KR20140004748A - Copper alloy sheet material and process for producing same - Google Patents

Abstract

It contains 1.0 mass% or more and 5.0 mass% or less, 0.1 mass% or more and 2.0 mass% or less of Si, and has the composition which remainder consists of copper and an unavoidable impurity, Cube orientation in the crystal orientation analysis by electron backscattering diffraction method. The crystal grains having an orientation in which the deviation from the {001} <100> is within 15 ° is 5% or more and 50% or less, and the deviation from the cube orientation {001} <100> is within 15 °. In the copper alloy sheet material dispersed in 40 or more and 100 or less in this 60 micrometer square, and its manufacturing method, it is excellent in bending workability, has excellent strength, and the anisotropy of the rolling parallel direction and the rolling vertical direction of each characteristic is excellent. The present invention provides a copper alloy sheet material suitable for connectors, terminal materials, relays, switches, and the like for automotive automobiles, such as lead frames, connectors, and terminal materials for electric and electronic devices.

Description

Copper alloy sheet and its manufacturing method {COPPER ALLOY SHEET MATERIAL AND PROCESS FOR PRODUCING SAME}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper alloy sheet material applied to lead frames, connectors, terminal materials, relays, switches, sockets, and the like for electrical and electronic equipment, and a method of manufacturing the same.

The characteristic items required for the copper alloy material used for electrical and electronic equipment applications include electrical conductivity, yield strength (yield stress), tensile strength, bending workability, stress relaxation resistance, and the like. In recent years, with the miniaturization, weight reduction, high functionality, high density mounting of electric and electronic devices, and high temperature of the use environment, demands for these characteristics have increased.

BACKGROUND ART In general, copper-based materials such as phosphor bronze, single copper, and brass are widely used as materials for electric and electronic devices. These alloys improve strength by a combination of solid solution strengthening of Sn and Zn, and work hardening by cold working such as rolling or drawing. In this method, the electrical conductivity is insufficient, and high strength is obtained by applying cold rolling at a high rolling rate, so that bending workability and stress relaxation resistance are insufficient.

As a reinforcement method which replaces this, there exists a precipitation reinforcement method which precipitates a fine 2nd phase in a material. This reinforcing method is performed in many alloy systems because in addition to increasing strength, there is an advantage of simultaneously improving the electrical conductivity. However, with the miniaturization of parts used in electronic devices and automobiles in recent years, copper alloys have been made to bend in small radius by materials of higher strength, and copper alloy sheet materials excellent in bending workability are strongly demanded. It is becoming. In addition, even in a plate material having high strength, high spring characteristics and good bending workability, it is not preferable that there is a characteristic difference in the rolling parallel direction and the rolling vertical direction, and it is important to exhibit good characteristics in any direction. In particular, when used as a microminiature terminal, it is important that fine processing is performed in a pin shape with a narrow width, and exhibit good characteristics in any direction here as well. In the conventional Cu-Ni-Si-based copper alloy, in order to obtain high strength, the rolling rate was increased to obtain a large work hardening, but this method deteriorates the bending workability as described above, resulting in high strength and good bending workability. It was difficult to make it compatible.

Several proposals are made | formed to solve this request | requirement of the improvement of bending workability by control of a crystal orientation. For example, the following proposal is made | formed in Cu-Ni-Si type copper alloy. Patent Literature 1 discloses a crystal orientation in which a grain diameter and X-ray diffraction intensity I from {311}, {220}, and {200} planes satisfy certain conditions in a Cu-Ni-Si-based copper alloy. In the case of, it is disclosed that it is excellent in bending workability. In addition, Patent Document 2 discloses that, in the case of the crystal orientation in which the X-ray diffraction strength from the {200} plane and the {220} plane satisfies certain conditions in the Cu-Ni-Si-based copper alloy, it is excellent in bending workability. Is disclosed. In addition, Patent Document 3 discloses that the Cu-Ni-Si-based copper alloy has excellent bending workability by controlling the ratio of the cube orientation {001} <100> to 50% or less. In Patent Document 4, in a Cu-Ni-Si-based copper alloy, a crystal structure in a state deformed by strong cold working is recrystallized, and the elongation is improved while changing to a crystal structure with small anisotropy. It turns out that bending workability becomes favorable by this. Patent Document 5 discloses that the Cu-Ni-Si-based copper alloy has a small strength anisotropy and excellent bending workability by controlling the ratio of grain size and cube orientation {001} <100> to 20 to 60%. It is. Patent Document 6 discloses that Cu-Ni-Si-based copper alloys impair mechanical strength, electrical conductivity, and bending workability by controlling the ratio of grain size and cube orientation {001} <100> to 5 to 50%. It is disclosed to improve fatigue characteristics without work.

In the inventions described in Patent Literature 1 and Patent Literature 2, the analysis of crystal orientations by X-ray diffraction from a specific plane relates to a very specific part of a specific surface in a distribution of crystal orientations having a certain area. In addition, in invention of patent document 3, control of a crystal orientation is performed by reduction of the rolling work rate after solution heat treatment. In addition, the area and dispersibility of cube orientation crystal grains are not described, and the bending workability and the anisotropy of strength are not disclosed. In the invention described in Patent Literature 4, crystal structures in a state deformed by strong cold rolling are recrystallized, crystal structures with small anisotropy are realized, and good bending workability is realized by improvement in elongation. Did not improve the characteristics. In the invention described in Patent Literature 5, the cube orientation is integrated by adjusting processes such as a reduction ratio in cold rolling before the solution treatment, a temperature increase rate in the solution treatment, and anisotropy in strength and bending workability. I reduce it. However, in patent document 5, since the temperature increase rate in solution treatment is slow, the temperature rise time is long, As a result, a cube orientation grain is coarse, and the equal dispersion of a cube orientation grain is inferior, Anisotropy is also great. In addition, in the invention described in Patent Document 6, the cold rolling before the solution treatment is performed at a high reduction ratio of 85 to 99.9%, and the cube orientation is integrated by adjusting the heating temperature and the holding time in the subsequent solution treatment. And improves fatigue properties. However, in patent document 6, the cube orientation crystal grains obtained as a result of the solution treatment are coarse, and the equal dispersion of the cube orientation crystal grains is inferior, and the anisotropy of strength is also large.

