TW202208643A - Copper alloy ingot, copper alloy foil, and method of producing copper alloy ingot wherein the copper alloy ingot has a composition containing at least one additive element, Cu, and inevitable impurities - Google Patents

Abstract

An object of the present invention is to provide a copper alloy ingot with further improved uniformity of physical properties. The copper alloy ingot of the present invention has a composition containing at least one additive element, and the balance is composed of Cu and inevitable impurities. The at least one additive element is a trace element with a concentration of 10 to 50 quality ppm. The variation in the concentration of the trace element in the longitudinal direction is within the range of +/-3.5 quality ppm with respect to the average concentration of the trace element.

Description

Copper alloy ingot, copper alloy foil, and method for producing copper alloy ingot

The invention relates to a copper alloy ingot, a copper alloy foil and a manufacturing method of the copper alloy ingot.

Conventionally, in copper alloys, the physical properties of copper alloy rolled products (copper alloy foils, plates, etc.) produced from the added copper alloy ingots can be improved by adding copper or copper alloys to small amounts of additive elements. For example, Patent Document 1 discloses that, in order to obtain a copper alloy foil for a flexible printed circuit board having finer crystals and excellent bendability and etching properties, adding P, Ti, One or more additional elements selected from the group of Sn, Ni, Be, Zn, In, and Mg. prior art literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2017-141501

[Technical problem to be solved by invention]

Among them, for example, the above-mentioned copper alloy (microalloyed copper alloy) containing a small amount of additive elements can be obtained by: from a melting furnace for melting copper as a base material, and a copper molten material melted using the melting furnace, A small amount of additive elements are added while being supplied into the tundish furnace through a pipe, and the copper alloy is obtained in the form of, for example, an ingot by guiding it from the tundish furnace to a casting facility for casting (continuous casting). In addition, by producing the ingot in this manner, the base material can be uniformly contained in the additive element, and can be produced continuously and efficiently.

However, in recent years, in electronic products having copper alloy rolled products including copper alloy foils produced by rolling microalloyed copper alloy ingots as components, better performance has been demanded, and accordingly, A higher degree of uniformity of physical properties is required for the copper alloy foil and also for the ingot.

Therefore, in one Embodiment of this invention, the objective is to provide the manufacturing method of a copper alloy ingot, a copper alloy foil, and a copper alloy ingot whose physical property uniformity is further improved.

[Methods for solving technical problems]

In one embodiment, the copper alloy ingot of the present invention has a composition containing at least one additive element in a concentration of 10 to 50 mass ppm, the balance being composed of Cu and unavoidable impurities For trace elements, the deviation of the concentration of the trace elements in the longitudinal direction is within a range of ±3.5 mass ppm with respect to the average concentration of the trace elements.

In one Embodiment, the copper alloy foil of this invention is obtained by rolling from the above-mentioned copper alloy ingot.

In one embodiment, the method for producing a copper alloy ingot of the present invention is the method for producing the above-mentioned copper alloy ingot, which includes adding a molten copper material containing Cu to the molten copper material while flowing in one direction. In the step of adding trace elements, when the required concentration of the trace elements in the copper alloy ingot is denoted as concentration D, in the step of adding, adjusting the trace elements within 1 second The addition amount M1 of the trace element is adjusted to be less than twice the theoretical addition amount M2 of the trace element per second, and the theoretical addition amount M2 is the concentration D and the copper molten material flowing in one direction per 1 The flow F in seconds is calculated.

[Effect of invention]

According to the present invention, it is possible to provide a copper alloy ingot, a copper alloy foil, and a method for producing a copper alloy ingot in which the uniformity of physical properties is further improved.

Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail, but the present invention is not limited to this embodiment.

The copper alloy ingot of the present embodiment is a dilute copper alloy ingot, and has a composition containing at least one additive element and the balance consisting of Cu and unavoidable impurities, and the at least one additive element is For the trace elements (dilute elements) with a concentration of 10 to 50 mass ppm, the variation in the concentration of the trace elements in the longitudinal direction is within a range of ±3.5 mass ppm with respect to the average concentration of the trace elements. The copper alloy ingot of the present embodiment is not particularly limited, and can be used for the production of copper alloy rolled products (for example, copper alloy sheets and foils) in a rolling step. Moreover, the copper alloy foil manufactured from this ingot can be used for the use of a flexible printed circuit board, for example.

