JPWO2014091632A1 - Method for manufacturing electrode material for thermal fuse - Google Patents

Abstract

The present invention relates to a thermal fuse electrode material using a clad material formed by joining two or more kinds of metal materials having different properties, and a method of manufacturing the same. A multi-layer clad wire is formed by using a wire made of Cu or Cu alloy as a base material, fitting a pipe made of an Ag-Cu alloy and a pipe made of a bonding layer to the base material, and applying clad processing and plastic processing. Alternatively, a multi-layer clad material is subjected to internal oxidation treatment and plastic processing to form a thin plate, thereby having an internal oxide layer on both front and back surfaces of the thin plate, and an Ag—Cu alloy layer on both front and back surfaces of the substrate layer Or an electrode material for a thermal fuse having a multilayer structure in which an Ag—Cu alloy layer alloy and a bonding layer are formed.

Description

  TECHNICAL FIELD The present invention relates to an electrode material for a thermal fuse to be attached to an electronic device or an electric appliance for home appliances in order to prevent those devices from becoming abnormally high temperature, and a method for manufacturing the same.

  A thermal fuse that is installed to prevent electronic and electrical equipment from becoming extremely hot is that the temperature-sensitive pellet melts at the operating temperature, unloads the force of the strong compression spring, and the strong compression spring extends. As a result, the electrode material and the lead wire that are in pressure contact with each other by the strong compression spring are separated from each other to interrupt the current.

  As an electrode material used for this thermal fuse, an Ag-oxide alloy is becoming mainstream (for example, Patent Document 1 and Patent Document 2).

  The electrode material is a thin plate of 0.1 mm or less due to the thermal fuse mechanism, and the contact surface with the lead wire is kept energized for a long time, so it is welded to the lead wire or metal case. Phenomenon easily occurs, and welding resistance is required as a material property. In recent years, there has been a demand for a reduction in the material price of Ag-oxide alloys.

  This demand for welding resistance and material cost reduction can be addressed by increasing the oxide content in the Ag-oxide alloy and decreasing the Ag content.

  However, with an increase in oxide, the Ag-oxide alloy has a marked reduction in rolling workability, making it difficult to process into a thin plate in the rolling step after internal oxidation.

Japanese Patent Laid-Open No. 10-162704 Japanese Patent No. 4383859

  Recently, the content of Ag, which is an expensive noble metal, has been reduced for the purpose of further reducing the material price while maintaining various characteristics such as welding resistance, low contact resistance and workability required for electrode materials for thermal fuses. Further reduction is required.

  However, in the conventional manufacturing method, as the Cu content in the Ag-Cu alloy approaches 50 mass%, the contact resistance increases and the conductivity deteriorates as the oxide content increases. It rises and becomes unsuitable for electrode materials for thermal fuses. For this reason, it was difficult to further reduce the material price by reducing the Ag content in the Ag—Cu alloy.

  Moreover, since the internal oxide layer is hard to contain oxides, the rolling processability is poor, and it is necessary to reduce the oxide content in order to improve the rolling processability.

  An object of the present invention is to solve such a problem.

  Therefore, in the present invention, a substrate layer and an Ag—Cu alloy layer are formed by forming a multilayer structure having Ag—Cu alloy plates on both front and back surfaces in the longitudinal direction of a substrate made of Cu or Cu alloy. By applying the treatment, the above problem was solved by using a thermal fuse electrode material having a multilayer structure in which an internal oxide layer was formed on the surface layer of the Ag-Cu alloy layer. In order to further improve the bonding strength, a bonding layer capable of improving the bonding strength may be provided as necessary at the interface between the substrate layer and the Ag—Cu alloy layer.

  The thermal fuse electrode material having a multilayer structure as described above allows the material cost to be further reduced as compared with the conventional manufacturing method because the inexpensive substrate layer that occupies most of the material does not contain Ag. Further, since the substrate layer is rich in workability, it has succeeded in improving workability when rolling the material after internal oxidation while maintaining the oxide content in the internal oxide layer.

  As the composition of each layer, pure Cu containing inevitable impurities is preferable in the substrate layer, but for the purpose of improving heat resistance, conductivity or mechanical properties, Ti, Cr, Be, Si, Fe, Co, Zr Cu alloy containing at least one of Zn, Sn, Ni, P, and Pb may be used.

  The Ag-Cu alloy plate contains 1 to 50% by mass of Cu and the balance contains Ag and inevitable impurities, or contains 1 to 50% by mass of Cu, and further includes Sn, In, Ti, Fe, Ni and Co. An alloy containing 0.01 to 5% by mass of at least one selected from the group consisting of Ag and inevitable impurities is preferable.

  Here, the reason why the addition amount of Cu in the Ag-Cu alloy is set to 1 to 50% by mass is that, after the internal oxidation treatment, if the Cu content is less than 1% by mass, the oxide is insufficient and the thermal fuse is used. This is because welding resistance sufficient for use as an electrode material cannot be obtained. When the Cu content exceeds 50% by mass, the workability of the internal oxide layer is remarkably lowered due to an increase in the oxide content, Cracks are likely to occur in the internal oxide layer. Furthermore, even if oxygen is allowed to penetrate into the metal layer by internal oxidation treatment, oxygen is mainly bonded to Cu to form an oxide film near the surface, and oxide particles are dispersed in the metal layer. It becomes difficult to let you.