Moreover, as one of the characteristic items calculated | required by the copper alloy material used for an electric / electronic device use, the thing with low Young's modulus (a vertical elastic modulus) is calculated | required. In recent years, with the progress of miniaturization of electronic components such as connectors, the dimensional accuracy of terminals and tolerances of press working have become difficult. By reducing the Young's modulus of the material, the influence of the dimensional variation on the contact contact pressure can be reduced, so that the design becomes easy. Two methods of the Young's modulus are calculated from the inclination of the elastic region of the stress-strain curve by the tensile test and the method of calculating from the inclination of the elastic region of the stress-strain curve when the beam (cantilever beam) is bent. There is this.

Japanese Laid-Open Patent Publication No. 2006-009137 Japanese Laid-Open Patent Publication No. 2008-013836 Japanese Laid-Open Patent Publication No. 2006-283059 Japanese Laid-open Patent Publication 2005-350695 Japanese Laid-Open Patent Publication No. 2011-162848 Japanese Laid-Open Patent Publication No. 2011-012321

In view of the problems of the prior art as described above, the present invention is excellent in bending workability, has excellent strength, and has a low anisotropy between the rolling parallel direction and the rolling vertical direction of each characteristic. To provide a copper alloy sheet material suitable for connectors, terminal materials, relays, switches, and the like for automotive vehicle materials, such as terminal materials. Moreover, it is another subject to provide the manufacturing method suitable for obtaining the said copper alloy plate material.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly research about the copper alloy suitable for an electric and electronic component use, and in the Cu-Ni-Si type copper alloy plate material, in order to greatly improve bending workability, strength, and electroconductivity, the integration ratio of a cube orientation And correlation was found between bending workability. In addition, in the copper alloy sheet material having the crystal orientation and characteristics, an alloy composition having a function of further improving the strength is found, and in addition, the strength can be improved without impairing the conductivity or bending workability in the present alloy system. The copper alloy plate material which added the function element was found. Further, in order to realize the above crystal orientation, a manufacturing method having a specific process has been found based on the correlation between the accumulation ratio of the cube orientation and the bending workability. This invention is made | formed as a result of examination based on these knowledge.

That is, according to the present invention, the following means are provided.

(1) 1.0 mass% or more and 5.0 mass% or less, Ni 0.1 mass% or more and 2.0 mass% or less, and remainder has the composition which consists of copper and an unavoidable impurity,

In the crystal orientation analysis by the electron backscattering diffraction method, the area ratio of crystal grains having an orientation in which the deviation from the cube orientation {001} <100> is within 15 ° is 5% or more and 50% The copper alloy plate material which is below 40 and is disperse | distributed to 40 or more and 100 or less in 60 micrometer square in the deviation from the cube orientation {001} <100> within 15 degrees. .

(2) from 1.0% by mass to 5.0% by mass of Ni, from 0.1% by mass to 2.0% by mass of Si, from Sn, Zn, Ag, Mn, B, P, Mg, Cr, Zr, Fe and Hf; 0.005 mass% or more and 1.0 mass% or less are contained in total at least 1 selected, and remainder has the composition which consists of copper and an unavoidable impurity,

In the crystal orientation analysis by the electron backscattering diffraction method, the area ratio of crystal grains having an orientation in which the deviation from the cube orientation {001} <100> is within 15 ° is 5% or more and 50% or less, and the cube orientation {001} The copper alloy plate material characterized by the dispersion | distribution to 40 or more and 100 or less crystal grains which have a deviation from <100> within 15 degrees in 60 micrometer square.

3, the cube orientation {001} <100> shift is 15 ° or more than the average grain area of crystal grains having an orientation of from ² 1.8㎛ less 45.0㎛ ² (1) or (2) The copper alloy sheet material according to item.

(4) The copper alloy sheet material according to any one of (1) to (3), wherein the average grain area of the crystal grains of the base material is 50 µm ² or less.

(5) The difference between the bending coefficient in the rolling parallel direction and the bending coefficient in the rolling vertical direction is 10 GPa or less in absolute value, and the difference in the strength in the rolling parallel direction and the yield strength in the rolling vertical direction is 10 MPa or less in absolute value. The copper alloy sheet material of claim 1.

(6) Homogenization heat treatment and hot rolling are performed on the ingot obtained by casting a copper alloy material, and further formed into a thin plate by cold rolling, and then an intermediate solution heat treatment for resolving the solute atoms in the thin plate is performed. As a manufacturing method of the copper alloy plate material to perform,

The copper alloy material is made of an alloy composition of the copper alloy sheet material according to the above (1) or (2),

Performing the homogenization heat treatment at 800 ° C. or higher and 1020 ° C. or lower for 3 minutes to 10 hours,

After performing the cold rolling at a rolling rate of 80% or more and 99.8% or less

Intermediate annealing is carried out for 5 seconds to 20 hours at a temperature of 400 ° C or more and 700 ° C or less which is less than the recrystallization temperature,

After heating to 100 degreeC or more and 400 degrees C or less, after carrying out the intermediate warm rolling of 5% or more and 50% or less under the temperature,

The intermediate solution heat treatment is performed at 600 ° C. or higher and 1000 ° C. or lower for 5 seconds to 1 hour,

The manufacturing method of the copper alloy plate material which consists of each process which performs the aging precipitation heat treatment for 5 minutes-10 hours at 400 degreeC or more and 700 degrees C or less in this order.

According to the copper alloy sheet material of the present invention, the copper alloy sheet material having excellent bending workability and excellent strength and having low anisotropy in the rolling parallel direction and the rolling vertical direction of each characteristic can be provided. Therefore, it is possible to provide a copper alloy sheet material having properties particularly suited for connectors, terminal materials, relays, switches, and the like for automotive automobiles, such as lead frames, connectors, and terminal materials for electric and electronic devices.

Moreover, according to the manufacturing method of this invention, the said copper alloy plate material can be manufactured suitably.

