JP6678757B2 - Copper plate material for insulating substrate with copper plate and method of manufacturing the same - Google Patents

Description

  The present invention relates to a copper plate material for an insulating substrate with a copper plate, and particularly to a copper plate material suitable for an insulating substrate with a copper plate of a power device and a method of manufacturing the same.

  In general, a power device uses a high voltage and a large current, so that a large amount of heat is generated, and there is a problem of deterioration of the material accompanying the heat. Therefore, in recent years, insulation and heat dissipation measures have been taken by using an insulating substrate with a copper plate in which a ceramic substrate having excellent insulating properties and heat dissipation properties is joined to a copper plate.

  For the joining method of the ceramic substrate and the copper plate, mainly, a joining method of joining via a silver brazing material or a joining method utilizing a eutectic reaction of copper without using a brazing material is used. However, in each case, heat treatment at a high temperature of 700 ° C. or more is required. In addition, aluminum nitride, alumina, silicon nitride, and the like are used for the ceramic substrate, but their thermal expansion coefficients are different from those of copper constituting the copper plate. Therefore, when the ceramic substrate and the copper plate are joined at a high temperature, a large strain tends to be generated on the entire insulating substrate due to a difference in thermal expansion coefficient. Further, since the copper plate has a higher coefficient of thermal expansion between the ceramic substrate and the copper plate, when heat treatment is performed, a tensile stress is applied to the ceramic substrate and a compressive stress is applied to the copper plate. As a result, not only the entire insulating substrate is deformed and a dimensional change is caused, but also the separation between the ceramic substrate and the copper plate material is liable to occur. Furthermore, in high-purity copper used for a copper plate material, crystal grains grow remarkably at a high temperature of 700 ° C. or more, and it becomes difficult to homogenize the structure. For this reason, there is a problem that the bonding property is deteriorated, and when strain occurs, it becomes a starting point of grain boundary destruction.

  For example, Patent Document 1 discloses a pure copper plate made of pure copper having a purity of 99.90 mass% or more and having a specified X-ray diffraction intensity ratio, as a pure copper plate used for a heat dissipation substrate. Patent Document 2 discloses a copper alloy plate having a tensile strength of 350 MPa or more and controlling the degree of integration of crystal orientation at a predetermined position as a copper alloy plate suitable for a heat-dissipating electronic component, a high-current electronic component, and the like. Is disclosed.

JP 2014-189817 A Japanese Patent No. 5475914

  However, the pure copper plate disclosed in Patent Literature 1 is said to have excellent adhesion to other members because the surface is unlikely to have irregularities due to etching. Is not considered at all. Further, the copper alloy plate disclosed in Patent Document 2 has been studied for heat resistance, but only heat resistance by heat treatment at 200 ° C. for 30 minutes is considered. Furthermore, the copper alloy plate disclosed in Patent Document 2 has a tensile strength of 350 MPa or more, and does not correspond to a range of 150 to 330 MPa suitable as a copper plate material used for an insulating substrate with a copper plate.

  Therefore, an object of the present invention is to continuously reduce the longitudinal modulus from the rolling direction to the sheet width direction, furthermore, to excel in tensile strength and electrical conductivity, and to heat-treat at a high temperature (for example, at 700 ° C to 800 ° C for 10 minutes to 5 minutes). It is an object of the present invention to provide a copper plate material for an insulating substrate with a copper plate in which the growth of crystal grains is suppressed when heat treatment for not more than time is performed, and a method for producing the same.

  The present inventors controlled the longitudinal modulus of elasticity of the copper sheet material and suppressed the growth of crystal grains at a high temperature of 700 ° C. or higher, so that the copper sheet material and the ceramic substrate could be joined at the time of joining the copper sheet material and the ceramic substrate. It has been found that the stress applied to the entire substrate caused by the difference in the thermal expansion coefficient can be reduced, and the inhomogeneity of the structure due to the growth of crystal grains and the decrease in the bonding property can be suppressed.

