JPS6137113B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a laminate molded product in which a ribbon or thin plate of an amorphous alloy is sandwiched between thermoplastic resin films and then molded and fused. Amorphous alloys include, for example, chromium, cobalt,
It is an amorphous alloy in which one or more of nickel, etc. is the basic component, and one or more of phosphorus, carbon, silicon, molybdenum, boron, etc. is added as an auxiliary component. Since this alloy is amorphous, it has characteristic electrical, magnetic, chemical, and mechanical properties that cannot be obtained from ordinary metal materials. For example, amorphous alloys have a very large magnetic shielding effect. However, due to problems with the cooling rate, amorphous alloys are currently only available in thin plates with a thickness of about 100 μm or less, and there is a problem that they lack rigidity and are difficult to deform plastically. The present invention solves the above problems and provides a method for easily processing amorphous alloys into various molded products. That is, the method of the present invention involves laminating thin plates of amorphous alloy with predetermined dimensions and a thermoplastic resin film, and subjecting this laminate to a molding process (hereinafter referred to as , simply referred to as the molding step) and at a temperature above the melting point of the resin and below the crystallization temperature of the amorphous alloy.
This consists of carrying out a step of holding and fusing under a pressure of 5 to 5 kg/cm ² (hereinafter simply referred to as a fusing step) by changing this order. This results in a lightweight and highly rigid laminate molded article having the favorable properties of an amorphous alloy. The above-mentioned molding step and fusion step may be performed in any order, or if molding can be carried out even if the amorphous alloy thin plate and resin film are not fused, the molding step may be performed first. However, when amorphous alloy thin plates and resin films are laminated in multiple layers and then molded, if they are molded as is, there is a risk that the layers will rub and the quality of the molded product will be impaired. Further, there is a similar possibility when manufacturing a molded product having a somewhat complicated shape. In such cases, the fusion process is performed first to produce a simple preform, such as a plate-shaped molded product or a simple intermediate molded product, and then the molding process is performed to produce the molded product in the desired shape. However, if a fusing step is then added again as necessary, molded products of a wider range of shapes can be obtained. Many types of thermoplastic resin films can be used to laminate the amorphous alloy thin plate in the method of the present invention. The reason for this is that the surface of an amorphous alloy manufactured by the molten metal quenching method has fine irregularities on both the free solidification surface and the roll cooling surface, so by using a resin with excellent wettability, an anchor effect can be obtained. This is because the thin alloy plate and the resin film can be tightly adhered to each other. However, it is preferable to use thermoplastic resins that can be fused to inorganic materials. However, amorphous alloys tend to gradually crystallize and lose their favorable properties at high temperatures, and may also become brittle at temperatures well below the crystallization temperature. Therefore, the melting point of the resin used is preferably 200°C or lower. Examples of such resins include:
For example, ethylene-vinyl acetate copolymer (trade name
Examples include Modic-E1OOH (manufactured by Mitsubishi Yuka Co., Ltd. or trade name Bond Fast E (trade name: manufactured by Konishi Co., Ltd.)), and copolymerized nylon. These resins are generally used in the form of a film with a thickness of 4 to 250 μm, but they may also be dissolved or dispersed in a solvent or dispersant and applied to an amorphous alloy thin plate. Examples of the amorphous alloy used in the present invention include the following. : Fe ₄₀ Ni ₄₀ P ₁₄ B ₆ ,
Fe ₈₀ P ₁₃ C ₇ , Fe ₇₆ Si ₁₀ B ₁₄ , Fe _{62 .4} Ni _{15 .6} Si ₁₀ B ₁₂ ,
_{Fe78Si10B12 , Fe81B13.5Si3.5C2 , Fe6Co74B20 and Fe5Co70Si15B10 . _ _ _ _ _ _ _ _} Lamination of the amorphous alloy thin plate and the thermoplastic resin film is carried out by making the alloy thin plate and the resin film to predetermined dimensions and stacking them alternately until the desired thickness is achieved. Both surfaces are generally formed of resin films. However, if necessary, one or both of the upper and lower surfaces may be made of thin alloy plates. Several sets of the laminates obtained in this way may be further laminated, and in this case, as shown in Example 1 below, each set of laminates is stacked with their directions shifted from each other depending on the shape of the desired molded product. Good too. To manufacture a large-sized molded product using a narrow amorphous alloy ribbon, a plurality of alloy ribbons are stacked in parallel in the width direction between resin films, as shown in Example 2 below. At this time, if the longitudinal directions of the ribbons of the laminated alloy thin plates that overlap in the vertical direction with the resin film interposed are made to be substantially perpendicular to each other, a particularly good magnetic shielding effect can be imparted to the obtained molded product. The laminate thus laminated is molded by, for example, inserting or pressing the laminate into a mold by bending. At this time, the molding temperature must be higher than the softening point of the resin, such as about 50° C., and lower than the melting point. In this temperature range, resin easily deforms due to external force, and amorphous alloys also bend and deform.