  As the bonding layer, pure Ag containing inevitable impurities or an alloy containing 0.01 to 28% by weight of Cu and the balance containing Ag and inevitable impurities is most preferable. Any metal material may be used as long as it has appropriate bondability, such as noble metals such as Au, Mg, Cr, Sn, In, Ti, Fe, Ni or Co.

  This bonding layer improves the bondability between the substrate layer and the Ag—Cu alloy layer, and prevents peeling due to a difference in elongation during processing, vibration or impact. In order to further improve the bonding property, in at least one of the substrate layer, the bonding layer, and the Ag—Cu alloy layer, a part of the constituent components may be diffused or alloyed to other adjacent layers by heat treatment. Further, this bonding layer is subjected to an internal oxidation process on the surface layer of the bonding layer during the internal oxidation process, and oxygen enters the substrate layer and Cu is oxidized until immediately before the adjacent substrate layer is subjected to the internal oxidation process. It also has a function of preventing peeling of the internal oxide layer that may be caused by this.

  Here, the reason why the added amount of Cu contained in the alloy of the bonding layer is 0.01 to 28% by mass is that when the Cu content exceeds 28% by mass, the bonding property to the adjacent plate material is preferable. This is because there is not. Although depending on the internal oxidation conditions, the bonding layer in which the Cu content exceeds 28% by mass is more oxygenated during the internal oxidation treatment than the bonding layer in which the Cu content is 28% by mass or less. It has a high function of preventing peeling of the internal oxide layer that may be caused by Cu entering and oxidizing Cu.

  As a manufacturing method of the temperature fuse electrode material according to the present invention, a pipe cladding method is preferable. In the pipe clad method, a wire material serving as a substrate layer is covered with an outer tube constituting an Ag-Cu alloy layer or a joining layer, and these are joined by hot wire drawing to form a linear shape composed of a plurality of the various layers. This is a method of forming a multilayer structure material.

  The linear multilayered structural material is processed into a plate shape by rolling. Then, an internal oxidation layer is formed in the surface layer of the Ag-Cu alloy layer of both front and back surfaces of a plate-shaped multilayer structure material by performing an internal oxidation treatment. The linear multi-layer structure material may be processed into a plate shape by rolling after forming an internal oxide layer on the surface layer of the Ag—Cu alloy layer by performing internal oxidation treatment while maintaining the linear shape.

  Alternatively, the outer tube constituting the Ag-Cu alloy layer in which the internal oxidation layer is formed by performing the internal oxidation treatment in advance on the wire to be the substrate layer and the outer tube constituting the bonding layer as necessary are covered. May be joined by hot wire drawing to form a linear multilayered structure material composed of a plurality of the various layers, and then processed into a plate shape by rolling.

  As another manufacturing method of the multilayer structure material, a plating method or a sputtering method is preferable. The plating method is a method of performing electrolysis or electroless plating on a substrate layer using a plating solution containing a metal salt constituting an Ag—Cu alloy layer or a bonding layer. In the sputtering method, a thin film is formed on a substrate layer using a target material constituting an Ag—Cu alloy layer or a bonding layer and, if necessary, an oxygen atmosphere.

  Further, other examples of the manufacturing method of the multilayer structure material include plasma spraying, gas spraying, high-speed flame spraying, laminating by spraying such as a cold spray method, intermittent discharge in the air or liquid, pulse, etc. There are a stacking by discharge, and a stacking by vapor deposition such as PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition).

  The method for manufacturing the thermal fuse electrode material according to the present invention may be a method combining the above manufacturing methods. For example, the substrate layer may be a material central portion, both surfaces may be clad, and the bonding layer may be plated.

  The internal oxidation treatment is a process in which, in the Ag—Cu alloy layer, Cu previously contained in the Ag matrix is precipitated as an oxide in the Ag matrix by being combined with oxygen stored in the Ag matrix from the material surface layer. Take. At this time, Cu, which is a solute element, diffuses from the material inside the Ag—Cu alloy layer toward the surface layer. In addition, the definition of the surface layer said by this invention means the range below the total thickness of an Ag-Cu alloy layer and a joining layer from the material surface.

  The phenomenon in which the solute element diffuses from the inside of the material toward the surface layer is caused by the internal oxide layer formed by the oxide precipitated from the material surface of the Ag-Cu alloy layer toward the inside, and the precipitation over time. This is a phenomenon in which a difference in Cu concentration occurs between the unoxidized layer and the non-oxidized layer, and Cu diffuses from the unoxidized layer toward the surface layer in order to fill the concentration gradient. For this reason, oxygen is always supplied in excess of the amount of oxygen necessary for the oxidation of other elements in the Ag matrix.

  In the diffusion process, by adding at least one selected from the group of Sn, In, Ti, Fe, Ni, and Co in the Ag-Cu alloy layer, the diffusion phenomenon due to the concentration gradient is suppressed, As a result, by suppressing the aggregation due to the movement of the deposited oxide, the oxide structure is made finer and a uniform dispersion can be obtained. Furthermore, it becomes a complex oxide with Cu, for example, (Cu-Sn) Ox, and has an effect of improving the welding resistance.

  Here, in the Ag-Cu alloy layer, the reason why at least one of Sn, In, Ti, Fe, Ni, or Co is 0.01 to 5% by mass is that when the content is less than 0.01% by mass, internal oxidation is performed. This is because the movement of the solute element during the treatment cannot be sufficiently suppressed, and a uniform dispersion of the oxide cannot be obtained. If the amount exceeds 5% by mass, a coarse oxide is formed at the grain boundary and the contact resistance is increased. It is for inviting.