The copper alloy ingot of the present embodiment (hereinafter, simply referred to as "ingot") can have a high degree of homogenization of physical properties by having the above-mentioned composition.

More specifically, since the ingot of the present embodiment contains trace elements at a concentration of 10 to 50 ppm by mass, for example, when processing is performed in a rolling step, the crystal grains in the composition can be appropriately refined, and the A copper alloy rolled product having strength and high bending resistance was obtained.

In addition, in the case of using as a copper alloy rolled product, the user may perform heat treatment on the copper alloy rolled product during use (for example, in the case of copper alloy foil, when the copper alloy foil and resin are laminated heat treatment, etc.), by making the variation of the concentration of the trace elements in the longitudinal direction of the ingot within the range of ±3.5 mass ppm relative to the average concentration of the trace elements, recrystallization can be appropriately performed after the heat treatment.

That is, the user of the copper alloy rolled product produced from the ingot usually sets the copper alloy rolled product to be used on the basis of a certain part of the copper alloy rolled product (for example, the part where the trace element is the average concentration). Overall heat treatment conditions. However, when the concentration of trace elements exceeds the upper limit or falls below the lower limit in a certain part of the copper alloy rolled product in the longitudinal direction, it is difficult for that part of the copper alloy rolled product to fully comply with the regulations. heat treatment conditions. As a result, when the concentration exceeds the upper limit, recrystallization hardly occurs, and when the concentration is lower than the lower limit, the recrystallized grains become coarse.

Therefore, by making the variation of the concentration of the trace elements in the longitudinal direction of the ingot within a range of ±3.5 mass ppm with respect to the average concentration of the trace elements, for example, in the copper alloy rolled product produced from the ingot, the copper alloy can be Since the unevenness of physical properties in the longitudinal direction of the rolled alloy product becomes sufficiently small, when a user performs heat treatment under predetermined conditions using the rolled product of copper alloy, it is possible to avoid discomfort in the rolled product of copper alloy. The heat treatment conditions should be specified without properly recrystallizing the part.

The trace element in the composition of the copper alloy ingot of the present embodiment is not particularly limited and may be any element, but is preferably an element that can refine crystal grains, more preferably P, Zr, Cr, Ti, Sn, Ni, One or more selected from the group of Be, Zn, In, Mg, V, Mo, W, Ba, Sr, and Y, and P is more preferred. These elements can further facilitate the refinement of crystal grains in a copper alloy rolled product obtained by processing using a copper alloy ingot.

In addition, the concentration of trace elements in the ingot is 10 to 50 mass ppm. By setting the concentration of the trace elements within such a range, for example, when processing as a copper alloy rolled product by a rolling process, the crystal grains in the composition can be appropriately refined. Specifically, by setting the concentration to 10 mass ppm, the crystal grains in the composition can be made finer, and the strength and bending resistance of the copper alloy rolled product can be improved. In addition, when the concentration is 50 mass ppm or less, the recrystallization temperature does not rise too high, and when the copper alloy rolled product is heat-treated, recrystallization can occur, so that the strength can be prevented from becoming too high, and the bending resistance can be ensured. Foldability.

In addition, when an ingot contains several trace elements, the density|concentration of each trace element is in the said range (for example, 10-50 mass ppm).

The variation in the concentration of trace elements in the longitudinal direction is within a range of ±3.5 mass ppm relative to the average concentration of trace elements, more preferably within a range of ±2 mass ppm, and still more preferably within a range of ±1 mass ppm. By making this deviation within the range of ±3.5 mass ppm, for example, in a copper alloy rolled product produced from an ingot, the unevenness of physical properties in the longitudinal direction of the copper alloy rolled product can be made sufficiently small. When heat treatment under predetermined conditions is performed using this copper alloy rolled product, it is possible to avoid the occurrence of a portion in the copper alloy rolled product that does not meet the predetermined heat treatment conditions and the desired physical properties cannot be obtained.