The laminate can be molded into a desired shape. The melting point of the resin (generally 100 to 240
C)) and below the crystallization temperature of the amorphous alloy (generally 350 to 500 DEG C.) and held under a pressure of 0.1 to 5 kg/ ^cm2 for 1 to 10 minutes. The reason for applying pressure is to improve wettability with the amorphous alloy. It is particularly important that this fusion be performed at a temperature below the crystallization temperature of the amorphous alloy. Otherwise, the amorphous alloy will crystallize and deoxidize, making it impossible to obtain a molded product with the desired high rigidity. Therefore, fusion bonding is usually carried out at 100-240°C. The fused laminate is cooled under pressure, and after the resin has solidified, the pressure is returned to normal to obtain a molded or preformed product. A laminate molded product made of an amorphous alloy and a thermoplastic resin obtained by the method of the present invention is lighter and more rigid than a molded product made of conventional metal materials. This excellent property will be explained in detail in the following test examples. Test Example 1 Amorphous alloy ribbon 2 with a thickness of 25 μm and a width of 10 mm having a composition of Fe ₄₀ Ni ₄₀ P ₁₄ B ₆ manufactured by a molten metal quenching method.
and commercially available thermoplastic ethylene with a thickness of 25 μm.
Sheets 1 of vinyl acetate copolymer (Modic-E100H) are alternately stacked in 10 layers as shown in Figure 1, and the laminate is heated at 100 to 240°C above the melting point of the resin and below the crystallization temperature of the amorphous alloy. After holding the mold under a pressure of 1 kg/cm ² for 3 minutes in a heated mold, the mold temperature was cooled to 40°C while the pressure remained, and the pressure was returned to normal to form a 1.7 mm thick laminate. Obtained. A test piece with a width of 10 mm and a length of 200 mm was cut out from this laminate, and its bending elastic modulus (Young's modulus) was measured using the following formula: Bending rigidity = 1/12 x E x b x t ³ [In the formula, E is Young's modulus] Ratio (Kg/mm ² ) b is the board width (mm) t is the board thickness (mm). ] When the bending rigidity was determined using the general calculation method shown in Table 1, a value of 8200 Kg×mm ² was obtained. The weight of the laminate in this test example was reduced to about half that of a steel plate with a thickness of about 0.8 mm and having the same bending rigidity.

[Table] We also investigated the relationship between the above mold temperature and the shear tensile strength of the adhesive surface between the resin and the amorphous alloy ribbon, and found that it was 30 to 60 kg/cm ² in the mold temperature range of 100 to 240°C.
The above-mentioned good shear tensile strength was obtained. Furthermore, we investigated the relationship between the thickness of the thermoplastic resin sheet and the shear tensile strength of the adhesive surface.
