy article. The have two or more pairs of opposed to that standing walls around, characterized in that, respectively that of the vertical wall opposite of the two or more sets has a second joint portion between the first joining portion The magnesium alloy article according to any one of claims 1 to 4 . The magnesium alloy article according to any one of claims 1 to 5, wherein the first joint portion and the second joint portion are disposed in an intermediate portion in the height direction of the standing wall. A bottom surface, at least one pair of opposing standing walls disposed around the bottom surface and projecting upward from the bottom surface, and a first joint disposed on each of the standing walls and projecting outward from the standing wall and a second joint portion, a second junction located between the center and the other end of the first joint and the standing wall which is located between the center and one end of the upstanding wall The first joint and the second joint are hydroxide, carboxylate, phosphate, silicate, carbonate, sulfate, thiosulfate, nitrate, Magnesium alloy member characterized by being coated with dehydrated silanol-containing triazine thiol derivative through a chemical conversion film containing at least one selected from the group consisting of nitrite, permanganate, amino compound and metal acetylacetonate . The magnesium alloy member according to claim 7 , wherein the first joint and the second joint are separated from each other. The magnesium alloy member according to claim 7 , wherein the first joint portion and the second joint portion are in contact with each other. Wherein the first junction and the second junction according to any one of claims 7-9 in which the thickness is equal to or smaller than the height of the at least one pair of standing walls of the counter Magnesium alloy member. The have two or more pairs of opposed to that standing walls around, characterized in that, respectively that of the vertical wall opposite of the two or more sets has a second joint portion between the first joining portion The magnesium alloy member according to any one of claims 7 to 10 . The magnesium alloy member according to any one of claims 7 to 11, wherein the first joint portion and the second joint portion are disposed at an intermediate portion in a height direction of the standing wall.

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