In addition, when an ingot contains several trace elements, the dispersion|variation of the density|concentration of each trace element is all in the said range (for example, in the range of ±3.5 mass ppm).

Here, the concentration of the trace elements in the ingot refers to the surface at the center of the width direction of the ingot, along the longitudinal direction of the ingot at every 1 m point (excluding the range of 2.25 cm from both ends in the longitudinal direction of the ingot) ) was sampled, and each obtained sample was measured by ICP emission spectrometry, and the measured values were averaged (and this value was recorded as the average concentration of trace elements in the ingot). In addition, the deviation of the concentration within the range of ±3.5 mass ppm relative to the average concentration of trace elements means that the concentration of each sample sampled and measured by the above-mentioned method is lower than the concentration of trace elements obtained by the above-mentioned method. (Average value) Within the range between the concentration (upper limit value) higher by 3.5 quality ppm and the concentration (lower limit value) lower than the average concentration by 3.5 quality ppm.

In the present embodiment, the copper alloy contains trace elements and at least one kind of additive element. When an element other than a trace element is contained as an additive element, the additive element other than the trace element is not particularly limited, and examples thereof include Ag, Sn, and Zr. Moreover, the density|concentration of the additive element other than this trace element is not specifically limited, It can be 0.01-0.2 mass %.

In addition, in this embodiment, the balance consists of Cu and unavoidable impurities. Here, the unavoidable impurity refers to an impurity element unavoidably mixed into the material in the manufacturing process.

The ingot of the present embodiment is not particularly limited, but may be, for example, 150 to 220 mm in thickness, 3 to 6 m in length, and 500 to 700 mm in width. Moreover, the shape of an ingot is not specifically limited, For example, it can be a rectangular parallelepiped shape.

In addition, the ingot of the present embodiment is preferably used in applications (for copper alloy sheets, copper alloy foils, etc.) for producing copper alloy rolled products by the rolling step, as described above, and particularly preferably in applications for copper alloy foils.

Specifically, the copper alloy rolled product produced from the ingot of the present embodiment is not particularly limited, and the above-mentioned ingot can be rolled and produced by a known method. In addition, the copper alloy rolled product preferably has the same composition as that of the ingot. Specifically, it has a composition containing at least one additive element and the balance is composed of Cu and unavoidable impurities. The concentration of at least one additive element is 10 For trace elements of to 50 mass ppm, the variation in the concentration of the trace elements in the longitudinal direction is within a range of ±3.5 mass ppm with respect to the average concentration of the trace elements.

It should be noted that the concentration of trace elements in the copper alloy rolled product refers to the surface at every 10,000 m in the longitudinal direction in the width direction center of the copper alloy rolled product (distance from both ends in the longitudinal direction). Except for the range of 1 m), take samples, measure each obtained sample by the same method as ingots, and average the measured values (in addition, this value is recorded as the amount of trace elements in the copper alloy rolled product). average concentration). In addition, the variation in concentration, within the range of ±3.5 mass ppm relative to the average concentration of trace elements, means that the concentration of each sample obtained by sampling and measurement using the above-mentioned method is lower than the concentration (average value) of trace elements. The range between the concentration (upper limit value) that is 3.5 quality ppm higher and the concentration (lower limit value) that is 3.5 quality ppm lower than the concentration (average value) of trace elements.

Moreover, when manufacturing a copper alloy foil from the ingot of this embodiment, it is preferable that the thickness of this copper alloy foil is 0.003-0.017 mm.

Next, the manufacturing method of the copper alloy ingot of this embodiment is demonstrated.

The method for producing a copper alloy ingot according to the present embodiment (hereinafter, also referred to as a method for producing an ingot) is a method for producing the copper alloy ingot according to the above-described embodiment of the present invention, including: The step of adding trace elements to the copper molten material in a molten state while flowing in one direction.