30-60Kg/ ^cm2 for sheet thickness 4-250μm
The above-mentioned good shear tensile strength was obtained. Test Example 2 An amorphous alloy ribbon with a thickness of 25 μm and a width of 10 mm having a composition of Fe ₄₀ Ni ₃₈ Mo ₄ B ₁₈ manufactured by a molten metal quenching method and a commercially available thermoplastic film film with a thickness of 80 μm and dimensions of 1550 x 150 mm. A sheet of ethylene-vinyl acetate copolymer (Modic-E100H) was used. These ribbons 2 and sheets 1 were alternately stacked in 10 layers as shown in FIG. At this time, 15 amorphous alloy ribbons 2 each having a length of 150 mm were lined up and stacked so as to be sandwiched between the resin sheets 1. This laminate was set in a mold heated to 140℃ and weighed 3Kg/
After pressurizing at cm ² for 3 minutes, the mold was cooled to 40° C. while still being pressurized, and returned to normal pressure to obtain a laminate. A test piece with a width of 10 mm and a length of 200 mm was cut out from the 1.7 mm thick laminate thus obtained, and its bending rigidity was measured. As a result, a bending stiffness value of approximately 9000 Kg/mm ² was obtained. Compared to a steel plate with a thickness of about 0.8 mm that has the same bending rigidity, the weight of the laminate in this test example was reduced to about half. Next, the method for manufacturing a molded article of the present invention will be explained in detail based on Examples. Example 1 An amorphous alloy ribbon with a thickness of 25 μm and a width of 50 mm having a composition of Fe ₇₆ Si ₁₀ B ₁₄ manufactured by a molten metal quenching method,
A sheet of commercially available film-like thermoplastic resin ethylene-vinyl acetate copolymer (Modic-E100H) with a thickness of 80 μm and dimensions of 50×100 mm was used. Figure 3A
As shown in the figure, two sets of laminates 3 were prepared by sandwiching the thin ribbon 2 between two resin sheets, and after stacking these laminates 3 and 3 in a criss-cross pattern, they were heated at 60°C.
It ^is bent at a temperature of
Hold for minutes. This molded product was heated to 40°C while it was still under pressure.
The box-shaped case 5 shown in FIG. When the box and lid of the box-shaped case 5 thus produced were made and used as a magnetic shielding box, it had an excellent magnetic shielding effect. Example 2 (1) An amorphous alloy ribbon of Fe ₇₆ Bi ₁₀ B ₁₄ produced by a molten metal quenching method and a commercially available film-like thermoplastic resin ethylene vinyl acetate copolymer (Modic-E100H) with a thickness of 80 μm and dimensions of 150 x 150 mm were used. A sheet was used. As shown in FIG. 4, two sets of laminates 3 were prepared by arranging amorphous alloy phosphors 2 each having a length of 150 mm and laminating them between three resin sheets. 3 were stacked so that the longitudinal directions of the alloy ribbons were perpendicular to each other. This laminate was set in a mold heated to 140°C, and pressurized at 3 kg/cm ² for 3 minutes.The mold was then cooled to 40°C while still under pressure, and then returned to normal pressure to remove the laminate. Obtained. Thickness 0.5 mm, dimensions 150 thus obtained
A 150mm x 150mm laminate was pressed onto the roll surface of a 40mm diameter steel roll heated to 70°C to form a cylindrical shape, and then the 5mm overlap portion was heated to 140°C to yield 1Kg/ ^cm2 . The pressure was maintained for 3 minutes. After that, it is cooled to 40℃ and the diameter is 40℃.
