WO2019244842A1

WO2019244842A1 - Resistance material for resistors and method for producing same, and resistor

Info

Publication number: WO2019244842A1
Application number: PCT/JP2019/023923
Authority: WO
Inventors: 紳悟川田; 岳己磯松; 樋口　優
Original assignee: 古河電気工業株式会社
Priority date: 2018-06-20
Filing date: 2019-06-17
Publication date: 2019-12-26
Also published as: CN111971405A; JP6762438B2; TW202000938A; JPWO2019244842A1; KR20210020869A; TWI731343B; CN111971405B

Abstract

The purpose of the present invention is to provide: a copper alloy sheet material having both of a small resistance temperature coefficient and good press-moldability; a method for producing the copper alloy sheet material; and a resistor material for resistors. The purpose of the present invention can be achieved by a copper alloy sheet material which contains 5.0 to 20.0% by mass of Mn, 0 to 5.0% by mass of Ni and 0 to 5.0% by mass of Sn, wherein Ni and Sn are contained in the total amount of 0.1 to 10.0% by mass, the remainder is made up by Cu and unavoidable impurities, and the difference between the elongation in a direction parallel with the rolling direction and the elongation in a direction vertical to the rolling direction, which is a sheet width direction and is vertical to the direction parallel with the rolling direction, is 10% or less.

Description

Resistor material for resistor, method of manufacturing the same, and resistor

The present invention relates to a copper alloy sheet, a method for producing the same, and a resistor material for a resistor.

The metal material of the resistor used in the resistor must have a small temperature coefficient of resistance (hereinafter sometimes referred to as “TCR”) so that the resistance of the resistor is stable even when the environmental temperature changes. Required. The temperature coefficient of resistance represents the magnitude of the change in resistance value due to temperature in parts per million per degree Celsius, and is expressed by TCR (× 10 ⁻⁶ / K) = (R−R ₀ ) / R ₀ It is represented by the formula of × 1 / (T−T ₀ ) × 10 ⁶ .

Here, T represents a test temperature (° C.), T ₀ represents a reference temperature (° C.), R represents a resistance value (Ω) at the test temperature T, and R ₀ represents a resistance value (Ω) at the test temperature T ₀ . . Cu—Mn—Ni alloys and Cu—Mn—Sn alloys have a very small TCR, and are therefore widely used as metal materials constituting resistance materials (for example, see Patent Document 1).

JP 2016-69724 A

(4) With the recent trend toward smaller and more integrated electrical and electronic components, resistance materials have also been reduced in size. Along with this miniaturization, the cross-sectional shape of a resistor material manufactured by press forming a metal material has a greater effect on the variation in the resistance value of the resistor. It is required to improve the press formability of a metal material of a resistance material having a fractured surface shape with reduced burrs and agglomerations.

The object of the present invention is to provide a copper alloy sheet material having both a low temperature coefficient of resistance and good press formability, a method for producing the same, and a resistor material for a resistor.

The object of the present invention has been achieved by the following.
1) 5.0 to 20.0% by mass of Mn, 0 to 5.0% by mass of Ni, 0 to 5.0% by mass of Sn, and 0.1 to 10.0% by mass of Ni and Sn in total A copper alloy sheet material containing, the balance being Cu and unavoidable impurities, wherein a difference between elongation in a rolling parallel direction and elongation in a rolling width direction and a rolling vertical direction perpendicular to the rolling parallel direction is 10% or less.
2) 5.0 to 20.0% by mass of Mn, 0 to 5.0% by mass of Ni, 0 to 5.0% by mass of Sn, and 0.1 to 10.0% by mass of Ni and Sn in total The balance is composed of Cu and inevitable impurities, and the τ-fiber obtained from the EBSD measurement results has an azimuth density of Φ = 20 to 35 ° of 4 or more and an azimuth density of Φ = 40 to 80 ° of less than 4 A copper alloy sheet material.
3) The method as described in 1 or 2 above, which contains 0.01 to 0.5% by mass of Fe, 0.01 to 0.5% by mass of Si, and 0.01 to 0.5% by mass in total of Fe and Si. The described copper alloy sheet.
4) The copper alloy according to any one of the above items 1 to 3, which has a tensile strength of 400 MPa or more, an elongation of 20% or more, and a volume resistivity of 20 to 70 μΩcm in both the rolling parallel direction and the rolling vertical direction. Board material.
5) The method for producing a copper alloy sheet according to any one of the above 1) to 4), wherein the casting [Step 1], the homogenizing heat treatment at a temperature of less than 900 ° C. [Step 2], and the hot rolling [Step 1]. 3], face milling [step 4], cold rolling 1 [step 5], trimming [step 6], annealing 1 [step 7], surface polishing [step 8], cold rolling 2 [step 9], 10 ° C Heating at a heating rate of not less than / min, holding at 400 to 850 ° C for 1 second to 5 hours, and then cooling to normal temperature at a cooling rate of not less than 20 ° C / min 2 [Step 10], Straightening [Step 11] And a step of annealing 3 [Step 12] in this order, the method for producing a copper alloy sheet material.
6) A resistor material using the copper alloy sheet according to any one of 1) to 5).