More specifically, in the method for manufacturing an ingot of the present embodiment, a manufacturing apparatus including a melting furnace for melting a material (for example, copper) as a base material before adding trace elements can be used; A pipe through which the molten copper material (molten copper) melted by a melting furnace flows in one direction; a tundish furnace, through which the copper molten material is supplied to the tundish furnace; a casting device, which introduces the copper molten material from the tundish furnace into the tundish furnace casting device. In addition, the manufacturing apparatus includes an addition path that communicates with the pipe and extends vertically upward, and a belt conveyor whose tip is positioned at an opening on the vertical upward side of the addition path.

In the case of using such a manufacturing apparatus, the ingot is manufactured by causing the copper molten material to flow in one direction (from one end of the pipe to the other end) in the pipe, while making the trace elements conveyed by the belt conveyor flow from the The tip of the belt conveyor is dropped and thrown into the opening on the upper side in the vertical direction of the addition path, whereby trace elements can be added to the molten copper material.

In addition, in the above-mentioned manufacturing apparatus, a low-frequency induction furnace can be used as a melting furnace, for example, and it is preferable to perform melting in an oxygen-free state.

The pipe can be a cylindrical channel. In order to prevent oxidation of the molten copper material (molten copper) flowing through the pipe, it is preferable to fill the interior of the pipe with an inert gas such as nitrogen (the molten copper material flows under the pipe, and the space above the material flows). filled with inert gas).

The addition path may be a cylindrical path that communicates with the duct, extends vertically upward (or may be inclined), and has an opening on the vertical upward side of the addition path. The opening may have an expanded shape, or a funnel may be attached to the opening in order to allow the trace elements conveyed by the belt conveyor to fall and easily enter the inside of the addition path.

The belt conveyor can be used to automatically transport trace elements, and the transported trace elements are dropped from the tip of the belt conveyor and put into the opening of the addition path. In order to transport and inject trace elements quantitatively using a belt conveyor, the belt conveyor preferably has a weighing function capable of measuring the weight of the trace elements before and after falling. Such a belt conveyor with a metering function, for example, in order to input a predetermined amount of trace elements per unit time, can adjust the input of trace elements by measuring the quality change of the trace elements carried on the belt; specifically , When the actual input amount (quality change amount) exceeds a predetermined amount, the transportation by the belt conveyor is stopped for a certain period of time, so that the input of trace elements can be adjusted.

The tundish furnace is a furnace in which molten copper material is temporarily stored, and the molten copper material is stirred in the furnace to remove impurities and the like. The trace element is preferably added to the copper molten material flowing in the pipe in the present embodiment, but may be added to the copper molten material in the tundish furnace.

Casting equipment, which is fed with a certain amount of copper molten material from the tundish furnace and allowed to cool, can produce ingots.

Here, in the method for producing an ingot of the present embodiment, in the step of adding the trace elements to the copper molten material, the addition amount M1 of the trace elements per second can be adjusted to be smaller than the amount M1 of the trace elements per second 2 times the theoretical addition amount M2, which is calculated using the concentration D (the desired concentration of trace elements of the ingot) and the flow rate F per 1 second of the copper molten material flowing in one direction.

It should be noted that "the added amount of trace elements M1 per second" refers to the quality of the trace elements added to the copper molten material in one second actually, and refers to the quality of the trace elements themselves in the diluted particles. .

In addition, "the theoretical addition amount M2 of trace elements per second" is calculated using the concentration D of the trace elements in the ingot and the flow rate F per second of the molten copper material flowing in one direction. In other words, in order to make The concentration of the trace element in the copper alloy is the quality of the trace element that should be added to the copper molten material per second calculated at the desired concentration D. That is to say, in the case where trace elements are directly added (in the form of elemental substances) to the copper molten material, the concentration D of the trace elements in the ingot can be derived by D=M2/(F+M2). The theoretical addition amount M2 per second becomes M2=D×F/(1-D). Therefore, the addition amount M1 of the trace element in 1 second becomes M1<2×M2=2×D×F/(1−D).