These and other features and advantages of the present invention will become more apparent from the following description, with reference to the attached drawings as appropriate.

FIG. 1 is a diagram for explaining equal dispersion in a case where at least four groups are adjacent to four neighboring blocks.

EMBODIMENT OF THE INVENTION One Embodiment with which the copper alloy plate material of this invention is preferable is demonstrated. In addition, the "board material" in this invention shall also include "a crude material."

The copper alloy plate material of this invention contains 1.0 mass% or more and 5.0 mass% or less of Ni, 0.1 mass% or more and 2.0 mass% or less, and has the composition which remainder consists of copper and an unavoidable impurity. Preferably, Ni is made into 3.0 mass% or more and 5.0 mass% or less, and Si is made into 0.5 mass% or more and 2.0 mass% or less. Especially preferably, Ni is 4.0 mass% or more and Si is 1.0 mass% or more.

In the crystal orientation analysis by the electron backscattering diffraction method, the area ratio of the cube orientation {001} <100> (hereinafter also referred to as cube orientation area ratio) is 5% or more and 50% or less, preferably Is 10% or more and 45% or less, more preferably 15% or more and 40% or less, particularly preferably 20% or more and 35% or less.

Or a copper alloy plate material contains 1.0 mass% or more and 5.0 mass% or less of Ni, 0.1 mass% or more and 2.0 mass% or less of Si, Sn, Zn, Ag, Mn, B, P, Mg, Cr, Zr, Fe and It is good also as what contains 0.005 mass% or more and 1.0 mass% or less in total at least 1 chosen from the group which consists of Hf. The at least one sum selected from the group consisting of Sn, Zn, Ag, Mn, B, P, Mg, Cr, Zr, Fe and Hf is preferably 0.01% by mass or more and 0.9% by mass or less, more preferably 0.03 It is mass% or more and 0.8 mass% or less, Especially preferably, they are 0.05 mass% or more and 0.5 mass% or less. Also in this case, preferable content, especially preferable content of Ni and Si, and the preferable range and especially preferable range of cube orientation area ratio are the same as the above-mentioned range.

In addition, in each of the copper alloy sheet, the average grain area of crystal grains is offset from the cube orientation {001} <100> having an orientation within 15 ° is preferably not more than ² 1.8㎛ 45.0㎛ least ^2, more preferably it is more than ² 3.8㎛ 36.0㎛ ² below. And more preferably ² or more 6.0㎛ 28.8㎛ ² or less, and particularly preferably ² or more 10.0㎛ 25.0㎛ ² below.

In the present specification, the average grain area of crystal grains having an orientation in which the deviation from the cube orientation {001} <100> is within 15 ° is omitted, and the cube orientation area ratio or the area ratio of the cube orientation {001} <100>, or the like. Sometimes. In addition, the crystal grain which has an orientation from which the deviation | deviation from cube orientation {001} <100> is less than 15 degrees is abbreviate | omitted, and may be called cube orientation crystal grain or the crystal grain of cube orientation {001} <100>.

The average crystal grain size of the base material including crystal grains of the cube orientation is preferably 40㎛ ² or less, more preferably 5~30㎛ ^2. The average value of the grain area was computed from the EBSD measurement result in the range of 300x300 micrometers of a board plane, and it was set as the average grain area.

In the crystal orientation analysis by the electron backscattering diffraction method, 40 or more and 100 or less crystal grains of the cube orientation {001} <100> are distributed within 60 µm square and have equal dispersion. The crystal grains of the cube orientation {001} <100> are distributed in 60 µm square, preferably 45 or more and 95 or less, and particularly preferably have 50 or 90 or less and are equally dispersed. have.

Furthermore, as bending workability in the rolling parallel direction and the rolling vertical direction, it is preferable that no crack occurs on the bending surface by 180 ° U close bending in narrow bending processing of width 1 mm or less.

Furthermore, the difference between the bending coefficient in the rolling parallel direction (//) and the bending coefficient in the rolling vertical direction is, in absolute terms, preferably 10 GPa or less, more preferably 8 GPa or less, particularly preferably 5 GPa. It is as follows. The difference between the yield strength in the rolling parallel direction and the yield strength in the rolling vertical direction is an absolute value, preferably 10 MPa or less, more preferably 8 MPa or less, and particularly preferably 5 MPa or less. The smaller these differences are, the smaller they are, the higher the isotropy. Ideally, it is most preferable that all of these differences are 0 (zero), that is, the values in the rolling parallel direction and the rolling vertical direction are the same.

The copper alloy sheet material of the present invention has an area ratio of cube orientation {001} <100> and its average grain area, and more preferably, when the average grain area of the base material is all within the above range, Good bending characteristics can be obtained without cracking at the apex of the bent portion, resulting in reduced bending anisotropy and bearing anisotropy. On the other hand, when the area ratio is too small, or when the average grain size is too large, or when the average grain size of the base material is too large, cracks are likely to occur at the apex of the bent portion, thereby failing to obtain good bending characteristics. Strength anisotropy increases.

The copper alloy plate material of this invention contains 1.0 mass%-5.0 mass% of Ni, and 0.1 mass%-2.0 mass% of Si. As a result, a Ni-Si-based compound (Ni ₂ Si phase) precipitates in the Cu matrix, thereby improving strength and conductivity. On the other hand, if the content of Ni is too small, the strength is not obtained. If the content of Ni is too high, precipitation occurs that does not contribute to the strength improvement during casting or hot working, and the strength suitable for the added amount is not obtained, and the hot workability and the bending workability are further deteriorated. do. In addition, since Si forms Ni and Ni ₂ Si phases, when the amount of Ni is determined, the amount of Si is determined. However, when the amount of Si is too small, strength cannot be obtained. Therefore, it is preferable to make the addition amount of Ni and Si into the said range.

Next, the area ratio of cube orientation {001} <100> is demonstrated.