That is, the gist configuration of the present invention is as follows.
(1) The total content of metal components selected from the group consisting of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr is 0.1 to 2.0 ppm, and the copper content is 99.96 mass. %, And when the crystal orientation distribution function obtained from the texture analysis by EBSD is represented by Euler angles (φ1, φ, φ2), φ2 = 0 °, φ1 = 0 °, φ The average value of the azimuth density in the range of = 0 ° to 90 ° is not less than 3.0 and less than 35.0, and is in the range of φ2 = 35 °, φ1 = 45 ° to 55 °, and φ = 65 ° to 80 °. The copper plate material for an insulating substrate with a copper plate, having a rolled texture in which the maximum value of the orientation density is 1.0 or more and less than 30.0.
(2) The content of the copper is 99.99 mass% or more, and the average value of the longitudinal elastic modulus is 115 GPa or less, and the longitudinal elastic modulus is a rolling direction, a sheet width direction, and a direction therebetween. The copper plate material for an insulating substrate with a copper plate according to (1), which is measured by:
(3) The copper plate material for an insulating substrate with a copper plate according to (1) or (2), wherein the average crystal grain size is 3 μm to 100 μm.
(4) The insulating substrate with a copper plate according to any one of (1) to (3), wherein the average crystal grain size is 50 μm to 200 μm under a heat history of 700 to 800 ° C. for 10 minutes to 5 hours. Copper plate material.
(5) The copper plate material for an insulating substrate with a copper plate according to any one of (1) to (4), wherein the tensile strength is 150 to 330 MPa and the conductivity is 95% IACS or more.
(6) The method for producing a copper plate material for an insulating substrate with a copper plate according to any one of (1) to (5),
A homogenizing heat treatment step of performing a homogenizing heat treatment on the ingot obtained by casting the copper material having the composition,
After the homogenizing heat treatment step, a hot rolling step of performing hot rolling,
After the hot rolling step, a cooling step of cooling,
A facing step of facing both sides of the material to be rolled after the cooling step,
A first cold rolling step of performing cold rolling having a total working ratio of 75% or more after the facing step;
After the first cold rolling step, conditions in which the temperature raising rate is 1 to 100 ° C./sec, the reached temperature is 100 to 500 ° C., the holding time is 1 to 900 seconds, and the cooling rate is 1 to 50 ° C./sec. A first annealing step of performing a heat treatment at
After the first annealing step, a second cold rolling step of performing cold rolling with a total working ratio of 60 to 95%,
After the second cold rolling step, conditions in which the temperature rising rate is 10 to 100 ° C./sec, the reached temperature is 200 to 550 ° C., the holding time is 10 to 3600 seconds, and the cooling rate is 10 to 100 ° C./sec. A second annealing step of performing a heat treatment at
After the second annealing step, a finish rolling step of performing further rolling,
After the finish rolling step, a final annealing step of performing a final heat treatment,
After the final annealing step, a surface oxide film removing step of performing pickling and polishing,
A method for producing a copper plate material for an insulating substrate with a copper plate, comprising:

  According to the present invention, the longitudinal modulus is continuously low from the rolling direction to the sheet width direction, the tensile strength and the electrical conductivity are excellent, and the heat treatment is performed at a high temperature (for example, at 700 ° C to 800 ° C for 10 minutes to 5 hours). Heat treatment), a copper plate material for an insulating substrate with a copper plate, in which the growth of crystal grains is suppressed, and a method for manufacturing the same.

FIG. 1 is a diagram showing the results of analyzing the rolled texture of the copper sheet material of the present invention by EBSD, wherein (A) is a sectional view at φ2 = 0 °, and (B) is a sectional view at φ2 = 35 °. FIG.

  Hereinafter, preferred embodiments of the copper plate material of the present invention will be described in detail. In addition, the numerical range represented by using “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit.

  In the copper plate material of the present invention, the total content of metal components selected from the group consisting of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr is 0.1 to 2.0 ppm, and the copper content is Is 99.96 mass% or more, and when the crystal orientation distribution function obtained from the texture analysis by EBSD is represented by Euler angles (φ1, φ, φ2), φ2 = 0 °, φ1 = The average value of the azimuth density in the range of 0 °, Φ = 0 ° to 90 ° is 3.0 or more and less than 35.0, and φ2 = 35 °, φ1 = 45 ° to 55 °, Φ = 65 ° to It has a rolling texture in which the maximum value of the orientation density in the range of 80 ° is 1.0 or more and less than 30.0.

  The copper material means that a copper material (before processing and having a predetermined composition) is processed into a predetermined shape (for example, a plate, a strip, a foil, a bar, a wire, and the like). Among them, the “plate material” refers to a material having a specific thickness, being stable in shape, and spreading in the surface direction, and includes a strip material in a broad sense. In the present invention, the thickness of the copper plate material is not particularly limited, but is preferably 0.05 to 7.0 mm, and more preferably 0.1 to 6.0 mm.