A cylindrical molded product with a length of 150 mm and a length of 150 mm was obtained. (2) The total thickness of the amorphous alloy manufactured in (1) above
A 50 μm cylindrical molded product was used to measure its magnetic shielding effect. The measurement follows the ASTM test method, placing the above cylinder inside a Helmholtz coil, measuring the magnetic field H inside the cylinder and the magnetic field Ho generated from the Helmholtz coil, and calculating the magnetic shielding coefficient S = Ho / H. This was done by doing this. This measurement is performed in a DC magnetic field and an AC magnetic field (60
Hz), the cylindrical molded product of this example showed a high magnetic shielding coefficient of 50 or more in both cases. Generally, the effectiveness of a magnetic shielding material is better as the thickness of the metal plates that make up the shielding material increases, but if the thickness of the metal plates is the same, several thinner metal plates are stacked and used. Although the interval between these overlaps is increased, the magnetic shielding effect increases and the rigidity of the shielding material also increases. In light of these facts, in the molded product manufactured by the method of the present invention, not only the amorphous alloy itself has an excellent magnetic shielding effect, but also the combination of the amorphous alloy thin plate and the resin film has an excellent magnetic shielding effect. This fully satisfies the above requirements for increasing the Furthermore, as in Example 2 above, by changing the longitudinal direction of the alloy ribbon forming each amorphous alloy thin plate layer and shielding magnetic lines of force in each direction, the magnetic shielding effect of the molded product can be further enhanced. . Therefore, the molded product manufactured by the method of the present invention had several times the shielding effect and much higher rigidity than the conventional magnetic shield material molded product woven from an amorphous alloy. Furthermore, the molded product manufactured by the method of the present invention can have a magnetic shielding effect and an electromagnetic shielding effect if a low-resistance metal material that has an electromagnetic shielding effect is used in combination with the amorphous alloy and thermoplastic resin. It can be made into a molded product that has both. As explained above, the present invention provides an easy method for obtaining molded products that take advantage of the characteristics of amorphous alloys, and the molded products obtained by this method can be used in various fields such as magnetic shielding parts. It is an excellent molded product that can be applied.

[Brief explanation of the drawing]

Fig. 1 is a diagram showing the laminated state of the laminate of Test Example 1, Fig. 2 is a diagram showing the laminated state of the laminate of Test Example 2, and Fig. 3 A, B, and C are of the molded product of Example 1. An explanatory view of the molding process, FIG. 3D is a perspective view of the molded product of Example 1, and FIG. 4 is a diagram showing the laminated state of the laminated plates used for manufacturing the molded product of Example 2. 1... Thermoplastic resin film, 2... Amorphous alloy thin plate, 3
...a set of laminates, 4...mold, 5...molded product.

Claims (1)

[Claims] 1. Laminating at least one layer of an amorphous alloy thin plate of a predetermined size and a thermoplastic resin film, and shaping the resulting laminate into a predetermined shape at a temperature above the softening temperature and below the melting point of the resin. molding, and then at a temperature above the melting point of the resin and below the crystallization temperature of the amorphous alloy.
A method for producing a laminate molded product, which comprises holding and fusing under a pressure of 0.1 to 5 kg/cm ² . 2 A predetermined number of amorphous alloy ribbons arranged in the width direction of the ribbons are used as the thin plates of the amorphous alloy, and the longitudinal directions of the ribbons of the thin plates are overlapped vertically with a thermoplastic resin film in between. 2. A method as claimed in claim 1, in which orthogonality is achieved. 3. The method according to claim 1, wherein the amorphous alloy thin plate and the thermoplastic resin film are laminated by applying a thermoplastic resin dissolved or dispersed in a solvent or a dispersant to the amorphous alloy thin plate. . 4 A thin plate of an amorphous alloy of a predetermined size and at least one layer of a thermoplastic resin film are laminated, and the resulting laminate is heated at a temperature of 0.1 or higher than the melting point of the resin and lower than the crystallization temperature of the amorphous alloy. After fusing by holding under pressure of 5 kg/cm 2 to 5 kg/cm ² , the molded product is molded into a predetermined shape at a temperature higher than the softening point of the resin and lower than the melting point, and the molded product is heated again to a temperature higher than the melting point of the resin and higher than the above non-containing temperature. 0.1 to 5 kg/at a temperature below the crystallization temperature of the crystalline alloy
A method for producing a laminate molded product, which comprises holding the product under pressure of cm ² for 1 to 10 minutes to fuse it. 5 A predetermined number of amorphous alloy ribbons arranged in the width direction of the ribbons are used as thin plates of amorphous alloy, and the longitudinal direction of the ribbons of the thin plates that overlap vertically through a thermoplastic resin film is mutually aligned. 5. A method as claimed in claim 4 in which orthogonality is achieved. 6. The method according to claim 4, wherein the amorphous alloy thin plate and the thermoplastic resin film are laminated by coating the amorphous alloy thin plate with a thermoplastic resin dissolved or dispersed in a solvent or a dispersant. .