In addition, when the addition of trace elements is calculated using the diluted particles diluted in Cu as described below, when the concentration of the trace elements in the diluted particles is written as the concentration d, the concentration D of the trace elements in the ingot can be obtained by D=M2/(F+M2/d) is derived, and the theoretical addition amount M2 of trace elements per second becomes M2=D×F/(1-D/d). Therefore, the addition amount M1 of the trace element per second becomes M1<2×M2=2×D×F/(1−D/d).

The flow rate F of the above-mentioned molten copper material can be obtained from, for example, the amount of molten copper material supplied from the melting furnace, the supply time, and the like, and can be calculated by an arbitrary method.

In addition, in the present embodiment, by adjusting the addition amount M1 of the trace elements in one second to be less than twice the theoretical addition amount M2 of the trace elements per second, the trace elements in the longitudinal direction of the ingot can be reduced. concentration deviation. That is, when the addition amount M1 per second is more than twice the theoretical addition amount M2 per second, a portion with an excessively high concentration of trace elements occurs in the copper molten material. And at the same time, when the addition amount M1 in 1 second is too much, the addition amount M1 of trace elements in the next 1 second will be adjusted to 0, or, the addition amount M1 of trace elements will be adjusted in the next few seconds. If the addition amount M1 is decreased continuously, in addition to the portion where the concentration of the above-mentioned trace element is too high, the portion where the concentration of the trace element is too low will be generated in the copper molten material. Therefore, by adjusting the addition amount M1 of the trace element per second to be less than twice the theoretical addition amount M2 per second, it is possible to reduce the unevenness of such trace elements in the copper molten material, so it is possible to The variation in the concentration of trace elements in the longitudinal direction of the ingot is reduced.

Here, in the method for producing an ingot of the present embodiment, as a method of adjusting the addition amount M1 of the trace element per second to be less than twice the theoretical addition amount M2 per second, the following can be mentioned. method.

That is, as a method of adjusting the addition amount M1 of trace elements in 1 second to be less than twice the theoretical addition amount M2 per second, there is a method in which, in an ingot manufacturing apparatus, The height (thickness) of the additive element carried on the belt conveyor into which the copper molten material flowing in the route is fed is relatively small. That is, when the height (thickness) of the additive element carried on the belt conveyor is large, it is conveyed in a state in which many trace elements are carried in the height direction, and thus there is a possibility that the height (thickness) of the added element is carried from the top of the belt conveyor. There is a tendency for a large amount of trace elements to drop each time to the opening of the addition path (the trace elements accumulated in the height direction tend to drop a large amount from the top each time). Conversely, by reducing the height of the added elements carried on the conveyor belt, the trace elements falling from the top of the belt conveyor to the opening of the adding path can be reduced, and the added amount M1 of the trace elements in 1 second can be easily adjusted. Make adjustments. In addition, adjustment can also be performed by changing the conveyance speed of the belt conveyor itself.

In addition, as a method other than the above-mentioned method, in the ingot manufacturing apparatus, the belt width (orthogonal to the traveling direction of the belt) of the belt conveyor for throwing in the copper molten material flowing into the pipe through the addition path may be mentioned. length in the direction) is relatively small method. That is, when the bandwidth of the belt conveyor is large, the trace elements are transported in a state in which the trace elements are widely carried in the width direction, whereby the trace elements are moved from the tip of the belt conveyor to the end of the adding path every time. There is a tendency for the addition amount to increase in the opening drop (the trace elements accumulated along the width direction tend to drop more from the top each time). Conversely, by reducing the bandwidth, it is possible to reduce the amount of trace elements falling from the tip of the belt conveyor to the opening of the addition path, and to easily adjust the addition amount M1 of the trace elements in one second.

In addition, as a method other than the above-mentioned method, when the trace element is in the form of particles described below, a method of making the particle diameter of the trace element relatively small can be mentioned. By reducing the particle diameter of the trace element, when the trace element falls from the top of the belt conveyor to the opening of the adding path, the particle diameter is small, so it gradually falls little by little (the trace element does not fall from the top every time. A large amount), so the addition amount M1 of trace elements in 1 second can be easily adjusted.

