JPH08300119A - Production of highly conductive copper alloy - Google Patents

Abstract

PURPOSE: To produce an inexpensive Ni-P-contg. highly conductive copper alloy having high quality by smooth addition of alloy additive elements at a high yield without entailing the pollution of molten copper. CONSTITUTION: An (Ni-P base alloy) or (Ni-P base alloy + metal of the m. p. lower than the m. p. of the molten copper) is used as a phosphorus compd. of Ni and is supplied to the prescribed copper melt in a tundish at the time of adjusting the copper alloy melt prior to continuous casting and thereafter, continuous casting is executed, by which the ingot of the Ni-P-contg. highly conductive copper alloy is produced. As a result, the operation with saved energy is made possible.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper alloy containing at least Ni and P, which is used in a method for producing a highly conductive copper alloy, particularly in the field of electronic materials such as semiconductors which require high conductivity. The present invention relates to a manufacturing method.

[0002]

2. Description of the Related Art A general method for producing a copper alloy by adding another metal to copper is to load various metals together with copper into a melting furnace and melt them to produce an alloy solution. The batch method was adopted. However, in the method of manufacturing various copper alloys by a batch method in one furnace, the inside of the melting furnace must be cleaned every time the type of alloy solution is changed, and therefore a large amount of molten metal is required. It was necessary and there was a problem in workability. Further, in this method, there is a problem that productivity is low and manufacturing cost is high because continuous operation is not possible and the operation rate of the melting furnace is low. Further, in the melting furnace, it is difficult to uniformly mix the copper and the additive element, and contamination due to the previous operation occurs, which causes a problem that the quality of the finished alloy solution is poor.

On the other hand, it is possible to melt a copper alloy in a shaft furnace which is a continuous melting furnace, but there are fundamental problems such as non-uniformity of molten metal and contamination of the furnace, and it has been put to practical use. Absent. However, alloying by adding the additive element in the pre-stage of casting (such as a continuous casting machine) is sufficiently possible to achieve alloying, especially with a low melting point like Sn and hundreds to thousands. It can be applied to alloys with low ppm level content. As a technique for dealing with the above-mentioned continuity, a device is provided in which a runner (gutter) is provided on the upstream side of a basin (tundish), and an alloy component in a solid state is added through this runner (see JP-A-63-62829). ) Or a heating furnace (high frequency furnace) provided between the basin and the runner, and an apparatus for adding the additive to the runner through an additive feeding path (JP-A-63-6).
No. 2830) are proposed.

[0004]

However, in the above-mentioned prior art, when continuously producing a highly conductive copper alloy, it was difficult to control the content depending on the additive element. For example, in the case of a copper alloy containing Ni, the melting point of Ni is 1455.
℃, much higher than that of copper (1085 ℃), Cu-
Even with 30 wt% Ni and Cu-50 wt% Ni mother alloys, their melting points are 1200 ° C. and 1300 ° C., respectively. Can not be expected to be added. Further, when considering the addition of P, since P is an element having a low density and a low boiling point, it is impossible to add it as a simple substance, and in general, shot Cu-P is used.
It is usually added in the form of a master alloy.

In this regard, in order to realize the precipitation of fine Ni-P compounds required as a highly conductive copper alloy,
If a Cu-Ni master alloy and a Cu-P master alloy are used together, the control of the Ni / P quantity ratio is disturbed, and the composition of the precipitate,
The quantity and size vary and the characteristics are not stable. Moreover, the amount of Cu to be melted (the relative amount of Cu to be added as a master alloy) is increased. As a result, the molten copper temperature is lowered due to melting of the mother alloy, and extra heat energy is required to ensure that amount, which hinders smooth alloy addition.

The main object of the present invention is to propose an advantageous process for the production of a homogeneous, highly conductive copper alloy. Another object of the present invention is to produce a high-quality and inexpensive Ni-P-containing high-conductivity copper alloy without causing contamination of other pure copper products through high yield and smooth addition of alloying additive elements. It is in. Still another object of the present invention is to achieve the homogeneous addition of minutely added components through effective addition immediately before the mold and to establish a thermally advantageous copper alloy production technique.