[Component composition]
The copper content is at least 99.99 mass%, preferably at least 99.99 mass%. When the content of copper is less than 99.96 mass%, the thermal conductivity is reduced, and a desired heat radiation property cannot be obtained. Further, the total content of metal components selected from the group consisting of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr is 0.1 to 2.0 ppm, and 0.1 to 1.0 ppm. It is preferred that The lower limit of the total content of these metal components is not particularly limited, but is 0.1 ppm in consideration of unavoidable impurities. On the other hand, if the total content of these metal components exceeds 2.0 ppm, a desired orientation density cannot be obtained. In addition, the copper plate material contains unavoidable impurities as a balance other than copper and metal components selected from the group consisting of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr. Is also good. The unavoidable impurity means an impurity of a content level that can be unavoidably included in a manufacturing process.

  The GDMS method can be used for quantitative analysis of the above metal components other than copper. The GDMS method is an abbreviation of Glow Discharge Mass Spectrometry. Specifically, a solid sample is used as a cathode, the sample surface is sputtered using a glow discharge, and the emitted neutral particles collide with Ar and electrons in the plasma. This is a technique for analyzing the ratio of trace elements contained in metal by measuring the number of ions with a mass spectrometer.

[Rolled texture]
The copper plate material of the present invention has a rolled texture, and the rolled texture is obtained by converting a crystal orientation distribution function (ODF) obtained from texture analysis by EBSD to Euler angles (φ1, φ, φ2). ), The average value of the azimuth density in the range of φ2 = 0 °, φ1 = 0 °, φ = 0 ° to 90 ° is 3.0 or more and less than 35.0, preferably 15 or less, and The maximum value of the azimuth density in the range of φ2 = 35 °, φ1 = 45 ° to 55 °, and φ = 65 ° to 80 ° is 1.0 or more and less than 30.0, and preferably 10 or more. When the rolling direction is the RD direction, the sheet width direction (the direction perpendicular to the RD direction) is the TD direction, and the direction perpendicular to the rolling surface (RD surface) is the ND direction, the azimuth rotation about the RD direction as an axis. , Azimuth rotation about the ND direction as φ1, and azimuth rotation about the TD direction as φ2. Orientation density is a parameter used when quantitatively analyzing the abundance ratio and dispersion state of the crystal orientation in the texture, and performs EBSD and X-ray diffraction to obtain (100), (110), (112), and the like. It is calculated by a crystal orientation distribution analysis method by a series expansion method based on measurement data of three or more types of positive electrode point diagrams. In a cross-sectional view obtained by texture analysis by EBSD and fixing φ2 at a predetermined angle, the distribution of azimuth density in the RD plane is shown.

  FIGS. 1A and 1B are diagrams showing the results of analyzing the rolling texture of the copper sheet material of the present invention by EBSD. FIG. 1A is a cross-sectional view at φ2 = 0 °, and FIG. 1B is a cross-sectional view at φ2 = 35 °. A state in which the crystal orientation distribution is random is assumed to be one in which the orientation density is 1, and the number of accumulations with respect to the orientation density is represented by a contour line. 1A and 1B, a white portion indicates a high azimuth density, a black portion indicates a low azimuth density, and a gray portion indicates that the azimuth density is higher as the color is closer to white.

  In the present invention, the average value of the azimuth density in the range of φ2 = 0 °, φ1 = 0 °, and φ = 0 ° to 90 ° is 3.0 or more and less than 35.0, and φ2 = 35 ° and φ1 = When the maximum value of the azimuth density in the range of 45 ° to 55 ° and Φ = 65 ° to 80 ° is 1.0 or more and less than 30.0, the growth of crystal grains is suppressed even at a high temperature of 700 ° C or more. If the average value of the orientation density in the range of Φ = 0 ° is less than 3.0, at a high temperature of 700 ° C. or more, the crystal grains grow remarkably to a grain size of 300 μm or more, and the bonding property decreases and the load during thermal expansion decreases. Becomes larger. On the other hand, when the average value of the azimuth density in the range of Φ = 0 ° is 35.0 or more, the strength of the plate material is reduced, and when used as a copper plate material for an insulating substrate with a copper plate, deformation is likely to occur. When the maximum value of the azimuth density in the range of φ2 = 35 °, φ1 = 45 ° to 55 °, and φ = 65 ° to 80 ° is 30.0 or more, the strength of the plate material decreases, and the insulating substrate with a copper plate is provided. When it is used as a copper plate material for use, deformation tends to occur. The azimuth density in the range of φ2 = 0 °, φ1 = 0 °, and φ = 0 ° to 90 ° is generally high, but φ2 = 35 °, φ1 = 45 ° to 55 °, and φ = 65 ° to 80. The orientation density in the range of ° is locally high. Therefore, an average value is defined for the former, and a maximum value is defined for the latter.