Further, as a method other than the above-mentioned method, when the trace element conveyed by the belt conveyor is dropped and charged, a gas, more preferably an inert gas such as nitrogen gas, is blown toward the opening of the addition path. method. Specifically, when the trace element is put into the copper molten material flowing in the pipe through the addition path, in the addition path, the heat of the copper molten material causes an updraft to be generated, so the falling in the addition path of the trace element does not cause inconvenience. uniformity. However, by blowing gas toward the opening of the addition path, the trace elements can be made to fall more stably. In addition, in the ingot manufacturing method of the present embodiment, in particular, when the copper molten material flows in a state where the inert gas is filled in the pipe, the gas may flow back in the addition path, so the By blowing gas toward the opening of the addition path, the trace elements can be dropped more stably. In addition, when an inert gas is used, oxidation of trace elements can be prevented.

In the above, in the ingot manufacturing method of the present embodiment, the method of adjusting the addition amount M1 of trace elements per second to less than twice the theoretical addition amount M2 per second has been described. The adjustment method in the manufacturing method of an ingot is not limited to the above-mentioned, An arbitrary method can be employ|adopted, and any one of the above-mentioned methods or a combination thereof can also be employ|adopted for an adjustment method.

Further, in the method for producing an ingot of the present embodiment, the addition of trace elements is preferably performed using particulate trace elements, and more preferably, using diluted particles (specifically, trace elements and copper) diluted with copper. mixed product) was added. By using particulate trace elements, the addition amount M1 of the trace elements in one second can be easily adjusted to an appropriate amount. In addition, by using diluted particles, the added amount can be increased, making it easier to adjust the amount of trace elements added. Addition amount M1 in 1 second. In addition, chemical changes such as oxidation of trace elements can be suppressed, and the handleability of trace elements can also be improved.

In addition, the particle diameter is preferably 2.0 to 4.0 mm. It should be noted that the particle diameter refers to the volume average particle diameter, that is, the value (D ₅₀ ) of 50% of the volume particle diameter distribution.

When the particle diameter is less than 2.0 mm, it is advantageous in that it can be rapidly dissolved in the copper molten material, but it tends to become lumps during transportation, and it tends to be difficult to adjust the addition amount M1 in 1 second. In addition, when the particle diameter is less than 1.0mm, it may be oxidized and may also be affected by airflow. On the other hand, if the particle diameter is larger than 4.0 mm, although handling is easy, it tends to be difficult to adjust the addition amount M1 in 1 second.

The diluted particles are not particularly limited, but the concentration d of the trace element is preferably 50 mass % or less, and more preferably 20 mass % or less. Within such a range, the addition amount M1 in one second can be adjusted by increasing the input amount.

Further, when the ingot contains an additive element other than a trace element, the addition of the additive element other than the trace element in the method for producing an ingot of the present embodiment may be performed using an addition route as in the method for adding trace elements, or The additive element itself may be contained in the material melted in the melting furnace, or the additive element may be added in the tundish furnace.

Further, in the method for producing an ingot of the present embodiment, when the trace element is P, it is preferable to use diluted particles containing 8 mass % or more of P in Cu (specifically, a product obtained by mixing P and Cu). Thereby, a copper alloy ingot with further improved uniformity of physical properties can be produced.

More specifically, by using the diluted particles, the addition amount is increased as compared with the addition of the elemental P element, and the addition rate of P can be easily adjusted to an appropriate rate. In addition, chemical changes such as oxidation of P can be suppressed, and the handleability of P can also be improved.

Furthermore, since P contains 10 mass % or more of diluted particles in Cu, the melting point is high and close to the melting point of Cu. Therefore, when adding P with diluted particles, P gradually dissolves in the copper molten material ( The dissolution rate is reduced), P can be easily dispersed in the copper molten material. In addition, when the concentration of P is 13 mass % or more, the hardness of the diluted particles is relatively large, and it is difficult to generate fine powder in the diluted particles in the process of producing the diluted particles. In the case where there are many fine powders in the diluted particles, when P is added, the fine powders are rapidly dissolved in the copper molten material (the dissolution rate increases), and P exists locally in the copper molten material, thereby suppressing the generation of the above-mentioned fine powders , the localization of the P can be suppressed.