  The present invention is characterized in that, in this internal oxidation treatment, only the surface layers on both the front and back surfaces of the material have an internal oxide structure, and the internal oxidation conditions for this are set at 500 ° C. in an internal oxidation furnace at a desired plate thickness. It is adjusted under the conditions of ˜750 ° C., 0.25 hours or more, and oxygen partial pressure of 0.1 to 2 MPa. As a result, an internal oxide layer can be formed on the front and back surfaces of the material, and a substrate layer can be formed at the center of the material. The average particle diameter of the oxide particles dispersed in the internal oxide layer is 0.5 to 5 μm, preferably 1 to 4 μm, and more preferably 2 to 3 μm. When the average particle size of the oxide particles is less than 0.5 μm, the oxide particles are fine at the contact portion between the lead wire and the movable electrode, so that the oxide particles are easily welded. On the other hand, the average particle size of the oxide particles is 5 μm. If it is larger, the contact resistance becomes higher, so that welding becomes easier.

  The oxygen partial pressure during the internal oxidation treatment is important for adjusting the average particle size of the oxide particles to 0.5 to 5 μm. The oxygen partial pressure during the internal oxidation treatment under internal oxidation conditions is preferably 0.1 to 2 MPa. That is, when the oxygen partial pressure is less than 0.1 MPa, it is difficult to form the internal oxide layer uniformly, the average particle size of the oxide particles is greater than 5 μm, and when the oxygen partial pressure is greater than 2 MPa, The average particle size becomes less than 0.5 μm, and it becomes easy to weld as described above.

  As described above, the temperature during the internal oxidation treatment is preferably 500 ° C. to 750 ° C. When the temperature is lower than 500 ° C., the oxidation reaction does not proceed sufficiently. On the other hand, when the temperature is higher than 750 ° C., it becomes difficult to control the thickness of the internal oxide layer and the size of the oxide particles.

  The time of the internal oxidation treatment includes the target internal oxide layer thickness, unoxidized layer thickness, Ag—Cu alloy composition, bonding layer and Ag—Cu alloy layer thickness, and the aforementioned internal oxidation temperature. It is necessary to adjust appropriately according to the oxygen partial pressure.

  Although it depends on the thickness of the target internal oxide layer, it is preferably 0.25 hours or longer. That is, when the internal oxidation time is less than 0.25 hours, it is difficult to form the internal oxide layer uniformly. If the internal oxidation time is less than 0.25 hours, it is difficult to form the internal oxide layer uniformly and sufficiently, and there is a risk of causing a welding phenomenon with the lead wire or the metal case when used as an electrode material for a thermal fuse. is there. There is no particular upper limit to the internal oxidation time, and the thickness of the internal oxide layer increases in proportion to the increase in internal oxidation time. However, if the substrate layer is internally oxidized, each layer may be peeled off. Therefore, the ratio of the layer thickness of the Ag-Cu alloy layer or the bonding layer to the substrate layer should be increased so that the substrate layer is not subjected to internal oxidation treatment. In addition, it is necessary to insert an internal oxidation treatment in a state where the multilayer structure material is thick. Alternatively, a layer for preventing oxidation may be provided at the interface with the substrate layer.

  In addition, the temperature, pressure, and time of internal oxidation are correlated with each other. For example, in order to shorten the internal oxidation time in a short time, the temperature and pressure are increased and adjusted. It is necessary to select a proper condition.

  The electrode material for the thermal fuse has various component compositions and various final plate thicknesses depending on the use application of the thermal fuse, but a thin plate material of 0.1 mm or less is used because of the mechanism of the thermal fuse. However, since it is difficult to uniformly perform the internal oxidation treatment on the thin plate material and it is difficult to uniformly clad the thin plate material, it is necessary to thin the material after the internal oxidation by rolling. In addition, in the material after internal oxidation, when workability is poor and cracks and breaks during rolling, cracks in the internal oxide layer, and the like occur, shearing or heat treatment may be performed as necessary. Or you may wire-draw the material after internal oxidation to a thin plate material with a deformed die.

  As a difference from the conventional manufacturing method in the rolling process and annealing process after internal oxidation of the present invention, by providing a substrate layer made of Cu or Cu alloy with high workability at the center part of the electrode material for the thermal fuse, It was possible to greatly improve the rolling processability without reducing the oxide content of the internal oxide layer, and succeeded in rolling with a reduction rate of 80% or more in cross-section reduction rate. Furthermore, by providing a workable substrate layer, it is possible to improve the workability of various other layers that are relatively inferior with a single layer. The sheet material was successfully rolled to a thin sheet material of 0.1 mm or less while maintaining the ratio and the multilayer structure.

  According to the electrode material of the present invention, even if the content of Ag is decreased by increasing the Cu content in the Ag-Cu alloy layer to 50% by mass and increasing the oxide content after the internal oxidation treatment, In the processing after the internal oxidation, it is possible to perform a rolling process with a cross-section reduction rate of 80% or more.