[0007]

[Means for Solving the Problems] Overcoming the above-mentioned problems,
As means for achieving the above object, the present invention is
Each manufacturing method according to the gist configuration described below is proposed. (1) When continuously casting a melt of a copper alloy containing Ni and P to produce a highly conductive copper alloy, while containing molten copper in a tundish, the molten copper in the tundish contains Ni. And P are added in the form of a Ni-P compound, and then continuously cast, which is a method for producing a highly conductive copper alloy. However, as the above Ni-P compound,
A Ni-P master alloy or a compound of a Ni-P master alloy and a metal having a melting point lower than the molten copper temperature is used. (2) In producing a highly conductive copper alloy by continuously casting a melt of a Ni-P-containing copper alloy, while containing molten copper in the tundish, the tundish contains the Ni-P compound and Zr. , Mg or Si, which is a copper mother alloy with an active metal surrounded by copper, In, Sn, Cd or Pb
Low melting point metal consisting of Zn, Sb, Al or A
A method for producing a highly conductive copper alloy, characterized in that other metal consisting of g is added intermittently or continuously in the state of either melt, wire or shot, and then continuous casting . (3) At least 0.1 to 2.0 wt% Ni and 0.02 to 0.4 wt% P
And 0.03 to 3.0 wt% of one or more low melting point metal selected from In, Sn, Cd and Pb, and at least one of Zn, Sb, Al and Ag, if necessary. 0.03 to 3.0 added ingredients consisting of seeds
In producing a highly conductive copper alloy containing wt% and the balance substantially Cu, Ni and P are Ni-P.
Use a copper tube, copper strip or copper foil that surrounds the mother alloy, use a melt for low melting point metal, and
For other additive components, those in the form of lines or shots are used, and each is added by intermittently or continuously charging or supplying into the tundish,
After that, continuous casting is performed, and a method for producing a highly conductive copper alloy. (4) It is preferable to use the Ni-P master alloy having a component composition containing 5 to 25 wt% of P and the balance being Ni.

[0008]

One of the features of the present invention is that when a molten copper alloy is prepared prior to continuous casting, it is added to a predetermined copper melt as a Ni compound (Ni-P master alloy) or (Ni-P master alloy). N) by using a metal having a melting point lower than the molten copper temperature) and supplying this into the tundish to continuously cast N
The point is that the i-P-containing highly conductive copper alloy ingot is manufactured.

Another feature of the method for producing a high-conductivity copper alloy according to the present invention is that the addition of each component element into the tundish is carried out in the following different and separate methods depending on the characteristics of each element. To do in. It was mainly studied from the viewpoint of thermo-economics and homogeneous alloying.

(1) Method of charging Ni-P master alloy In the present invention, Ni and P are used in the form of Ni-P master alloy. That is, an ingot of a Ni-P compound having a brittle composition is produced, crushed and classified, and a certain amount of the ingot is filled into a copper tube through a packing machine, and a tubular product is produced using a copper strip. Then, the one filled while being surrounded by the copper foil or the one surrounded by the copper foil is directly and intermittently charged into the tundish at a constant interval using a constant pitch feeder. Alternatively, the crushed ingot may be charged in the form of shots, but it is preferable to use one surrounded by copper. (2) Method of supplying low melting point metal In, Sn, Cd, Pb, etc. (all are mp = 350 ° C.
For the following), the metal ingots of these metals are melted in a melting furnace, the melt is controlled to a constant flow rate through a flow control valve, and added directly by piping into a tundish. To do. However, when a strict content control is required, for example, in the case of a small amount addition, it is preferable to continuously feed in the form of a line. That is, the processed wire is added from a bobbin to a gutter or directly into a tundish using a constant speed roller. (3) Method of supplying other metals For Zn, Sb, Al and Ag (mp = 350 to 1000 ° C.), these metals are processed into wire or shot, and then the bobbin is moved to a constant speed roller. Use or classify and add into the gutter or directly into the tundish using a metering belt feeder.