Therefore, by adding P using diluted particles containing 8 mass % or more of P in Cu, it is easier to adjust the addition of P, and the dispersibility of P in the copper molten material can be improved. A copper alloy ingot with further improved uniformity.

In the diluted particles, the concentration of P is preferably 8 to 16 mass %, and more preferably 14 to 16 mass %.

As mentioned above, although embodiment of this invention was described, the manufacturing method of the copper alloy ingot, copper alloy foil, and copper alloy ingot of this invention is not limited to the said example, It can change suitably.

[Example]

Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited to the following examples.

(Example 1)

In Example 1, copper alloy ingots were produced as follows, and the concentrations of trace elements in the ingots and their deviations were measured.

In the copper alloy ingot of Example 1, trace elements were added to the copper molten material while flowing the copper molten material, and the addition amount M1 of the trace elements in 1 second at this time was adjusted to be less than the trace element per 1 second. The theoretical addition amount of the clock M2 is twice that of M2, and it is manufactured at the same time.

Specifically, the composition of the copper alloy ingot was copper and phosphorus as a trace element, and 5t copper was used for the production of the copper alloy ingot. The addition of trace elements was performed using diluted particles (Osaka Alloy Industry Co., Ltd., product name 15PCuA, phosphorus concentration 15 mass %, particle diameter 2.0 to 3.7 mm) diluted in copper.

A manufacturing apparatus for manufacturing an ingot, comprising: a melting furnace; a pipe through which a copper molten material melted using the melting furnace passes; a tundish furnace for supplying the copper molten material to the tundish furnace through the pipe; The tundish furnace introduces the copper molten material into the casting device; an addition path communicates with the pipe and extends vertically upward; and a belt conveyor is located at the opening on the vertical upward side of the addition path at the top end. In addition, in the belt conveyor of the manufacturing equipment, the height of the trace elements (diluted particles) carried on the belt conveyor is adjusted so that the addition amount M1 of the trace elements in one second is less than the theoretical value per second. Add 2 times the amount of M2.

The ingot produced as described above had a thickness of 178 mm, a width of 635 mm and a length of 5 m.

In addition, five samples were sampled from the ingot, and the concentration of phosphorus in the ingot was measured by the method of ICP emission spectrometry. As a result, the calculated phosphorus concentration (average value) was in the range of 10 to 50 mass ppm. Furthermore, the difference between the phosphorus concentration of each sample and the phosphorus concentration (average value) of the ingot was -0.2 quality ppm, -0.2 quality ppm, +0.8 quality ppm, -1.2 quality ppm, +0.8 quality ppm, and the deviations were relative The average concentration of trace elements is within the range of ±3.5 mass ppm.

In addition, the copper alloy ingots of Comparative Examples 1 and 2 were carried out in the same manner as in the above-mentioned Example 1, except that the addition amount M1 of trace elements per second was twice or more the theoretical addition amount M2 per second. method to manufacture. Specifically, the addition amount is adjusted by changing the conveying speed of the belt conveyor itself.

The phosphorus concentration (average value) calculated by sampling five samples from the ingots of Comparative Examples 1 and 2 was in the range of 10 to 50 mass ppm.

Further, the phosphorus concentration of each sample in Comparative Example 1 was -6.0 mass ppm, -2.0 mass ppm, +3.0 mass ppm, +4.0 mass ppm, and +1.0 mass ppm, and the deviations were relative to the average concentration of trace elements in Outside the range of ±3.5 quality ppm. The phosphorus concentration of each sample in Comparative Example 2 was -5.4 mass ppm, -2.4 mass ppm, +1.6 mass ppm, +3.6 mass ppm, and +2.6 mass ppm, and the deviation was ±3.5 relative to the average concentration of trace elements. quality outside the ppm range.

(Example 2)

In Example 2, the influence of the variation of elements on the copper alloy foil was confirmed. Specifically, after laminating a copper alloy foil produced by rolling a copper alloy ingot and a resin under heating, whether or not the composition in the copper alloy foil is properly recrystallized, the following examples are used. 2. Comparative Examples 3 and 4 were discussed.