  The EBSD method is an abbreviation of Electron Backscatter Diffraction, and specifically, is a crystal orientation analysis technology using reflected electrons generated when a sample is irradiated with an electron beam in a scanning electron microscope (SEM). In the analysis by EBSD, the measurement area and the scan step may be determined according to the size of the crystal grain of the sample. For analysis of the crystal grains after measurement, for example, analysis software OIM Analysis (trade name) manufactured by TSL can be used. Information obtained in the analysis of crystal grains by EBSD includes information up to a depth of several tens of nanometers at which an electron beam penetrates a sample. It is preferable that the measurement point in the plate thickness direction is near a position 1/8 to 1/2 times the plate thickness from the sample surface.

[Longitudinal modulus]
The average value of the modulus of longitudinal elasticity is preferably 115 GPa or less, more preferably 110 GPa or less. The lower limit of the average value of the longitudinal elastic modulus is preferably 80 GPa or more. The modulus of longitudinal elasticity is measured in the RD direction, the TD direction, and a direction therebetween. Specifically, the average value of the modulus of longitudinal elasticity is calculated by calculating the modulus of longitudinal elasticity in each direction rotated by a predetermined angle (for example, 10 °) from the RD direction to the TD direction, and then calculates the average value of the calculated values. Is calculated. If the average value of the longitudinal elastic modulus measured in the above range exceeds 115 GPa, the load stress due to thermal expansion tends to increase when heat treatment is performed to join the insulating substrate.

[Average crystal grain size]
In the copper plate material of the present invention, the average crystal grain size is preferably from 3 μm to 100 μm, more preferably from 10 μm to 90 μm. If the average crystal grain size is less than 3 μm, sufficient crystal orientation control may not be performed. On the other hand, when the average crystal grain size exceeds 100 μm, the tensile strength tends to decrease. Further, under a heat history of 10 minutes to 5 hours at 700 to 800 ° C., the average crystal grain size is preferably 50 μm to 200 μm, and more preferably 120 μm or more. If the average crystal grain size in the state subjected to the thermal history exceeds 200 μm, the bonding property decreases and the load during thermal expansion increases. Note that the crystal grain size can be measured by EBSD analysis on the RD plane of the copper sheet material. The crystal grain size in the state of having received the heat history can be measured by the same method after performing the heat treatment on the copper plate material.

[Characteristic]
In the copper plate material of the present invention, the tensile strength is preferably 150 to 330 MPa, and more preferably 190 MPa or more. If the tensile strength is less than 150 MPa, the strength is insufficient, and if the tensile strength exceeds 330 MPa, elongation and workability tend to decrease. Further, the conductivity is preferably 95% IACS or more. If the electrical conductivity is less than 95%, the thermal conductivity tends to decrease, and as a result, the heat dissipation tends to deteriorate.

  The copper plate material of the present invention can be joined to a known ceramic substrate to form a laminate. The method of joining the copper plate and the ceramic substrate is not particularly limited, but usually, the copper plate and the ceramic substrate are joined at a high temperature of 700 ° C. or higher. Since the growth of crystal grains is suppressed when the copper plate material of the present invention is subjected to heat treatment at a high temperature (for example, heat treatment at 700 ° C. to 800 ° C. for 10 minutes to 5 hours), it is bonded to a ceramic substrate. In the case of a laminate, peeling or the like is less likely to occur at a joint portion with the ceramic substrate. Therefore, the copper plate material of the present invention is excellent for an insulating substrate with a copper plate.

[Production method of copper plate material]
Next, an example of the method for producing a copper plate material of the present invention will be described.

  In the method for producing a copper sheet material according to the present invention, a melting / casting step [step 1], a homogenizing heat treatment step [step 2], a hot rolling step [step 3], a cooling step [step 4], a facing step [step] 5], first cold rolling step [step 6], first annealing step [step 7], second cold rolling step [step 8], second annealing step [step 9], finish rolling step [step 10]. And a final annealing step [Step 11] and a surface oxide film removing step [Step 12], and the processing composed of these steps is sequentially performed. In the present invention, in particular, by appropriately controlling the conditions of the first cold rolling step [Step 6], the first annealing step [Step 7], and the second annealing step [Step 9], from the RD direction of the copper sheet material. A copper plate material having a low longitudinal elastic modulus continuously in the TD direction and further having excellent tensile strength and electrical conductivity can be obtained.