According to the present invention, it is possible to provide a copper alloy sheet material having both a small temperature coefficient of resistance and press formability having a good fracture surface, a method for manufacturing the same, and a resistor material for a resistor.

It is a conceptual diagram of a good dripping. It is a conceptual diagram of a bad dripping.

Hereinafter, the present invention will be described in detail.
<Copper alloy sheet>
In the present invention, Mn is 5.0 to 20.0% by mass, Ni is 0 to 5.0% by mass, Sn is 0 to 5.0% by mass, and Ni and Sn are 0.1 to 10.0% in total. Mass%, the balance being Cu and unavoidable impurities, and a copper alloy sheet material having a difference of 10% or less in elongation in a rolling parallel direction and a rolling vertical direction in a sheet width direction and perpendicular to the rolling parallel direction, or Mn is 5.0 to 20.0% by mass, Ni is 0 to 5.0% by mass, Sn is 0 to 5.0% by mass, and Ni and Sn are contained in a total of 0.1 to 10.0% by mass. The balance of which consists of Cu and unavoidable impurities, and whose azimuthal density of τ-fiber obtained by EBSD measurement is 4 or more in Φ = 20 to 35 ° and less than 4 in Φ = 40 to 80 °. Alloy sheet material.

≪Ingredient composition≫
The copper alloy sheet of the present invention contains Mn at 5.0 to 20.0% by mass from the viewpoint of the effect of the interaction between the Kondo effect and lattice vibration in order to reduce the temperature coefficient of resistance. Further, when the Ni content is 0 to 5.0% by mass, the Sn content is 0 to 5.0% by mass, and the total content of Ni and Sn is 0.1 to 10.0% by mass, the temperature coefficient of resistance is more effectively improved. Can be controlled.

Preferably, Mn is 5.5 to 19.0% by mass, Ni and Sn in total are 0.01 to 5.0% by mass, more preferably 6.0 to 18.0% by mass of Mn, and Ni and Sn are The total is 1.0 to 5.0% by mass. Other copper alloys contain specific unavoidable impurities.

≪Optional ingredients≫
The copper alloy sheet of the present invention contains 0.01 to 0.5% by mass of Fe, 0.01 to 0.5% by mass of Si, and 0.01 to 0.5% by mass in total of Fe and Si. Is preferred. By including Fe and Si, the tensile strength can be improved, but since excessive addition increases the resistance, the content is preferably 0.01 to 0.5% by mass.

In the composition of the alloy of the present invention, “% by mass” may be simply referred to as “%”. The elemental component in which the lower limit of the content range is described as “0%” in the component composition of the alloy means that it is a component arbitrarily added to the copper alloy sheet as needed, and the elemental component is In the case of “0%”, it means that the element component is not contained in the copper alloy sheet material or has a content less than the detection limit value. Note that “to” includes the numerical ranges at both ends.

不可 The unavoidable impurities in the present invention mean trace elements that are unintentionally mixed in from the raw material or the furnace wall of the casting furnace during melting and casting. The total amount of unavoidable impurities is generally at most 50 ppm by mass, typically at most 30 ppm by mass, more typically at most 10 ppm by mass.