In order to improve the bending workability of the copper alloy sheet, the inventors investigated the causes of the occurrence of cracks in the bending portion. As a result, it was confirmed that plastic deformation was locally developed to form shear deformation zones, and local work hardening caused the formation and connection of microvoids to reach the molding limit. As a countermeasure, it was found that it is effective to increase the ratio of crystal orientation in which work hardening hardly occurs in bending deformation. That is, as mentioned above, when the area ratio of cube orientation {001} <100> is 5% or more and 50% or less, it discovered that favorable bending workability was shown.

When the area ratio of cube orientation {001} <100> is in the said range, the above-mentioned effect is fully exhibited. Moreover, since it does not fall remarkably, even if it does not carry out cold rolling after recrystallization at low rolling rate by being in the said range, it is preferable. That is, the cold rolling after the recrystallization treatment can be performed at a high rolling rate without significantly lowering the strength. On the other hand, when the area ratio of cube orientation {001} <100> is too low, bending workability will deteriorate, On the contrary, when the area ratio of cube orientation {001} <100> is too high, strength will fall. Therefore, although the area ratio of cube orientation {001} <100> is 5% or more and 50% or less from said viewpoint, this preferable range is 10% or more and 45% or less, and more preferable range is 15% or more and 40% or less. , A particularly preferable range is 20% or more and 35% or less.

Next, the other orientation of the cube orientation of the said range is demonstrated. In the copper alloy sheet material of the present invention, the S orientation {321} <436>, the copper orientation {121} <1-11>, the D orientation {4114} <11-811>, and the brass orientation {110} <1-12> , Goss orientation {110} <001>, RDW orientation {102} <010>, and the like. These azimuth components are allowed if the cube azimuth area ratio is in the above range with respect to the observed omnidirectional area.

As described above, the electron backscattering diffraction (hereinafter referred to as EBSD) method is used for the analysis of the crystal orientation in the present invention. The EBSD method is an abbreviation of Electron Back Scatter Diffraction, and is a reflection electron diffraction pattern (EBSP: electron back-scattering pattern) generated when an electron beam is irradiated to one point of a sample surface in a scanning electron microscope (SEM). Crystal orientation analysis technique that analyzes the crystal orientation and crystal structure of the local region by using.

About 1 mm square sample area containing 200 or more crystal grains, the crystal orientation was analyzed by scanning in 0.1 micrometer step. The measurement area was 300 micrometers x 300 micrometers from the magnitude | size of the crystal grain of a sample. The area ratio of each orientation is a ratio with respect to the total measurement area of the area of the crystal grain which has an orientation in which the deviation from the abnormal orientation of cube orientation {001} <100> is within 15 degrees. The information obtained by the orientation analysis by the EBSD method includes orientation information up to a depth of several tens of nm where the electron beam penetrates the sample, but is described as an area ratio in the present specification because it is small enough with respect to the area being measured. It was. In addition, since the orientation distribution is changing in the plate thickness direction, it is preferable that the azimuth analysis by the EBSD method arbitrarily takes any number in the plate thickness direction and takes the average. In this application, unless otherwise indicated, the area ratio of the crystal surface which has a certain crystal orientation shall be called what was measured in this way.

Next, the equal dispersion of the crystal grain of cube orientation {001} <100> is demonstrated.

In order to investigate the dispersibility of the cube orientation grains, the crystal orientation analysis by the EBSD method was used to scan a range of 300 µm x 300 µm in 0.1 µm steps. Was performed. The area ratio, number, average grain area, and average grain area of the base material including the cube orientation grains per cube orientation grains per block were checked, and the dispersibility was investigated. As mentioned above, the cube orientation area ratio is 5% or more and 50% or less, the number of cube orientation grains is 40 or more and 100 or less, and the average grain area per cube orientation grains is 1.8 µm ² or more and 45.0 µm per block. ² or less, and furthermore, the case where the average grain area of a base material containing cube orientation grains is 50 micrometers ² or less was quantified as equidispersity of the cube orientation crystal grains per one view (300 micrometer x 300 micrometers) in this invention. Equal dispersion multiplies the area of one block (60 μm × 60 μm = 3600 μm ² ) by the cube orientation area ratio of the block to obtain the total area of cube orientation grains per block, and the value of the total area is the cube orientation in one block. It calculates by dividing by the number of crystal grains, and calculating | requiring the average area per cube orientation crystal grain in one block. The calculated value is an average grain area. The term 'equal dispersion' here defines the average grain area and the number of cube orientation grains per block, and here, even if the distribution state of the cube orientation grains is skewed, when viewed as a whole of 300 × 300 μm in which 25 blocks are accumulated Equal dispersion can be confirmed. For example, when the bending part of the narrow width | variety pin (0.25 mm = 250 micrometer) of a microminiature connector becomes 250x250 micrometers, cube orientation group is contained in at least 4 or more blocks, and it can be said that it is equally dispersible. As shown in FIG. 1, even if a cube orientation is integrated in the corner of four adjacent blocks, dispersibility is the same, and anisotropy of rolling parallel and a perpendicular direction is small. The equal dispersion (when neighboring four blocks are at least four groups as one group) is more preferably defined as setting the area of one block smaller. For example, an area of one block is set to 30 µm square, and there are 10 to 25 cube orientation {001} <100> grains in one block, and the grain area ratio of cube orientation {001} <100> is 5 to 50%, and the average grain area of crystal grains of the cube orientation {001} <100> is 1.8~45.0㎛ ² is preferred. In this case, the average grain area of the crystal grains of the base material is preferably 40 µm ² or less.

If the average grain size of the cube orientation grains is too small, the solution heat treatment is insufficient, the unrecrystallized structure remains, and there is a possibility that the strength and the bending workability are deteriorated. On the other hand, when the average crystal area of cube orientation grains is too large, there is a high possibility that cracks (cracks) occur in portions of grains having orientations other than cube orientation grains during bending. Moreover, anisotropy may arise by the bending direction. Therefore, it is preferable that the average crystal area of the cube orientation grains is set in the above range.