In this respect, conventionally, Cu has a Cu- (1
5 wt%) In the form of Ni mother alloy, P is Cu- (15 wt%)
P master alloy (≈1000 ° C) is used, and these ingots are fed into the melting furnace. For low melting point metals such as Sn (mp: 232 ° C), the melting furnace or gutter is used in the form of wire. Continuous supply is performed, and the position of supply (addition) is at the melting furnace, the heating furnace on the upstream side of the tundish, or the runner (gutter) on the upstream side. That is, as long as the conventional method is followed, since the heating means is always provided on the downstream side of the addition position, insufficient heat quantity is hardly a problem, and therefore in the case of a low melting point metal, the wires, Ni and P are used.
For the above, the form of the master alloy with Cu is sufficient.

However, when added to a non-heated tundish directly connected to a continuous casting machine as in the present invention, heat compensation cannot be sufficiently performed as in the prior art,
It is necessary to devise the form of addition of each alloy component from the viewpoint of energy saving.

Therefore, in the present invention, it is decided to adopt the above-mentioned addition means depending on the added components. That is, for Ni and P, by using the form of Ni-P master alloy instead of Cu master alloy, firstly, the use of extra copper (in the case of Cu-Ni, Cu-P master alloy) Secondly, the heat of fusion is made unnecessary, and secondly, as is apparent from the phase diagram shown in FIG. 1, the low melting point of the Ni—P eutectic alloy (≈
(880 ℃) ensures rapid uniform diffusion into the molten copper to achieve high quality, and by taking such measures, the superheat of the molten copper is lowered and the quality is stabilized. And to reduce costs.

Further, for low melting point metals including Sn, Pb, and Zn in some cases, by directly sending the low melting point metal into the tundish or the trough in a molten state, wasteful consumption of heat energy and molten copper Try to prevent the temperature from dropping.

And other, mainly mp = 35
Metals (Sb, Al, Ag, etc.) at 0 to 1000 ℃ were processed and supplied in the form of linear or shot as before.

With the method of the present invention, with the above-mentioned structure, pure copper, especially a copper alloy based on acid-free copper can be manufactured at the same time with high productivity and low cost. In particular,
Since it is added and supplied in the tundish immediately before the continuous mold, there is no opportunity for copper contamination, and it is easy to switch to OFC operation.

[0017]

EXAMPLE FIG. 2 shows an essential part of a molten copper continuous casting apparatus used for carrying out the manufacturing method of the present invention. In order to manufacture a copper alloy by this apparatus, first, molten copper 1 from a melting furnace (not shown) is fed into a tundish 3 through a gutter 2 and the molten copper 1 is continuously fed through a pouring nozzle 4. Continuous casting is performed in the water-cooled mold 5 of the casting machine. Then, the copper slab that has started to solidify in the continuous casting mold 5 passes through the water spray type secondary cooling zone, reaches the pinch roll while being dropped, is withdrawn, and is further cut into a predetermined length to form a copper. A slab (cake) is obtained.

An example of producing a copper alloy having the following composition using the above apparatus will be described. A. Cast molten copper 1.0 wt% Ni-0.2 wt% P copper alloy 0.32 wt% Ni-0.08 wt% P-0.1 wt% In copper alloy 0.2 wt% Ni-0.05 wt% P-2.0 wt% Sn copper alloy 1.0 wt% Ni -0.2 wt% P-1.0 wt% Zn copper alloy 0.32 wt% Ni-0.08 wt% P-0.1 wt% Ag copper alloy