≫Elongation difference≫
The copper alloy sheet material of the present invention improves the fracture surface shape at the time of pressing by reducing the anisotropy of elongation in the rolling parallel direction (hereinafter, also referred to as RD direction) and the vertical direction of rolling (hereinafter, also referred to as TD direction). And a difference in elongation between the RD direction and the TD direction is 10% or less. Here, the difference in elongation refers to the absolute value of the difference in elongation between the RD direction and the TD direction.

By setting the difference between the elongation in the RD direction and the elongation in the TD direction to 10% or less, the difference in the amount of deformation up to the fracture in the rolling parallel direction and the rolling vertical direction during the shearing of the press punching process before being incorporated into the resistor. Since the anisotropy can be reduced, the sag ratio of the press fracture surface can be reduced. It is more preferably at most 8%, further preferably at most 5%.

≪Tensile strength and elongation≫
In the copper alloy sheet of the present invention, in order to suppress deformation and micro cracks when incorporated as a resistor, the tensile strength is 400 MPa or more and the elongation is 20% or more in both the RD direction and the TD direction.

引張 In both the RD direction and the TD direction, the tensile strength is preferably from 410 MPa to 800 MPa, more preferably from 420 MPa to 750 MPa. The elongation is preferably at least 22% and less than 50%, more preferably at least 25% and less than 50%. By setting the elongation to less than 50%, the elongation up to breakage during press punching can be reduced, and sag during press punching in both the parallel rolling direction and the vertical rolling direction can be controlled to be small.

≪Volume resistivity≫
When the copper alloy sheet of the present invention is used as a resistor, the resistivity is required to detect a voltage drop in an electronic circuit to be connected, and is preferably 25 to 70 μΩcm.

≪τ-fiber (tau-fiber) ≫
Since the difference between the elongation in the RD direction and the elongation in the TD direction of the copper alloy sheet of the present invention is 10% or less, in the present invention, τ-fiber (φ1 = 90 °, φ2 = 45 °, φ = 0 to (90 °) is controlled so that the azimuth density of Φ = 20 to 35 ° is 4 or more and the azimuth density of Φ = 40 to 80 ° is less than 4.

Here, the τ fiber is defined as {0 0 1} <− 1 -1 0> (φ1 = 90 °, φ2 = 45 °, Φ = 0 °) from {1 1 0} <0 0 1> (φ1 = 90 °, φ2 = 45 °, Φ = 90 °) is a general term for the azimuth that rotates when the azimuth density of Φ = 20 to 35 ° is 4 or more. The {4 4 11｝ <11 11 -8> set The development of the structure, that Φ = 40 to 80 ° being 4 or more, means that the rolled texture {1 1 0} <0 0 1> remains. That is, the former is increased in azimuth density and the latter is reduced in azimuth to improve the drooping surface.

Note that τ-fiber uses an OIM 5.0 (trade name) manufactured by TSL Solutions Co., Ltd. as a measuring device of the EBSD method, and uses the data of the measuring device as an OIM@Analysis7.31 (EBSD data analysis software) attached to the device. ).

By controlling τ-fiber within the above range, the deformation resistance value when plastically deforming the copper alloy sheet material changes, and compared to a state without τ-fiber control, the fracture in the rolling parallel direction and the vertical direction Can be reduced, and as a result, press punching can be performed with less stress, and sag in the fracture surface shape can be reduced.
τ-fiber can be controlled by the following manufacturing method.

<Production method of copper alloy sheet>
The method for producing a copper alloy sheet according to the present invention includes:
Casting [Step 1],
A homogenizing heat treatment [step 2] for holding at less than 900 ° C for 10 minutes to 10 hours
Hot rolling [step 3],
Facing [Step 4],
Cold rolling 1 [step 5],
Trimming [Step 6],
Annealing 1 [Step 7],
Surface polishing [Step 8],
Cold rolling 2 [step 9],
Heating 2 at a temperature rising rate of 10 ° C./min or more, holding at 400 to 850 ° C. for 1 second to 5 hours, and then cooling to room temperature at a cooling rate of 20 ° C./min or more [Step 10];
Straightening [Step 11],
And each step of annealing 3 [step 12] in this order.

Each process itself is a known process or a combination of improved processes. In particular, the homogenization heat treatment process in process 2 and the annealing and cooling in process 10 are important processes for controlling the τ-fiber of the present invention. is there.