  First, in a melting / casting step [step 1], a copper material having the above-described composition is melted and cast to obtain an ingot. That is, the copper material has a total content of metal components selected from the group consisting of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr of 0.1 to 2.0 ppm, and a copper content of It has a composition of 99.96 mass% or more. In the homogenizing heat treatment step [Step 2], the obtained ingot is subjected to a homogenizing heat treatment at a holding temperature of 700 to 1000 ° C and a holding time of 10 minutes to 20 hours. In the hot rolling step [step 3], hot rolling is performed so that the total working ratio is 10 to 90%. In the cooling step [Step 4], cooling (rapid cooling) is performed at a cooling rate of 10 ° C./sec or more. In the beveling step [step 5], both surfaces of the cooled material (rolled material) are beveled by about 1.0 mm each. Thereby, the oxide film on the surface of the plate material is removed.

  In the first cold rolling step [step 6], cold rolling is performed at a total working ratio of 75% or more, preferably a plurality of times. In the first cold rolling step [Step 6], if the total working ratio is less than 75%, a desired rolled texture cannot be obtained.

  In the first annealing step [Step 7], the temperature raising rate is 1 to 100 ° C./sec, the reached temperature is 100 to 500 ° C., the holding time is 1 to 900 seconds, and the cooling rate is 1 to 50 ° C./sec. Heat treatment is performed under the conditions. If the above conditions are not satisfied, a desired rolled texture cannot be obtained.

  In the second cold rolling step [step 8], cold rolling is performed at a total working ratio of 60 to 95%.

  In the second annealing step [Step 9], the temperature raising rate is 10 to 100 ° C./sec, the reached temperature is 200 to 550 ° C., the holding time is 10 to 3600 seconds, and the cooling rate is 10 to 100 ° C./sec. Heat treatment is performed under the conditions. If the above conditions are not satisfied, a desired rolled texture cannot be obtained.

  In the finish rolling step [Step 10], cold rolling is performed with a total working ratio of 10 to 60%. In the final annealing step [Step 11], heat treatment is performed under the condition that the ultimate temperature is 125 to 400 ° C. In the surface oxide film removing step [Step 12], pickling and polishing are performed for the purpose of removing and cleaning the surface of the plate material. The working ratio R (%) in the above rolling process is defined by the following equation.

R = (t0−t) / t0 × 100
In the formula, t0 is the thickness before rolling, and t is the thickness after rolling.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

(Examples 1 to 13 and Comparative Examples 1 to 17)
First, a copper material having a component composition shown in Table 1 was melted and cast to obtain an ingot [Step 1]. The obtained ingot was subjected to a homogenizing heat treatment at a holding temperature of 700 to 1000 ° C. and a holding time of 10 minutes to 20 hours [Step 2]. Then, hot rolling was performed so that the total working ratio was 10 to 90% [Step 3], and then rapid cooling was performed at a cooling rate of 10 ° C./sec or more [Step 4]. Both surfaces of the cooled material were chamfered by about 1.0 mm each [Step 5]. Next, the first cold treatment was performed at the total working rate shown in Table 2 [Step 6], and then the first annealing was performed at the heating rate, the attained temperature, the holding time, and the cooling rate shown in Table 2 [Step 6]. 7]. Next, the second cold rolling was performed at the total working ratio shown in Table 2 [Step 8] The second annealing was performed at the heating rate, the attained temperature, the holding time and the cooling rate shown in Table 2 [Step 9]. Thereafter, finish rolling was performed at a total processing rate shown in Table 2 [Step 10]. After the final annealing was performed under the condition that the reached temperature was 125 to 400 ° C. [Step 11], pickling and polishing were performed [Step 12] to prepare a copper plate material (test material).

(Measurement method and evaluation method)
<Quantitative analysis of metal components>
Each of the prepared test materials was analyzed using VG 9000 (manufactured by VG Scientific). The content (ppm) of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr contained in each test material, Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr (Table Table 1 shows the total content (ppm) of Cu and the content of Cu (mass%). Each test material may contain unavoidable impurities. Further, "-" in Table 1 means that the corresponding metal component was not detected.