In addition, since the cube orientation crystal grains are distributed in 40 or more and 100 or less in 60 µm square and have equal dispersion, good bending characteristics can be obtained without cracking at the apex of the bent portion, and flexural anisotropy and bearing anisotropy are small. Lose. On the other hand, if the number of cube orientation grains distributed in 60 µm square is too small, cracks are generated at the apex of the bent portion, so that good bending characteristics are not obtained, and flexural anisotropy and bearing anisotropy are increased. On the other hand, when the number of the said crystal grains is too large, although it is excellent in bending workability, bending anisotropy, and bearing anisotropy, strength falls.

Especially in the case of the narrow width pin (for example, width 0.25mm) for the microminiature connector which consists of the said copper alloy plate material, the area ratio is raised in the range of the area ratio of cube orientation {001} <100> grains effective for improvement of bending workability. In addition, when the average grain area of cube orientation grains is large and the distribution of cube orientation grains is uneven, there is a high possibility that cracks (cracks) occur in portions of grains having orientations other than cube orientation grains during bending. Moreover, anisotropy may arise by the bending direction. Therefore, in the crystal orientation analysis by the EBSD method, it is preferable that 40 or more cube orientation grains are distributed in 60 micrometer square, and it has equal dispersion property.

Therefore, in the copper alloy sheet material of the present invention, the average grain area and the dispersibility of the cube orientation grains are controlled. Specifically, in the intermediate warm rolling before recrystallization solution heat treatment, heating is performed to a temperature not recrystallized, and rolling is performed at a rolling rate of 5% or more under the temperature, so that the introduction and opening of deformation in the whole rolled material are performed in an appropriate state. It is possible to control. As a result, it is possible to realize equal dispersion of the cube orientation. At the same time, the average grain area of each crystal orientation can also be controlled. By controlling this dispersibility, the bending workability of a narrow width fin is raised and the anisotropy of intensity | strengths, such as bending anisotropy and a bearing anisotropy, is reduced.

Next, the subadditive element added to the copper alloy sheet material of this invention is demonstrated.

As described above, the copper alloy sheet material of the present invention is, in one preferred embodiment, in addition to the main additive elements of Ni and Si, as the subaddition elements Sn, Zn, Ag, Mn, B, P, Mg, Cr, Zr, At least one element selected from the group consisting of Fe and Hf may be included, and the content thereof is 0.005% by mass or more and 1.0% by mass or less, preferably 0.01% by mass or more and 0.9% by mass or less, based on the total of the additives. More preferably, they are 0.03 mass% or more and 0.8 mass% or less, Especially preferably, they are 0.05 mass% or more and 0.5 mass% or less. When these subaddition elements are 1.0 mass% or less in total amount, it will become difficult to produce the distortion which reduces an electrical conductivity. Moreover, as long as it is the said range, the following addition effect is fully utilized and electrical conductivity does not fall remarkably. If it is in especially preferable range, a high addition effect and a high electrical conductivity can be obtained. On the other hand, when there is too little content of an additive element, an addition effect will not fully express. On the other hand, when there is too much content of an additive element, electrical conductivity becomes low and it is unpreferable. Below, the addition effect of each subaddition element is demonstrated.

Among the subaddition elements, Mg, Sn and Zn improve the stress relaxation resistance of the copper alloy sheet. The stress relaxation resistance is further improved by the synergistic effect when added together than when added alone. In addition, there is an effect that the solder embrittlement is remarkably improved. The stress relaxation resistance is measured under conditions of 150 ° C. and 1000 hours in accordance with the Japan Electronic Materials Industry Association standard standard EMAS-3003. The cantilever method loads the initial stress of 80% of the proof strength, and sets the displacement amount after the test at 150 ° C. for 1000 hours as the stress relaxation resistance.

Among the sub-additives, Mn, Ag, B, and P improve the hot workability of the copper alloy sheet and improve the strength.

Among the sub-addition elements, Cr, Zr, Fe, and Hf are finely precipitated in the base metal in the compound and the single substance. As a single substance, Preferably it precipitates in 75 nm or more and 450 nm or less, More preferably, it precipitates in 90 nm or more and 400 nm or less, Especially preferably, it precipitates in 100 nm or more and 350 nm or less, and contributes to precipitation hardening. Furthermore, it precipitates in the magnitude | size of 50 nm-500 nm as a compound. In either case, the growth of the crystal grains is suppressed by suppressing the growth of the crystal grains, and the dispersion state of the crystal grains in the cube orientation {001} <100> is improved, thereby improving the bending workability satisfactorily.

Next, the bending workability of the copper alloy sheet material of the present invention will be described.

It is preferable that bending workability performs the 180 degree close contact bending process of the test piece which carried out the 90 degree W bending process, and the crack (crack) does not generate | occur | produce at the apex of the bending part.

In other words, the copper alloy sheet material of the present invention is a bending workability in a rolling parallel direction and a rolling vertical direction, and is 180 ° U close bending in a narrow width bending process of 1 mm or less in width, so that cracks do not occur on the bending surface. It is preferable not to.

Next, the anisotropy of the bending coefficient and the anisotropy of the proof strength will be described.

It is preferable that the difference between the bending coefficient in the rolling parallel direction (//) and the bending coefficient in the rolling vertical direction is 10 GPa or less in absolute value, and in this case, the anisotropy of the bending coefficient is small. Moreover, it is preferable that the difference of the strength of a rolling parallel direction and the strength of a rolling perpendicular | vertical direction is 10 Mpa or less in absolute value, and in this case, the anisotropy of a bearing strength is small.

Next, preferable embodiment of the manufacturing method of the copper alloy plate material of this invention is described.

In order to manufacture the copper alloy sheet material of the present invention, the ingot obtained by casting a copper alloy material is subjected to heat treatment (homogenization treatment) and hot rolling, and further formed into a thin plate by cold rolling, and then After annealing below the recrystallization temperature and heating to 100 ° C. or higher and 400 ° C. or lower, a rolling rate of 5% or more (hereinafter referred to as an intermediate warm rolling) is performed under the temperature, and thereafter, An intermediate solution heat treatment for resolving solute atoms is carried out.