(4) In the homogenization heat treatment [Step 2], the crystal grains are suppressed from being coarsened by maintaining the temperature at less than 900 ° C. for 10 minutes to 10 hours, thereby facilitating formation of a texture later. When heat treatment is performed at 900 ° C. or higher, it is difficult to obtain an intended τ fiber.

In the annealing 2 [step 10], τ is obtained by heating at a heating rate of 10 ° C./min or more, holding at 400 to 850 ° C. for 1 second to 5 hours, and then cooling to a normal temperature at a cooling rate of 20 ° C./min or more. Controls the azimuth integration of the fiber. In particular, when the rate of temperature rise is slow, and when the holding time is out of the above range, a predetermined orientation density cannot be obtained, and anisotropy of elongation and anisotropy of sag occur.

In the present invention, treatments such as shape correction, oxide film removal, degreasing, and rust prevention may be performed between adjacent steps or after the final recrystallization annealing step. The copper alloy sheet of the present invention is extremely useful as a resistor, for example, a resistance material for a shunt resistor.

The present embodiment is an example of the present invention, and the present invention is not limited to the present embodiment. In addition, various changes or improvements can be added to the present embodiment, and embodiments to which such changes or improvements are added can be included in the present invention.

(Example 1)
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
An ingot having a predetermined alloy composition (% by mass) shown in Table 1 is produced by casting [Step 1], and a homogenizing heat treatment by holding at less than 900 ° C. for 10 minutes to 10 hours before hot rolling [Step 2]. Hot rolling (step 3) for rolling at a total processing rate of 50% or more in order to break the cast structure and obtain a uniform structure, and to remove surface oxide on both surfaces by 0.5 mm or more in order to remove oxide scales [ Step 4], cold rolling 1 for rolling at a total processing rate of 60% or more to obtain a target shape [Step 5], removing both ends of the sheet material with a dimension of less than 5% of the entire width to adjust the shape of the material edge Trimming [Step 6], annealing 1 to hold the material at 300 to 600 ° C. for 10 seconds to 1 hour to remove distortion [Step 7], surface polishing to remove an oxide film on the material surface [Step 8], To obtain the target shape and for work hardening Cold rolling 2 [Step 9] for rolling at a total processing rate of 10 to 80%, heating at a heating rate of 10 ° C./min or more to release strain and obtain Tau-fiber, at 400 to 850 ° C. for 1 second Holding for 5 hours and cooling to room temperature at a cooling rate of 20 ° C./min or more [Step 10], straightening by applying a stress of 100 MPa or more in the parallel direction of rolling to correct the warpage and bending of the sheet material [ Step 11] In order to remove residual stress of the material, annealing 3 [Step 12] of performing a heat treatment at a holding temperature of 200 to 500 ° C. for 5 seconds to 1 hour is performed in this order, and a 0.2 mm thick plate material Got.

The alloy composition is as shown in Table 1, but the balance other than the alloy components shown in Table 1 is copper and unavoidable impurities. Further, the conditions of Step 2 and Step 10 are as shown in Table 2. The following evaluation was performed about the sample obtained in this way. The measurement was performed on samples manufactured from five places at intervals of 1 m in the rolling direction on the manufactured sample, and the average value was obtained. The results are shown in Table 3. In addition, unless otherwise indicated, it performed at 23 degreeC and 50% RH atmosphere.

(Measurement and analysis of crystal orientation by EBSD measurement)
The measurement was performed by the EBSD method under the conditions of a measurement area of 64 × 104 μm 2 (800 μm × 800 μm) and a scan step of 0.1 μm. The scan step was performed in 0.1 μm steps to measure fine crystal grains. In the analysis, a square distribution function ODF (Orientation Determination Function) was confirmed from the EBSD measurement result of 64 × 104 μm 2. The electron beam was generated from a field emission electron gun. The probe system at the time of measurement is 0.015 μm.

測定 OIM 5.0 (trade name) manufactured by TSL Solutions Co., Ltd. was used as a measuring device of the EBSD method. The plate material was cut out to a size of 30 × 30 mm, polished to 板 of the plate thickness by mechanical polishing, and then subjected to distortion removal and mirror finish by electrolytic polishing.