B. Continuous casting (1) Electrolytic copper is melted at 10 T / H in a low frequency induction furnace and the molten copper is transferred to the tundish 3 through the gutter 2 (temperature 1180 ° C, O ₂
Then, the cake was injected into the continuous casting mold 5 through the pouring nozzle 4 to continuously cast a cake having a cross section of 178 mm × 635 mm at a drawing speed of 165 mm / min. At this time, according to the method of the present invention, the charging port 6 on the upper part of the tundish 3
20 wt% P Ni-P mother alloy (copper alloy) ingot was crushed and put in a copper tube (57 g) (hereinafter referred to as "Ni-
P-containing copper tube ”) was charged at 1 second intervals.
As a result of investigating the variation of the component in the length direction of the obtained continuous cast cake, as shown in Table 1, it was found that the allowable range was sufficiently satisfied. Moreover, casting defects and surface defects were hardly observed. (2) In continuous casting under the same conditions as in (1) above, a "Ni-P powder-containing copper tube" containing 91 g of Ni-P alloy powder was charged at intervals of 5 seconds and melted in another melting furnace 7. While maintaining the melt at a temperature of 200 ° C and a pumping pressure of 0.8 kg / cm ² ,
Tundish 3 at a speed of 180 g / min through flow control valve 8
The copper alloy was poured into the inside of the container to adjust the copper alloy, and continuous casting was performed. As shown in Table 1, there was no particular problem in terms of quality and workability, and smooth casting was possible. (3) During continuous casting under the same conditions as in (1) above, the Sn melt melted in another furnace by introducing a “Ni-P powder-containing copper tube” containing 57 g of Ni-P alloy powder at 5 second intervals. The temperature of 300
℃, while keeping the pumping pressure of 1 kg / cm ² , while pouring into the tundish 3 through the flow regulating valve 8 at a rate of 3.6 kg / min to prepare the above copper alloy, and then continuously casting,
As shown in Table 1, there were no particular problems in terms of quality and workability, and smooth casting was possible. (4) During continuous casting under the same conditions as in (1) above, insert "Ni-P powder-containing copper tube" containing 57 g of Ni-P alloy powder at 1 second intervals, and pinch a 10 mmφ Zn wire from the charging port. It was thrown into the tundish 3 at a speed of 3.2 m / min by a roll to adjust the copper alloy, and then continuously cast,
There was no problem in quality and workability, and smooth casting was possible. (5) When performing continuous casting under the same conditions as in (1) above, insert "Ni-P powder-containing copper tube" containing 91 g of Ni-P alloy powder at 5 second intervals, and then pinch a 3 mmφ Ag wire from the charging port. It was put into the tundish 3 at a speed of 2.3 m / min by a roll to adjust the copper alloy, and then continuously cast,
There was no problem in quality and workability, and smooth casting was possible.

[0020]

[Table 1]

[0021]

As described above, according to the present invention, it is possible to produce a high-purity Ni, P-containing highly conductive copper alloy with high productivity and low cost through smooth continuous casting.
In particular, the Ni-P-containing copper alloy can be added by directly supplying it into the tundish without increasing the degree of superheat of the molten copper, so that the molten copper is less contaminated and energy-saving operation is possible. .

[Brief description of drawings]

FIG. 1 is a Ni—P alloy phase diagram.

FIG. 2 is a partial schematic view of a continuous casting device.

[Explanation of symbols]

 1 molten copper 2 gutter 3 tundish 4 pouring nozzle 5 continuous casting mold 6 inlet 7 melting furnace 8 flow control valve

Claims (4)

[Claims] 1. When producing a highly conductive copper alloy by continuously casting a melt of a copper alloy containing Ni and P, the molten copper is contained in a tundish and the molten copper in the tundish is placed in the molten tundish. , Ni and P are added in the form of a Ni-P compound, and then continuous casting is performed, and a method for producing a highly conductive copper alloy. 2. When continuously casting a melt of a copper alloy containing Ni and P to produce a highly conductive copper alloy, molten copper is accommodated in a tundish, and Ni- is contained in the tundish. A copper master alloy of an active metal composed of a P compound, Zr, Mg or Si, surrounded by copper, In, S
a low melting point metal composed of n, Cd or Pb, and Zn,
Highly conductive copper characterized by intermittently or continuously adding another metal consisting of Sb, Al or Ag in any state of melt, wire or shot, and then continuously casting Alloy manufacturing method. 3. At least 0.1-2.0 wt% Ni and 0.02-
Containing 0.4 wt% P, and further containing In, Sn, Cd and P
0.03 to 3. One or more low melting point metals selected from b.
0 wt%, and if necessary, an additive component consisting of at least one of Zn, Sb, Al and Ag.
In producing a highly conductive copper alloy containing 0.03 to 3.0 wt% and the balance being substantially Cu, for Ni and P, a Ni-P mother alloy is surrounded by a copper tube, copper strip or copper foil. For the low melting point metal, use the melt, and for the other additive components, use the ones in the form of lines or shots, and intermittently or continuously feed or supply each into the tundish. The method for producing a high-conductivity copper alloy, comprising: 4. The Ni-P master alloy contains 5 to 25 wt% of P.
%, And the component composition consisting of the balance Ni is used, and the manufacturing method according to claim 1.