In Example 2, the thickness of the copper alloy foil was 0.012 mm, and the copper alloy foil produced from the copper alloy ingot of Example 1 described above was used. The material of the resin was polyimide (Pixio FRS manufactured by KANEKA Co., Ltd.) with a thickness of 25 μm. Using a 350° C. roll, the copper alloy foil, the resin, and the copper alloy foil were stacked and pressed to perform lamination.

Next, in Comparative Examples 3 and 4, the same procedure as in Example 2 was carried out except that copper alloy foils were produced from the copper alloy ingots of Comparative Examples 1 and 2 described above, respectively.

As a result of the above, in Example 2, the recrystallization in the copper alloy foil was suitable, the average crystal grain size was 2.5 μm, and coarse grains 10 times or more the average crystal grain size were not found. In addition, in Comparative Examples 3 and 4, the copper alloy foil has a portion that is not recrystallized, and even if recrystallization is completed and the average crystal grain size is 2.5 μm, there are coarse grains 10 times or more the average crystal grain size. part, which is not properly recrystallized.

In addition, the average particle diameter of a crystal was calculated|required based on JIS H 0501 by observing the surface of each copper alloy foil using SEM (Scanning Electron Microscope). Among them, twins are measured as distinct grains. The measurement area is 100 μm×100 μm on the surface.

Based on the results of the above-mentioned Experimental Example 1, it can be seen that in the method for producing a copper alloy ingot, the addition amount M1 of the trace element per second is adjusted to be less than twice the theoretical addition amount M2 of the trace element per second. , the deviation of the concentration of trace elements in the ingot in the longitudinal direction can be made within the range of ±3.5 mass ppm relative to the average concentration of trace elements. In addition, from the above-mentioned Experimental Example 2, it was found that the copper alloy foil produced from the copper alloy ingot with a small variation in trace elements has high uniformity of physical properties.

[Industrial availability]

According to the present invention, it is possible to provide a copper alloy ingot, a copper alloy foil, and a method for producing a copper alloy ingot in which the uniformity of physical properties is further improved.

The above descriptions are only preferred feasible embodiments of the present invention, and any equivalent changes made by applying the description of the present invention and the scope of the patent application should be included in the patent scope of the present invention.

without

without

Claims (7)

A copper alloy ingot, has a composition containing at least one additive element and the balance consisting of Cu and unavoidable impurities, The at least one additive element is a trace element with a concentration of 10 to 50 mass ppm, The variation in the concentration of the trace elements in the longitudinal direction is within a range of ±3.5 mass ppm with respect to the average concentration of the trace elements. The copper alloy ingot according to claim 1, wherein the trace element is phosphorus. A copper alloy foil obtained by rolling the copper alloy ingot according to claim 1 or 2. A method for producing a copper alloy ingot is the method for producing a copper alloy ingot as claimed in claim 1 or 2, wherein, including the step of adding the trace element to the copper molten material while making the copper molten material containing Cu in the molten state flow in one direction, When the required concentration of the trace element of the copper alloy ingot is denoted as concentration D, In the step of adding, the addition amount M1 of the trace element in 1 second is adjusted to be less than twice the theoretical addition amount M2 of the trace element per second, the theoretical addition amount M2 It is calculated using the concentration D and the flow rate F per second of the copper molten material flowing in one direction. The method for producing a copper alloy ingot according to claim 4, wherein the addition of the trace element is performed using diluted particles obtained by diluting the trace element in Cu. The method for producing a copper alloy ingot according to claim 5, wherein the diluted particles contain 8 mass % or more of phosphorus in Cu. The method for producing a copper alloy ingot according to any one of claims 4 to 6, wherein, in the step of adding, The copper molten material flows in one direction in a pipe filled with an inert gas, The trace elements transported by the belt conveyor are dropped from the tip of the belt conveyor and put into the opening on the upper side in the vertical direction of the addition path that communicates with the pipe and extends toward the upper side in the vertical direction. This carries out the addition of the trace elements.