(Measurement of temperature coefficient of resistance and volume resistivity)
The plate surface of the plate material is mirror-polished, and the plate material before and after the mirror surface polishing is subjected to a method (four-terminal method) in accordance with JIS C2525 and JIS C2526 (four-terminal method) to have a temperature coefficient of resistance in the range of 20 ° C. to 50 ° C. TCR) was measured.

を When the absolute value of the temperature coefficient of resistance TCR at 20 ° C. to 50 ° C. was 50 ppm / K or less, and the volume resistivity ρ at 20 ° C. was 20 to 70 μΩcm, the acceptable level was evaluated as ○. The thickness of the plate was measured with a micrometer.

(Cross section after press punching)
The shape of the sheet material after press punching is determined by the ratio of the sag measured in accordance with the shear test method for copper and copper alloy thin strip specified in the Japan Copper and Brass Association Technical Standard JCBA T310: 2002. evaluated.

That is, the plate was punched out using a press, a square die or the like, a cross section orthogonal to the rolling direction of the plate (press fracture surface) was exposed, and the cross section was observed using a scanning electron microscope. The conditions for punching the plate material were previously tested, and as favorable conditions, the clearance was 10 μm, the pressing speed was 200 mm / s, and the lubrication condition was no lubrication.

において In FIG. 1, reference numeral 1 denotes sag during punching, 2 denotes a shear surface, and 3 denotes a fracture surface. Here, when the sagging dimension in the thickness direction of 1 was less than 20% of the entire board thickness, it was determined that the sagging was small and the dimensions were obtained as designed.

(Tensile strength, elongation)
Data obtained by performing a tensile test according to JIS Z 2241: 2011 for each sample material (n = 3) cut out in a direction (RD direction) parallel to the rolling direction of the plate material with a predetermined test piece size. Calculated from The average values of the calculated tensile strength and elongation are shown. In this example, a level of 400 MPa or more was regarded as a pass level.

As is clear from the above, the copper alloy sheet material manufactured by the process of the present invention has good press-formability while having a small temperature coefficient of resistance.

1 sagging 2 shear surface 3 fracture surface 4 burr

Claims

Mn is 5.0 to 20.0% by mass, Ni is 0 to 5.0% by mass, Sn is 0 to 5.0% by mass, and Ni and Sn are contained in a total of 0.1 to 10.0% by mass. A copper alloy sheet material having a balance of Cu and unavoidable impurities, wherein a difference between elongation in a direction parallel to the rolling direction and elongation in a rolling direction perpendicular to the direction parallel to the rolling direction is 10% or less.
Mn is 5.0 to 20.0% by mass, Ni is 0 to 5.0% by mass, Sn is 0 to 5.0% by mass, and Ni and Sn are contained in a total of 0.1 to 10.0% by mass. The balance of which consists of Cu and unavoidable impurities, and whose azimuthal density of τ-fiber obtained by EBSD measurement is 4 or more in Φ = 20 to 35 ° and less than 4 in Φ = 40 to 80 °. Alloy sheet material.
3. The method according to claim 1, which comprises 0.01 to 0.5% by mass of Fe, 0.01 to 0.5% by mass of Si, and 0.01 to 0.5% by mass in total of Fe and Si. Copper alloy sheet material.
The copper according to any one of claims 1 to 3, wherein in both the rolling parallel direction and the rolling vertical direction, the tensile strength is 400 MPa or more, the elongation is 20% or more, and the volume resistivity is 20 to 70 µΩcm. Alloy sheet material.
The method for producing a copper alloy sheet according to any one of claims 1 to 4, wherein casting [step 1], homogenizing heat treatment at a temperature lower than 900 ° C [step 2], and hot rolling [step 3]. , Face milling [step 4], cold rolling 1 [step 5], trimming [step 6], annealing 1 [step 7], surface polishing [step 8], cold rolling 2 [step 9], 10 ° C / min. After heating at the above temperature raising rate, holding at 400 to 850 ° C. for 1 second to 5 hours, and then cooling to room temperature at a cooling rate of 20 ° C./min or more, annealing 2 [Step 10], straightening [Step 11], and A method for producing a copper alloy sheet material, comprising the steps of annealing 3 [step 12] in this order.
[4] A resistor material for a resistor, comprising the copper alloy sheet according to any one of [1] to [5].