  In other words, compared to conventional electrode materials for thermal fuses, the internal oxide layer having a sufficient thickness on both the front and back surfaces of the electrode material and a substrate layer mainly composed of Cu at the center of the material are provided. Workability can be greatly improved without reducing the oxide content of the oxide layer. As a result, it is possible to provide a temperature fuse electrode material having stable quality and high reliability. In addition, by arbitrarily changing the material of the substrate at the center of the material, an electrode material for thermal fuse that adjusts heat resistance, conductivity, mechanical properties, etc. to desired characteristics while maintaining welding resistance It becomes possible to provide.

  Furthermore, it is possible to provide an inexpensive thermal fuse electrode material that can greatly reduce the amount of Ag and the like while maintaining various characteristics such as welding resistance and low contact resistance required for the thermal fuse electrode material. Is possible.

Explanatory drawing which shows the front direction cross section of the two-layer clad wire in Manufacturing Method 1 and Manufacturing Method 5 Explanatory drawing which shows the longitudinal direction cross section of the 3 layer clad board in the manufacturing method 1 and the manufacturing method 5 Explanatory drawing which shows the longitudinal cross section of the multilayer clad board after the internal oxidation process in the manufacturing method 1 and the manufacturing method 5 Explanatory drawing which shows the front direction cross section of the 3 layer clad line in the manufacturing method 2 and the manufacturing method 6 Explanatory drawing which shows the longitudinal cross section of the 5-layer clad board in the manufacturing method 2 and the manufacturing method 6 Explanatory drawing which shows the longitudinal direction cross section of the multilayer clad board in the manufacturing method 2 and the manufacturing method 6 Explanatory drawing which shows the front direction cross section of the two-layer clad wire after the internal oxidation process in Manufacturing Method 3 and Manufacturing Method 7 Explanatory drawing which shows the front direction cross section of the three-layer clad line after the internal oxidation process in Manufacturing Method 4 and Manufacturing Method 8 Explanatory drawing which shows the longitudinal direction cross section of the Ag-oxide alloy plate in a comparative example

  Examples of the present invention are shown in Tables 1 to 4, and a method for manufacturing these thermal fuse electrode materials will be described. In addition, an Example and a comparative example are electrode material kind No .. Table 2 is shown in a format corresponding to Table 1, and Table 4 is shown in a format corresponding to Table 3.

  Specifically, the component composition contained in the Ag—Cu alloy pipe and the joining pipe of the production methods 1 to 8 of the present invention is shown in Table 1, and the Ag—Cu alloy pipe and the joint pipe of the production methods 3 to 4 of the present invention are used. The component composition contained is listed in Table 3. Moreover, the component composition contained in the Ag-Cu alloy pipe of a comparative example is written together in Table 1 and Table 3. Corresponding to Table 1 or Table 3, internal oxidation temperature, internal oxidation time, oxygen partial pressure, average particle size of oxide, workability of rolling after internal oxidation treatment and after clad processing, electrode material for thermal fuse Table 2 or Table 4 shows the final plate thickness and the final processing rate. As an evaluation method for each item described in Tables 1 to 4, the component composition contained in the Ag-Cu alloy pipe and the joining pipe is quantitatively analyzed using a wavelength dispersive electron microscope and an ICP emission analyzer. The remaining Ag and inevitable impurities are described as remaining. In addition, the inevitable impurities described in the examples of the present invention indicate impurities having a content of less than 0.01% by mass.

  Bondability is determined by performing an adhesion bending test on each clad plate obtained by the manufacturing methods 1 to 8 after the complete annealing according to the pressing method defined in JIS Z 2248, after bending 180 °, and cracking the curved portion. Bondability was evaluated by the presence or absence of peeling. The case where cracks and peeling were observed in the curved portion was evaluated as x, and the case where cracks and separation were not observed in the curved portion and excellent in bondability was evaluated as ◯. In addition, even if evaluation of bondability is x, if the following evaluation of workability is AC and evaluation of other evaluation items is ◯, it can be suitably used as a movable electrode for a thermal fuse.

  Bending workability (bondability) is determined by fixing a test piece of various electrode materials processed to the final plate thickness by each manufacturing method and then performing a 90 ° repeated bending test until the test piece is cracked. The number of bends was measured, and the bondability was evaluated based on the number of bends. The number of bending was 10 times or more was evaluated as A, the number of 4 times or more and less than 10 times was evaluated as B, and the case of 2 times or more and less than 4 times was evaluated as C. In addition, when processing into a movable electrode having a predetermined shape, bending is performed once by pressing, but if the evaluation is A to C, the movable electrode can be processed with sufficient reliability. In any of the production methods of the present invention, the obtained movable electrode material did not cause interfacial delamination between layers, and was broken at the substrate layer to obtain a movable electrode material having extremely good bonding properties. .

  The workability was evaluated as “◯” when the final processing rate in the final thickness before the hardness adjustment by heat treatment was cold-rolled to 80% or more in terms of the cross-sectional reduction rate, and “×” when it was not possible. Reasons for evaluation x include cracks and breaks during rolling, cracks in the internal oxide layer, and the like. In any of the production methods of the present invention, good workability was obtained as compared with the comparative example. Furthermore, in manufacturing methods 1 to 4, oxygen-free Cu was used for the substrate layer, and in manufacturing methods 5 to 8, a Cu alloy was used for the substrate layer, but no difference in workability was observed.