<Azimuth density>
The azimuth density was measured by the EBSD method using OIM5.0HIKARI (manufactured by TSL). The measurement area was set to a range of 800 μm × 1600 μm including 200 or more crystal grains, and the scanning step was set to 0.1 μm. For analysis of the crystal grains after the measurement, analysis software OIM Analysis (trade name) manufactured by TSL was used. The crystal orientation distribution function obtained by the analysis was expressed in Euler angles. From the cross-sectional view of φ2 = 0 °, the average value of the azimuth density in the range of φ1 = 0 ° and φ = 0 ° to 90 ° (described as “range A” in Table 3) was calculated. In the sectional view of φ2 = 35 ° represented by the Euler angle, the maximum azimuth density in the range of φ1 = 45 ° to 55 ° and φ = 65 ° to 80 ° (described as “range B” in Table 3). The value was read. Table 3 shows the average value of the orientation density in the range A and the maximum value of the orientation density in the range B for each test material.

<Average crystal grain size>
The average crystal grain size was measured in the same manner as the orientation density. The average crystal grain size was calculated from all the crystal grains included in the measurement range. Table 3 shows the average crystal grain size of each test material.

<Longitudinal modulus>
From each test material, strip-shaped test pieces having a width of 20 mm and a length of 200 mm were collected in the RD direction, the TD direction, and the direction rotated every 10 ° from the RD direction to the TD direction. First, stress was applied in the length direction of the test piece using a tensile tester. Then, a strain amount of 80% of the strain amount at the time of yielding was set as a maximum displacement amount, and a displacement obtained by dividing the up to the maximum displacement amount into 10 was given. The proportional constants of strain and stress were calculated at the ten points, and the average value of each proportional constant was defined as the average value of the longitudinal elastic modulus. The case where the average value of the longitudinal elastic modulus was 115 GPa or less was evaluated as “good”, and the case where the average value exceeded 115 GPa was evaluated as “bad”. Table 3 shows the average value of the modulus of longitudinal elasticity of each test material.

<Conductivity>
The conductivity was calculated from the value of the specific resistance measured by a four-terminal method in a thermostat kept at 20 ° C. (± 0.5 ° C.). The distance between the terminals was 100 mm. The case where the conductivity was 95% IACS or more was evaluated as “good”, and the case where the conductivity was less than 95% IACS was evaluated as “poor”. Table 3 shows the conductivity of each test material.

<Tensile strength>
Three test pieces of JIS Z2201-13B were cut out from the RD direction of each test material. The tensile strength of each test piece was measured according to JIS Z2241, and the average value was calculated. The case where the tensile strength was 150 MPa or more and 330 MPa or less was evaluated as “good”, and the case where the tensile strength was less than 150 MPa or more than 330 MPa was evaluated as “bad”. Table 3 shows the tensile strength of each test material.

<Heat resistance>
After subjecting each test material to a heat treatment at 800 ° C. for 5 hours in a tube furnace under an argon atmosphere or a nitrogen atmosphere, the average crystal grain size is measured in the same manner as the above-mentioned average crystal grain size measurement method. did. When the average crystal grain size after the heat treatment was 200 μm or less, the heat resistance was evaluated as “good”, and when it exceeded 200 μm, the heat resistance was evaluated as “bad”. Table 3 shows the average crystal grain size of each test material after the heat treatment. Generally, the crystal grain size grows as the heat treatment is performed at a high temperature for a long time. That is, for a test material having an average crystal grain size of 200 μm or less after performing a heat treatment at 800 ° C. for 5 hours, the average crystal grain size is increased when the heat treatment is performed at a temperature of 700 to 800 ° C. for 10 minutes to 5 hours. It is obvious that the diameter is 200 μm or less.

  As shown in Tables 1 and 3, in Examples 1 to 13, the total content of metal components selected from the group consisting of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr is 0.1%. The composition had a composition of 1 to 2.0 ppm and a copper content of 99.96 mass% or more. In Examples 1 to 13, when the crystal orientation distribution function obtained from the texture analysis by EBSD is represented by Euler angles (φ1, φ, φ2), φ2 = 0 °, φ1 = 0 °, φ = 0. The average value of the azimuth density in the range of ° to 90 ° is not less than 3.0 and less than 35.0, and the azimuth in the range of φ2 = 35 °, φ1 = 45 ° to 55 °, φ = 65 ° to 80 ° It had a rolling texture in which the maximum value of the density was 1.0 or more and less than 30.0. Therefore, the average value of the longitudinal elastic modulus in the RD direction to the TD direction was as low as 115 GPa or less, the tensile strength was 150 to 330 MPa, and the electric conductivity was as high as 95% IACS or more. In addition, since the average crystal grain size after performing the heat treatment at 800 ° C. for 5 hours was 200 μm or less, it was found that the growth of the crystal grains was suppressed.