The said copper alloy material is 1.0 mass% or more and 5.0 mass% or less of Ni, 0.1 mass% or more and 1.0 mass% or less, and if necessary, Sn, Zn, Ag, Mn, B, P, Mg, Cr, Zr At least one selected from the group consisting of, Fe and Hf contains 0.005% by mass or more and 1.0% by mass or less in total, and the balance has a composition composed of copper and unavoidable impurities.

The rolling ratio here is a value obtained by dividing the value obtained by subtracting the cross-sectional area after rolling from the cross-sectional area before rolling, multiplying by 100 and multiplying by 100. That is, it is represented by the following formula.

[Rolling rate] = {([cross-sectional area before rolling]-[cross-sectional area after rolling]) / [cross-sectional area before rolling]} × 100 (%)

Specifically, the following manufacturing method is mentioned as a preferable example.

The copper alloy material is cast [Step 1] to obtain an ingot. The ingot is subjected to homogenization heat treatment [step 2], hot rolling [step 3], and then immediately cooled (for example, water cooled and water quenched) [step 4]. Next, in order to remove the oxide film of a surface, surface roughening (process 5) is performed. Thereafter, cold rolling [step 6] is performed to roll at a rolling rate of 80% or more to obtain a thin plate.

Then, after performing intermediate annealing [step 7] for 5 seconds to 20 hours at a temperature of 400 ° C. or more and 700 ° C. or less, which is a temperature at which the thin plate is partially recrystallized, it is heated to 100 ° C. or more and 400 ° C. or less, and then under medium temperature. As rolling [process 8], the intermediate warm rolling of the rolling rate of 5% or more and 50% or less is performed to a thin plate.

Thereafter, an intermediate solution heat treatment [step 9] for resolving the solute atoms is performed. In the recrystallized aggregate structure of the thin plate in this intermediate solution heat treatment, the cube orientation area ratio increases.

After this intermediate solution heat treatment [step 9], aging precipitation heat treatment [step 10], finish cold rolling [step 11], and temper annealing [step 12] are performed in this order.

On the other hand, in the conventional method for producing a precipitated copper alloy, a copper alloy material is cast [step 1] to obtain an ingot, homogenized heat treatment [step 2], hot rolling [step 3], and cooling (water cooling) [step 4]. ], Face grinding [step 5], cold rolling [step 6] are performed in this order, and it is made thin. After resolving the solute atoms by performing intermediate solution heat treatment [step 9] in the temperature range of 700 ° C. or more and 1000 ° C. or less, aging precipitation heat treatment [step 10] and finishing cold rolling [step 11] and crude annealing as necessary. It is a method of satisfying the required intensity | strength by [step 12]. In this series of steps, the aggregate structure of the material is largely determined by recrystallization occurring during the intermediate solution heat treatment, and finally determined by rotation of the orientation occurring during finish rolling.

In comparison with the production method of the present invention, two steps of the intermediate annealing [step 7] and the intermediate warm rolling [step 8] have not been performed in the past.

Next, embodiment which set the conditions of each process in the manufacturing method of this invention in detail is demonstrated.

In casting [process 1], at least 1.0 mass% or more and 5.0 mass% or less of Ni are contained, and 0.1 mass% or more and 1.0 mass% or less of Si are contained, and an element is mix | blended so that it may contain suitably about other subaddition elements as needed. The remainder is dissolved in an alloy material composed of Cu and unavoidable impurities by a high frequency melting furnace, and then cooled at a cooling rate of 0.1 ° C / sec or more and 100 ° C / sec or less to obtain an ingot. Then, the ingot is subjected to homogenization heat treatment [Step 2] for 3 minutes to 10 hours at 800 ° C. or higher and 1020 ° C. or lower. Thereafter, hot rolling [step 3] is performed, and water quenching (corresponding to cooling [step 4]) is further performed. Then, the oxide film is removed in the face step [Step 5]. Thereafter, cold rolling [step 6] with a rolling ratio of 80% to 99.9% is performed to obtain a thin plate.

Next, an intermediate annealing [step 7] is carried out for 5 seconds to 20 hours at 400 ° C. or higher and 700 ° C. or lower, and after heating under conditions of 100 ° C. or higher and 400 ° C. or lower, the rolling ratio is 5% or more and 50% or less. Warm rolling [process 8] is performed. Here, warm rolling means rolling at the temperature of the said 100 degreeC or more and 400 degrees C or less.

Thereafter, the intermediate solution heat treatment [step 9] is performed for 5 seconds to 1 hour at 600 ° C. or higher and 1000 ° C. or lower. Thereafter, preferably, an aging precipitation heat treatment [step 10] for 5 minutes to 10 hours at 400 ° C. or more and 700 ° C. or less in an inert gas atmosphere such as nitrogen or argon, and a cold rolling finish of 3% or more and 25% or less. Rolling [step 11], crude annealing [step 12] for 5 seconds to 10 hours at 200 ° C. or higher and 600 ° C. or lower is performed in this order to obtain the copper alloy sheet material of the present invention.

In the manufacturing method of this invention, when it is not necessary in particular in the property and state of the board | plate material obtained, one of each process of the said roughing [step 5], finishing cold rolling [step 11], and temper annealing [step 12] It is not necessary to omit the above.

In this embodiment, in hot rolling [process 3], in order to destroy a cast structure and segregation and to make it a uniform structure in the temperature range of 700 degreeC or more and reheat temperature (1020 degreeC), and dynamic, Processing for miniaturization of crystal grains by recrystallization is performed.

In the intermediate annealing (step 7), heat treatment is performed to such an extent that the entire surface of the alloy is not recrystallized. Then, it is the temperature range which is not recrystallized, Preferably it is 100 degreeC or more and 400 degrees C or less, More preferably, it is heated to 120 degreeC or more and 380 degrees C or less, Especially preferably, it is heated to 140 degreeC or more and 360 degrees C or less, Under the temperature, Preferably 5% or more and 50% or less, more preferably 7% or more and 45% or less, particularly preferably 10 to 40% or less at a rolling rate of intermediate warm rolling [step 8], to introduce and deform processing deformation. To control.