  The average particle size of the oxide particles was measured at 1000 times the cross section of the movable electrode material for the thermal fuse with a metal microscope. The average particle size is 0. In the range of 5 to 5 μm, the average particle size is 0. The thing outside the range of 5-5 micrometers was evaluated as x. In addition, in any internal oxidation conditions of the present invention, a good average oxide particle size was obtained.

Comparative Example As a comparative example, an internal oxidation treatment was performed on an Ag—Cu alloy plate having a thickness of 0.5 mm in an internal oxidation furnace under conditions of 500 ° C. to 750 ° C. for 48 hours and an oxygen partial pressure of 0.1 to 2 MPa. An Ag-oxide alloy plate 7 (FIG. 9) in which an inner oxide layer 4 containing an oxide on both surface layers and an oxide dilute layer 8 in the middle layer portion was formed, and after complete annealing, the final thickness (0 .1 mm or less), the electrode material type no. Details of 41 to 47 are also shown in Tables 1 to 4. The reason why the internal oxidation time of the comparative example is unified to 48 hours is that the oxide thin layer 8 can be reliably formed in the thickness of the Ag-Cu alloy plate of the comparative example.

  The definition of the diluted oxide layer 8 in the comparative example is located at the center of the longitudinal cross section of the Ag-Cu alloy plate subjected to the internal oxidation treatment, the oxide content is lower than 1% by mass, and the cross-sectional ratio Means a layer in the range of 10% or less.

Manufacturing method 1
Examples according to this production method are shown in Tables 1 and 2. An oxygen-free Cu containing an Ag—Cu alloy of each desired composition and inevitable impurities corresponding to the electrode material types No. 1 to 40 was prepared by a melting method. After subjecting the Ag—Cu alloy to rolling, an Ag—Cu alloy pipe (outer diameter φ36, inner diameter φ33) to be the Ag—Cu alloy layer 1 was obtained by pipe welding and tube drawing. The oxygen-free Cu was subjected to extrusion processing and wire drawing processing to obtain a core material (outer diameter φ32) to be the substrate layer 2. Thereafter, the core material is subjected to surface treatment, and the core material to be the substrate layer 2 is inserted into the Ag—Cu alloy pipe to be the Ag—Cu alloy layer 1, which is subjected to hot wire drawing and heat treatment to form two layers. A clad wire (outer diameter φ29) was obtained (FIG. 1). As conditions for the hot wire drawing, the temperature of the material was adjusted to 400 ° C. when the Ag—Cu alloy pipe and the core material passed through the die. The reason for fixing the temperature to 400 ° C. is to align the test conditions, and a range of 200 to 750 ° C. is preferable.

  The two-layer clad wire was subjected to cold drawing, cold rolling, shearing and heat treatment to obtain a three-layer clad plate having a thickness of 0.5 mm (FIG. 2).

  The three-layer clad plate was subjected to internal oxidation treatment in an internal oxidation furnace under the conditions of 500 ° C. to 750 ° C., 0.25 to 36 hours, and oxygen partial pressure of 0.1 to 2 MPa. At this time, conditions are selected within the above ranges depending on the composition and thickness of each layer, the internal oxide layer 4 containing the oxide 3 is formed on the front and back surfaces of the three-layer clad plate, and the unoxidized layer is formed in the middle layer portion. 5. A multi-layer structure (FIG. 3) having a substrate layer 2 at the center of the material is provided.

  Next, in order to make the test conditions uniform, the above-mentioned three-layer clad plate after internal oxidation is completely annealed and then cold-rolled with the multilayer structure shown in FIG. The electrode material for thermal fuses was produced.

Manufacturing method 2
Examples according to this production method are shown in Tables 1 and 2. Alloys having desired compositions to be the bonding layers 6 corresponding to the electrode material types No. 1 to 40 were produced by a melting method. The alloy having a desired composition to be the joining layer 6 was subjected to rolling, and then joined pipes (outer diameter φ36, inner diameter φ33) to be the joining layer 6 by pipe welding and tube drawing. Furthermore, it becomes Ag-Cu alloy pipes (outer diameter φ36, inner diameter φ33) and substrate layer 2 having the same composition and the same dimensions for the electrode material types No. 1 to 40 by the same manufacturing method as in manufacturing method example 1. A core material (outer diameter φ32) was obtained.

  Next, surface treatment is performed, a core material to be the substrate layer 2 is inserted into a joining pipe to be the joining layer 6, and hot drawing and heat treatment are performed on this to obtain a two-layer clad wire (outer diameter φ29). (FIG. 4). The conditions for the hot wire drawing were the same as those in Production Method Example 1 except that the Ag—Cu alloy pipe was replaced with a joined pipe.

  Thereafter, surface treatment was performed, and the two-layer clad wire was inserted into the Ag-Cu alloy pipe, and these were subjected to hot wire drawing and heat treatment to obtain a three-layer clad wire (outer diameter φ29) (FIG. 5). ). The conditions for hot wire drawing were the same as those in Production Method Example 1 except that the core material was replaced with a two-layer clad wire.

  The three-layer clad wire is subjected to cold drawing, cold rolling, shearing, and heat treatment, the plate thickness is 0.5 mm, and the bonding layer 6 and Ag- A multilayered five-layer clad plate (FIG. 6) having a Cu alloy layer 1 was formed.