  On the other hand, in Comparative Examples 1, 2, 4, 6, and 8, the total content of metal components selected from the group consisting of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr is 2 It exceeded 0.0 ppm, and the average value of the azimuth density in the range of φ2 = 0 °, φ1 = 0 °, and φ = 0 ° to 90 ° was less than 3.0. Therefore, the average values of the longitudinal elastic modulus in the RD direction to the TD direction each exceeded 115 GPa. Further, since the average crystal grain size after the heat treatment at 800 ° C. for 5 hours exceeded 200 μm, the growth of the crystal grains was confirmed.

  In Comparative Examples 3 and 7, the total content of metal components selected from the group consisting of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr was as large as 150.0 ppm and 130.0 ppm, respectively, and φ2 = 0 °, φ1 = 0 °, and the average value of the azimuth density in the range of φ = 0 ° to 90 ° are as low as 2.3 and 0.1, respectively, and φ2 = 35 ° and φ1 = 45 ° to 55 °. , Φ = 65 ° to 80 °, the maximum values of the azimuth density were as high as 31.0 and 37.0, respectively. Therefore, the average values of the longitudinal elastic modulus in the RD direction from the RD direction were as high as 135 GPa and 150 GPa, respectively. The average crystal grain size after heat treatment at 800 ° C. for 5 hours was as large as 368 μm and 399 μm, respectively, and the growth of crystal grains was confirmed.

  In Comparative Example 5, the total content of metal components selected from the group consisting of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr was as large as 250.0 ppm, and φ2 = 0 ° and φ1 = 0. °, the average of the azimuth density in the range of Φ = 0 ° to 90 ° is as low as 0.8, and the azimuth in the range of φ2 = 35 °, φ1 = 45 ° to 55 °, Φ = 65 ° to 80 ° The maximum value of the density was as high as 35.0. Therefore, the average crystal grain size after heat treatment at 800 ° C. for 5 hours was as large as 456 μm, and growth of the crystal grains was confirmed.

  In Comparative Example 9, the copper content was 99.00 mass%, and the maximum value of the azimuth density in the range of φ2 = 35 °, φ1 = 45 ° to 55 °, and φ = 65 ° to 80 ° was 31. It was as high as 0. Therefore, the conductivity was as low as 93.4% IACS. Further, the average crystal grain size after heat treatment at 800 ° C. for 5 hours was as large as 400 μm, and growth of the crystal grains was confirmed.

  In Comparative Examples 10, 12, 14, and 17, the average values of the azimuth densities in the range of φ2 = 0 °, φ1 = 0 °, and φ = 0 ° to 90 ° were 1.9, 2.5, 2.9, and 1.9, respectively. It was as low as 2.9. Therefore, the average value of the longitudinal elastic modulus in the RD direction from the RD direction was as high as 129 GPa, 143 GPa, 153 GPa, and 128 GPa, respectively. The average crystal grain size after heat treatment at 800 ° C. for 5 hours was as large as 402 μm, 420 μm, 400 μm, and 399 μm, respectively, and the growth of crystal grains was confirmed.

  In Comparative Example 11, the average value of the azimuth density in the range of φ2 = 0 °, φ1 = 0 °, and φ = 0 ° to 90 ° was as high as 42.5. Therefore, the tensile strength was as low as 145 MPa. The average crystal grain size after heat treatment at 800 ° C. for 5 hours was as large as 275 μm, and growth of the crystal grains was confirmed.

  In Comparative Example 13, the maximum value of the azimuth density in the range of φ2 = 35 °, φ1 = 45 ° to 55 °, and φ = 65 ° to 80 ° was as high as 39.0. Therefore, the average value of the longitudinal elastic modulus from the RD direction to the TD direction was as high as 165 GPa, and the tensile strength was as high as 385 MPa. The average crystal grain size after heat treatment at 800 ° C. for 5 hours was as large as 435 μm, and growth of the crystal grains was confirmed.