If the rolling ratio in this intermediate warm rolling [step 8] is too low, the work deformation is small, the grains coarsen in the intermediate solution heat treatment [step 9] of the next step, the bending wrinkles become large, and the characteristics are inferior. On the other hand, if the rolling ratio in the intermediate warm rolling [step 8] is too high, the cube orientation grown by the recrystallization solution heat treatment [step 9] rotates to another orientation, and the cube orientation area ratio decreases. In addition, when the heating temperature in the intermediate hot rolling [step 8] is lower than 100 ° C., the opening of the work strain decreases. On the contrary, when the heating temperature is higher than 400 ° C., the opening of the work strain proceeds and recrystallization proceeds. In the intermediate solution heat treatment [step 9] of the next step, the uniform dispersion of the cube orientation grains in the deformed organic grain boundary movement becomes insufficient. As a result, even in the case where the heating temperature in the intermediate warm rolling [step 8] is too high or too low, flexural anisotropy as anisotropy of bending and bearing anisotropy as anisotropy in strength are produced.

In the intermediate solution heat treatment [step 9], the cube orientation area ratio increases in the recrystallized texture. If the heat treatment temperature of the intermediate annealing [step 7] before the intermediate solution heat treatment [step 9] is higher than the temperature in the above range, an oxide film is formed, which is not preferable. For this reason, the heat processing temperature in this intermediate annealing [process 7] becomes like this. Preferably it is 400 degreeC or more and 700 degrees C or less. In particular, although it is difficult to determine it uniquely, by setting the heat treatment temperature in the above-described temperature range in the intermediate annealing [step 7], the cube orientation area ratio tends to increase in the intermediate solution heat treatment [step 9].

After the intermediate solution heat treatment [step 9], aging precipitation heat treatment [step 10], finish cold rolling [step 11], and temper annealing [step 12] are performed. In the recrystallized texture formed by the intermediate solution heat treatment [step 9], in order to increase the cube orientation area ratio due to the deformed organic grain boundary movement, it is effective to perform a predetermined process by intermediate warm rolling [step 8]. On the other hand, by controlling the crystal orientation in a constant direction by intermediate warm rolling [step 8], it contributes to the development of cube orientation grains. In addition, by performing the aging precipitation heat treatment [step 10], the mechanical strength can be increased by precipitation strengthening by precipitating the additional element from the solid solution. In addition, you may finally adjust plate | board thickness by performing finish cold rolling [step 11]. In addition, by performing temper annealing [step 12], the temper of the plate may be finally adjusted.

Further, the work strain was further added by cold rolling [step 6], and heat treatment was performed at 400 ° C. or more and 700 ° C. or less for 5 seconds to 20 hours in the intermediate annealing [step 7], followed by intermediate warm rolling [step 8]. This significantly increases the cube orientation area ratio in the recrystallized aggregate structure in the intermediate solution treatment (step 9).

The above-mentioned intermediate annealing [step 7] aims at obtaining an anisotropic structure which is not completely recrystallized but partially recrystallized. In the said intermediate warm rolling [process 8], the objective is to advance introduction and opening of microscopic nonuniform deformation | transformation by rolling with a heating temperature of 100 degreeC or more and 400 degrees C or less and a rolling rate of 5% or more.

The effect of the intermediate annealing [step 7] and the intermediate warm rolling [step 8] enables the growth of cube orientation grains in the intermediate solution treatment [step 9], and the miniaturization and equal dispersion of the cube orientation grains. In the intermediate warm rolling [step 8], the deformation by rolling and the opening of deformation by heating are performed. However, both of them are properly controlled, so that the strain organic grain boundary movement of the intermediate solution heat treatment [step 9] is performed. The cube orientation grains can be improved, and the cube orientation grains can be refined and evenly distributed. That is, the cube orientation grains can be developed by introducing strains, and the refinement and equal dispersion of the cube orientation grains can be enhanced by opening the strains. In the conventional conventional method, the heat treatment such as the intermediate solution treatment [step 9] is primarily intended to recrystallize the material and reduce the strength in order to reduce the load in the next step. However, the present invention is completely different from the purpose.

Although there is no restriction | limiting in particular in the plate | board thickness of the copper alloy plate material of this invention, Usually, it is 0.03-0.50 mm, Preferably it is 0.05-0.35 mm.

It is preferable that the copper alloy plate material of this invention satisfy | fills the above-mentioned requirements, for example, satisfy | fills and has the following characteristic calculated | required by the copper alloy plate material for connectors.

It is preferable that there is no crack in a bending surface part in 180 degree close_U bending test of one bending workability of a characteristic. These detailed conditions are as described in the Examples.

It is preferable that one bending coefficient of a characteristic is 130 GPa or less. These detailed conditions are as described in the examples. Although there is no restriction | limiting in particular in the lower limit of the bending coefficient which the copper alloy plate material of this invention shows, Usually, it is 90 GPa or more.

It is preferable that one strength of a characteristic is 700 Mpa or more. More preferably, it is 750 Mpa or more. These detailed measurement conditions are as described in the Examples. Although there is no restriction | limiting in particular in the upper limit of the yield strength which the copper alloy plate material of this invention shows, Usually, it is 900 Mpa or less.

It is preferable that one conductivity of a characteristic is 5% International Annealed Copper Standard (IACS) or more. More preferably at least 10% IACS, particularly preferably at least 20% IACS. These detailed measurement conditions are as described in the Examples. Although there is no restriction | limiting in particular in the upper limit of the electrical conductivity which the copper alloy plate material of this invention shows, Usually, it is 50% IACS or less.

Example

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail based on an Example, but this invention is not limited to them.

(Examples 1-14 and Comparative Examples 1-4)

An alloy containing each of the amounts of Ni, Si, and subaddition elements shown in Table 1, the balance being made of Cu and unavoidable impurities, was dissolved in a high frequency melting furnace, and cooled at a cooling rate of 0.1 ° C / sec to 100 ° C / sec. Casting was carried out to obtain a ingot.