  The 5-layer clad plate was subjected to internal oxidation treatment under the same conditions as in Production Method Example 1. At this time, conditions are selected within the above ranges depending on the composition and layer thickness in each layer, the internal oxide layer 4 containing oxide 3 is formed on the front and back surfaces of the five-layer clad plate, and the unoxidized layer is formed in the middle layer portion. 5. A multilayer structure (FIG. 7) having a substrate layer 2 at the center of the material and a bonding layer 6 at the bonding interface between the unoxidized layer 5 and the substrate layer 2 is provided.

  Next, in order to make the test conditions uniform, the above-mentioned internally oxidized 5-layer clad plate is completely annealed and then cold-rolled with the multilayer structure shown in FIG. The electrode material for thermal fuses was produced.

Manufacturing method 3
Examples according to this production method are shown in Tables 1 and 2. A two-layer clad wire produced under the same conditions as in Production Method Example 1 was subjected to internal oxidation under the same conditions as in Example 1. At this time, conditions are selected within the above ranges depending on the composition and layer thickness of each layer, an internal oxide layer 4 containing oxide 3 is formed on the surface layer of the two cladding lines, an unoxidized layer 5 is formed in the middle layer, and the material center A multi-layer structure (FIG. 8) having the substrate layer 2 in the part is provided. These were repeatedly subjected to wire drawing, rolling, shearing, and heat treatment to have a plate thickness of 0.5 mm and a multilayer structure similar to that of Example 1 (FIG. 3).

  Then, after complete annealing in order to make the test conditions uniform, cold rolling was performed while maintaining the multilayer structure, and the final plate thickness was processed to 0.1 mm or less to produce a thermal fuse electrode material.

Manufacturing method 4
Examples according to this production method are shown in Tables 1 and 2. A three-layer clad wire manufactured under the same conditions as in manufacturing method 2 was subjected to internal oxidation under the same conditions as in manufacturing method example 1. At this time, conditions are selected within the above ranges depending on the composition and layer thickness of each layer, the internal oxide layer 4 containing the oxide 3 is formed on the surface layer of the three-layer clad wire, the unoxidized layer 5 and the material in the middle layer portion A multilayer structure (FIG. 9) having the substrate layer 2 in the center and the bonding layer 6 at the bonding interface between the unoxidized layer 5 and the substrate layer 2 is provided.

  These were repeatedly subjected to wire drawing, rolling, shearing, and heat treatment to have a plate thickness of 0.5 mm and a multilayer structure similar to that of Example 2 (FIG. 6). Then, cold rolling was performed with the multilayer structure, and the final plate thickness was processed to 0.1 mm or less to produce a thermal fuse electrode material.

Manufacturing method 5
Examples according to this production method are shown in Tables 3 and 4. A Cu alloy containing 0.2% by mass of Sn was prepared by a melting method. The Cu alloy was subjected to extrusion processing and wire drawing processing to obtain a core material (outer diameter φ32 mm) to be the substrate layer 2.

  Next, in the same manner as in Production Method Example 1 except that the core material is replaced with the above Cu alloy instead of oxygen-free Cu, it has the multilayer structure shown in FIG. 3 and the final thickness is 0.1 mm or less. An electrode material for a thermal fuse was prepared.

Manufacturing method 6
Examples according to this production method are shown in Tables 3 and 4. A Cu alloy containing 0.2% by mass of Sn was prepared by a melting method. The Cu alloy was subjected to extrusion processing and wire drawing processing to obtain a core material (outer diameter φ32 mm) to be the substrate layer 2.

  Next, in the same manner as in Production Method Example 2 except that the core material is replaced by the above Cu alloy instead of oxygen-free Cu, it has the multilayer structure shown in FIG. 7 and the final plate thickness is 0.1 mm or less. An electrode material for a thermal fuse was prepared.

Manufacturing method 7
Examples according to this production method are shown in Tables 3 and 4. A Cu alloy containing 0.2% by mass of Sn was prepared by a melting method. The Cu alloy was subjected to extrusion processing and wire drawing processing to obtain a core material (outer diameter φ32 mm) to be the substrate layer 2.

  Next, it has the multilayer structure shown in FIG. 3 and has a final thickness of 0.1 mm or less in the same manner as in Production Method Example 3 except that the core material is replaced with the above Cu alloy instead of oxygen-free Cu. An electrode material for a thermal fuse was prepared.

Manufacturing method 8
Examples according to this production method are shown in Tables 3 and 4. A Cu alloy containing 0.2% by mass of Sn was prepared by a melting method. The Cu alloy was subjected to extrusion processing and wire drawing processing to obtain a core material (outer diameter φ32 mm) to be the substrate layer 2.

  Next, in the same manner as in Production Method Example 4 except that the core material is replaced by the above Cu alloy instead of oxygen-free Cu, it has the multilayer structure shown in FIG. 7 and the final plate thickness is 0.1 mm or less. An electrode material for a thermal fuse was prepared.

  The thermal fuse electrode materials of the examples and comparative examples are adjusted to a desired hardness by heat treatment as necessary, and then processed into a movable electrode having a predetermined shape by pressing or the like, so that the temperature sensitive material is at the operating temperature. A typical commercially available temperature-sensitive pellet type thermal fuse that melts and unloads the compression spring, and when the compression spring is extended, the movable electrode pressed by the compression spring and the lead wire are separated to interrupt the current. Can be suitably used.