  In Comparative Example 15, the maximum value of the azimuth density in the range of φ2 = 35 °, φ1 = 45 ° to 55 °, and φ = 65 ° to 80 ° was as high as 31.0. Therefore, the average value of the longitudinal elastic modulus in the RD direction from the RD direction was as high as 129 GPa. The average crystal grain size after heat treatment at 800 ° C. for 5 hours was as large as 380 μm, and growth of the crystal grains was confirmed.

  In Comparative Example 16, the average value of the azimuth density in the range of φ2 = 0 °, φ1 = 0 °, and φ = 0 ° to 90 ° was as low as 2.7, and φ2 = 35 ° and φ1 = 45 ° to 55. The maximum value of the azimuth density in the range of ° and Φ = 65 ° to 80 ° was as high as 32.0. Therefore, the average value of the longitudinal elastic modulus from the RD direction to the TD direction was as high as 130 GPa. Further, the average crystal grain size after heat treatment at 800 ° C. for 5 hours was as large as 432 μm, and growth of the crystal grains was confirmed.

  As described above, the copper sheet material of the present invention has a low longitudinal elasticity coefficient continuously from the rolling direction to the sheet width direction, and further has excellent tensile strength and electrical conductivity. Moreover, since the growth of crystal grains is suppressed when the copper plate material of the present invention is heat-treated at a high temperature, peeling or the like is less likely to occur at the joint portion with the ceramic substrate when joined to the ceramic substrate. Therefore, the copper plate material of the present invention is excellent for an insulating substrate with a copper plate.

Claims (6)

  When the total content of metal components selected from the group consisting of Al, Be, Cd, Mg, Pb, Ni, P, Sn and Cr is 0.1 to 2.0 ppm, and the copper content is 99.96 mass% or more. When a crystal orientation distribution function having a certain composition and obtained from texture analysis by EBSD is represented by Euler angles (φ1, φ, φ2), φ2 = 0 °, φ1 = 0 °, φ = 0 ° The average value of the azimuth density in the range of 90 ° to 90 ° is 3.0 or more and less than 35.0, and the azimuth density in the range of φ2 = 35 °, φ1 = 45 ° to 55 °, φ = 65 ° to 80 ° Characterized by having a rolled texture having a maximum value of 1.0 or more and less than 30.0.   The content of copper is 99.99 mass% or more, and the average value of the modulus of elasticity is 115 GPa or less, and the modulus of elasticity is measured in a rolling direction, a sheet width direction, and a direction therebetween. The copper plate material for an insulating substrate with a copper plate according to claim 1.   The copper plate material for an insulating substrate with a copper plate according to claim 1, wherein the average crystal grain size is 3 μm to 100 μm.   The copper for an insulating substrate with a copper plate according to any one of claims 1 to 3, wherein an average crystal grain size is 50 µm to 200 µm under a heat history of 10 minutes to 5 hours at 700 to 800 ° C. Board material.   The copper plate material for an insulating substrate with a copper plate according to any one of claims 1 to 4, wherein the tensile strength is 150 to 330 MPa and the electrical conductivity is 95% IACS or more. It is a manufacturing method of the copper-plate material for insulating substrates with a copper plate as described in any one of Claims 1 to 5,
A homogenizing heat treatment step of performing a homogenizing heat treatment on the ingot obtained by casting the copper material having the composition,
After the homogenizing heat treatment step, a hot rolling step of performing hot rolling,
After the hot rolling step, a cooling step of cooling,
A facing step of facing both sides of the material to be rolled after the cooling step,
A first cold rolling step of performing cold rolling having a total working ratio of 75% or more after the facing step;
After the first cold rolling step, conditions in which the temperature raising rate is 1 to 100 ° C./sec, the reached temperature is 100 to 500 ° C., the holding time is 1 to 900 seconds, and the cooling rate is 1 to 50 ° C./sec. A first annealing step of performing a heat treatment at
After the first annealing step, a second cold rolling step of performing cold rolling with a total working ratio of 60 to 95%,
After the second cold rolling step, conditions in which the temperature raising rate is 10 to 100 ° C./sec, the reached temperature is 200 to 550 ° C., the holding time is 10 to 3600 seconds, and the cooling rate is 10 to 100 ° C./sec. A second annealing step of performing a heat treatment at
After the second annealing step, a finish rolling step of performing further rolling,
After the finish rolling step, a final annealing step of performing a final heat treatment,
After the final annealing step, a surface oxide film removing step of performing pickling and polishing,
A method for producing a copper plate material for an insulating substrate with a copper plate, comprising:

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