  Therefore, the temperature fuse electrode materials of the examples and comparative examples are adjusted to a desired hardness by heat treatment as necessary, and then processed into a movable electrode having a predetermined shape by pressing, and the movable electrode is subjected to a temperature sensitive pellet type temperature. Tables 2 and 4 show the results of conducting an energization test and a current interruption test with a fuse mounted, DC30V, 20A, and a heating rate of 1 ° C per minute.

  In the energization test, the temperature fuse was energized for 10 minutes, and the temperature difference on the surface of the metal case of the temperature fuse before and after the test was less than 10 ° C., and the temperature difference of 10 ° C. or more was evaluated as x.

  In the current interruption test, the temperature fuse is energized for 10 minutes, and then the temperature of the test environment is raised to a temperature 10 ° C higher than the operating temperature at a heating rate of 1 ° C per minute while energization continues. I tried to cut off the current. After the test, a case where the movable electrode and the lead wire were not welded, that is, a case where the current could be interrupted, was evaluated as ◯.

1 Ag-Cu alloy layer 2 Substrate layer 3 Oxide 4 Internal oxide layer 5 Non-oxidized layer 6 Bonding layer 7 Ag-oxide alloy plate 8 Oxide dilute layer

The present invention, in the electronic equipment and household appliances, a method of manufacturing the electrode materials for thermal fuse mounting for those devices can be prevented from an abnormal high temperature.

Install them thermal fuse for electronic and electrical equipment can be prevented from an abnormal high temperature,
The temperature-sensitive pellet melts at the operating temperature, unloads the force generated by the strong compression spring, and the strong compression spring expands, so that the electrode material pressed by the strong compression spring and the lead wire are separated from each other and the current flows. Is to shut off.

Manufacturing method 2
Examples according to this production method are shown in Tables 1 and 2. Alloys having desired compositions to be the bonding layers 6 corresponding to the electrode material types No. 1 to 40 were produced by a melting method. The alloy having a desired composition to be the joining layer 6 was subjected to rolling, and then joined pipes (outer diameter φ36, inner diameter φ33) to be the joining layer 6 by pipe welding and tube drawing. Furthermore, the electrode material kind No.1~40 each composition to the on, and the same dimensions Ag-Cu alloy pipe (outer diameter Fai36, an inner diameter φ33) and the substrate layer 2 by the same manufacturing method and manufacturing how 1 A core material (outer diameter φ32) was obtained.

Next, surface treatment is performed, a core material to be the substrate layer 2 is inserted into a joining pipe to be the joining layer 6, and hot drawing and heat treatment are performed on this to obtain a two-layer clad wire (outer diameter φ29). It was. The conditions for hot drawing, but substituting Ag-Cu alloy pipe joint pipe was prepared how 1 under the same conditions.

Thereafter, surface treatment was performed, and the two-layer clad wire was inserted into the Ag-Cu alloy pipe, and these were subjected to hot wire drawing and heat treatment to obtain a three-layer clad wire (outer diameter φ29) (FIG. 4 ). ). The conditions for hot drawing, but substituting core in two layers clad wire was prepared how 1 under the same conditions.

The three-layer clad wire is subjected to cold drawing, cold rolling, shearing, and heat treatment, the plate thickness is 0.5 mm, and the bonding layer 6 and Ag- A five-layer clad plate (FIG. 5 ) having a multilayer structure having the Cu alloy layer 1 was formed.

Was internal oxidation treatment under the same conditions the 5-layer clad plate and manufacturing how 1. At this time, conditions are selected within the above ranges depending on the composition and layer thickness in each layer, the internal oxide layer 4 containing oxide 3 is formed on the front and back surfaces of the five-layer clad plate, and the unoxidized layer is formed in the middle layer portion. 5. A multilayer structure (FIG. 6 ) having a substrate layer 2 at the center of the material and a bonding layer 6 at the bonding interface between the unoxidized layer 5 and the substrate layer 2 is provided.

Manufacturing method 3
Examples according to this production method are shown in Tables 1 and 2. Was internally oxidized in a two-layer clad wire produced under the same conditions as in Production how 1 Example 1 under the same conditions. At this time, conditions are selected within the above ranges depending on the composition and layer thickness in each layer, the internal oxide layer 4 containing the oxide 3 is formed on the surface layer of the two- layer clad wire, the unoxidized layer 5 and the material in the middle layer portion A multilayer structure (FIG. 7 ) having a substrate layer 2 at the center is provided. These were repeatedly subjected to wire drawing, rolling, shearing, and heat treatment to have a plate thickness of 0.5 mm and a multilayer structure similar to that of Example 1 (FIG. 3).

Production how 4
Examples according to this production method are shown in Tables 1 and 2. Was internally oxidized in three layers clad wire manufacturing how 1 the same condition manufactured under the same conditions as in Production Method 2. At this time, conditions are selected within the above ranges depending on the composition and layer thickness of each layer, the internal oxide layer 4 containing the oxide 3 is formed on the surface layer of the three-layer clad wire, the unoxidized layer 5 and the material in the middle layer portion A multilayer structure (FIG. 8 ) having a substrate layer 2 at the center and a bonding layer 6 at the bonding interface between the non-oxidized layer 5 and the substrate layer 2 is provided.

These were repeatedly subjected to wire drawing, rolling, shearing, and heat treatment so as to have a plate thickness of 0.5 mm and a multilayer structure similar to that in Production Method 2 (FIG. 6). Then, cold rolling was performed with the multilayer structure, and the final plate thickness was processed to 0.1 mm or less to produce a thermal fuse electrode material.

Then, except that the core material was replaced by the Cu alloy instead anoxic Cu in the same manner as in Production how 1, has a multi-layer structure shown in FIG. 3, and the final plate thickness is 0.1mm or less An electrode material for a thermal fuse was prepared.

Then, except that the core material was replaced by oxygen-free Cu, not the Cu alloy in the same manner it produced how 2 has a multi-layer structure shown in FIG. 6, and the final thickness is 0.1mm or less, An electrode material for a thermal fuse was prepared.

Then, except that the core material was replaced by the Cu alloy instead anoxic Cu in the same manner as in Production how 3 has the multilayer structure shown in FIG. 3, and the final plate thickness is 0.1mm or less An electrode material for a thermal fuse was prepared.

Then, except that the core material was replaced by free in oxygen Cu without the Cu alloy in the 4 same production how has a multilayer structure shown in FIG. 6, and the final thickness is 0.1mm or less, An electrode material for a thermal fuse was prepared.

Claims (10)

Temperature at which the temperature sensitive material melts at the operating temperature, unloads the force generated by the compression spring, and the compression spring expands, causing the movable electrode and the lead wire, which are pressed by the compression spring, to separate and cut off the current. In the manufacturing method of the electrode material of the fuse,
As a material of the movable electrode, a process of fitting and clad a pipe made of an Ag-Cu alloy to the outer peripheral surface of a linear base material to form a two-layer clad wire, and plastic working the two-layer clad wire A multi-layer clad plate in which an Ag—Cu alloy layer is formed on both the front and back surfaces of the substrate layer, and a multilayer in which an internal oxide layer is formed on the Ag-Cu alloy layer by subjecting the three-layer clad plate to internal oxidation treatment A method for producing an electrode material for a thermal fuse, comprising a step of forming a structure and a step of thinning by plastic working while having the multilayer structure. Temperature at which the temperature sensitive material melts at the operating temperature, unloads the force generated by the compression spring, and the compression spring expands, causing the movable electrode and the lead wire, which are pressed by the compression spring, to separate and cut off the current. In the manufacturing method of the electrode material of the fuse,
As a material of the movable electrode, a step of fitting and cladding a joining pipe to the outer peripheral surface of a linear base material to form a two-layer clad wire, and an Ag-Cu to the outer peripheral surface of the two-layer clad wire A process of fitting and cladding a pipe made of an alloy to form a three-layer clad wire, and forming a three-layer clad wire by plastic working has a bonding layer on both front and back surfaces of the substrate layer and is adjacent to the bonding layer. A step of forming a five-layer clad plate having a Cu alloy layer and an internal oxidation treatment on the five-layer clad plate, thereby internally oxidizing the Ag-Cu alloy layer or the Ag-Cu alloy layer and the bonding layer; The manufacturing method of the electrode material for thermal fuses including the process of setting it as the multilayered structure which formed the layer, and the process of forming into a thin plate by carrying out plastic working with the said multilayered structure.   A process of forming a multilayer structure in which an internal oxidation layer is formed on an Ag-Cu alloy layer by subjecting the two-layer clad wire according to claim 1 to an internal oxidation treatment, and forming a thin plate by plastic processing of the multilayer structure. A method for producing a thermal fuse electrode material, comprising the step of forming a multilayer structure similar to Item 1.   A process of forming a multilayer structure in which an internal oxidation layer is formed on an Ag-Cu alloy layer by subjecting the three-layer clad wire according to claim 2 to an internal oxidation treatment, and forming a thin plate by plastic processing of the multilayer structure. A method for producing a thermal fuse electrode material, comprising the step of forming a multilayer structure similar to Item 2.   5. The method according to claim 1, wherein the internal oxidation treatment is performed in an internal oxidation furnace under conditions of 500 ° C. to 750 ° C., 0.25 hours or more, and an oxygen partial pressure of 0.1 to 2 MPa. A method for producing an electrode material for a thermal fuse.   The temperature fuse electrode material according to claim 1 or 2, wherein the material of the substrate and the substrate layer is Cu or a Cu alloy.   3. The thermal fuse electrode material according to claim 1 or 2, wherein the composition of the Ag-Cu alloy layer is an alloy containing 1 to 50% by mass of Cu and the balance containing Ag and inevitable impurities. An electrode material for a thermal fuse characterized by the above.   3. The thermal fuse electrode material according to claim 1 or 2, wherein the composition of the Ag-Cu alloy layer contains 1 to 50 mass% of Cu, and Sn, In, Ti, Fe, Ni and Co. An electrode material for a thermal fuse, comprising 0.01 to 5% by mass of at least one selected from the group consisting of an alloy containing Ag and inevitable impurities.   3. An electrode material for a thermal fuse produced by the manufacturing method according to claim 2, wherein the composition of the bonding layer includes 0.01 to 28% by mass of Cu, and the balance includes Ag and inevitable impurities, or inevitable impurities. An electrode material for a thermal fuse, characterized by being pure Ag containing the same.   The electrode material for a thermal fuse according to the manufacturing method according to claim 1 or 2, wherein the surface layer of the Ag-Cu alloy layer subjected to the internal oxidation treatment or a part of the bonding layer subjected to the internal oxidation treatment and the Ag-Cu An electrode material for a thermal fuse, wherein the alloy layer has an internal oxide layer, and the remaining part on the adjacent substrate layer side has an unoxidized layer.