The ingot was subjected to homogenization heat treatment [step 2] for 3 minutes to 10 hours at 800 ° C. or more and 1020 ° C. or lower, followed by hot rolling [step 3] as a hot working at 700 ° C. or higher and 10 ° C. or lower. Water quenching (corresponding to cooling [step 4]) was further performed to obtain a hot rolled plate. Next, the surface of this hot rolled sheet was surface-treated [process 5], and the oxide film was removed. Thereafter, cold rolling [step 6] was performed at a rolling rate of 80% to 99.8% to obtain a thin plate.

Next, an intermediate annealing [step 7] of the thin plate is performed by heat treatment at 400 ° C. or higher and 700 ° C. or lower for 5 seconds to 20 hours. The intermediate warm rolling [process 8] which rolls at a rolling rate was performed.

Thereafter, intermediate solution treatment [step 9] was performed at 600 ° C. or higher and 1000 ° C. for 5 seconds to 1 hour. Next, an aging precipitation heat treatment [step 10] is carried out for 5 minutes to 1 hour at 400 ° C. or more and 700 ° C. or lower in an inert gas atmosphere, and cold rolling [step 11], 200 is finished at a rolling rate of 3% to 25%. A crude annealing [step 12] was carried out for 5 seconds or more and 10 hours or less at a temperature of not less than 600 ° C. and not more than 600 ° C. to prepare a test material of copper alloy sheet (14 in Example 1 and 4 in Comparative Example 1). The final plate thickness of each test material was 0.08 mm.

About each composition and characteristic of 14 in these Example 1 and 4 in Comparative Example 1, it is as showing in Table 1 and Table 2.

On the other hand, after each heat treatment and rolling, pickling and surface polishing were corrected by a tension leveler depending on the shape depending on the state of oxidation and roughness of the material surface. In addition, the processing temperature in hot processing [process 3] was measured with the radiation thermometer provided in the side which rolled in and the side which came out.

The following characteristic investigation was done about each test material.

(a) Cube bearing area ratio

By EBSD method, the measurement area of 0.09 mm <2> (300 micrometer x 300 micrometers) was measured on the conditions of a scan step of 0.1 micrometer. In addition, in this measurement area, 60 micrometers x 60 micrometers was made into 1 block, and it was made possible to measure a total of 25 blocks (5 blocks x 5 blocks) in one view. The scan step in this case was set to 0.1 micrometer step as mentioned above in order to measure a fine crystal grain. In the analysis, the EBSD measurement result in the measurement area of 300 μm × 300 μm was divided into 25 blocks described above, and the base material including the cube orientation area ratio, average grain area, number of crystal grains, and cube orientation grains of each block. The average grain area of was confirmed. The electron beam used as a source the hot electrons from the tungsten filament of a scanning electron microscope.

(b) 180˚ close U bending test

It processed by the punch by the press so that it might become width 0.25mm and length 1.5mm perpendicularly to a rolling direction. Nippon Shindogyokai technical standard is defined as WW bending so that the axis of bending is perpendicular to the rolling direction, and BW bending so as to be parallel to the rolling direction. Based on JCBA-T307 (2007), after the 90 degree W bending process, 180 degree close contact bending process was performed, without attaching an inner radius with a compression tester. The bending surface was observed with a scanning electron microscope of 100 times, and the presence or absence of a crack was examined. No cracks were indicated as "(good)" and those with cracks were shown as "x" (inferior). The crack has a maximum width of 30 µm to 100 µm and a maximum depth of 10 µm or more.

(c) bending coefficient

The test piece was processed by the punching by the press so that width might be 0.25 mm perpendicular to a rolling direction, and 1.5 mm in length in parallel to a rolling direction. The front and back of the test piece were measured 10 times with a cantilever, and the average value was shown.

Flexural coefficient E (GPa) is represented by following formula (1).

E = 4a / b × (L / t) ³ (1)

Where a is the slope of the displacement f and the stress w, b is the width of the specimen, L is the distance between the fixed end and the load point, and t is the thickness of the specimen.

In this test, the anisotropy of the rolling parallel direction and the rolling vertical direction of bending was confirmed.

(d) Strength [Y]

In the measurement of the bending coefficient, the yield strength Y (MPa) was calculated from the following equation (2) from the indentation amount (displacement) up to the elastic limit of each test piece.

Y = {(3E / 2) × t × (f / L) × 1000} / L (2)

E is the bending coefficient, t is the plate thickness, L is the distance between the fixed end and the load point, and f is the displacement (indentation depth).

In this test, the anisotropy of the rolling parallel direction and the rolling vertical direction of bearing capacity was confirmed.

(e) The electrical conductivity was calculated by measuring the specific resistance by four-terminal method in the thermostat maintained at the electrical conductivity [EC] ± 0.5 ° C. On the other hand, the distance between terminals was 100 mm.

In Examples 1 to 14 and Comparative Examples 1 to 4 of the present invention, the main raw materials Cu, Ni, Si, and additive elements were blended, dissolved, and cast so as to have the composition shown in Table 1.

As shown in Table 2, in the manufacturing conditions of Examples 1-14, the intermediate | middle warm rolling [process 8] made the rolling rate into 5% or more after heating to 100 to 400 degreeC. Organizations, in Examples 1 to the area ratio of cube orientation 14 are greater than 5% to 50% or less, the average crystal grain size of the cube orientation grain 1.8㎛ ² or more than ² 45.0㎛, one block (60㎛ × 60㎛) sugar The number of cube orientation grains was 40 or more and 100 or less, and the average grain size of the base material including the cube orientation grains was 50 µm ² or less. In the characteristic of Examples 1-14, the result which was excellent in all 180 degree U close bending, bending anisotropy, and bearing anisotropy was shown.

In the comparative examples 1 to 4, since the prescription | regulation in the manufacturing method of this invention was not fulfilled, the case where the cube orientation area ratio and the number of cube orientation grains per block was not satisfied was shown.

[Table 1]

[Table 2]

As shown in Table 1, 2, 1.0 mass% or more and 5.0 mass% or less of Ni, 0.1 mass% or more and 2.0 mass% or less of Si, Sn, Zn, Ag, Mn, B, At least one selected from the group consisting of P, Mg, Cr, Zr, Fe, and Hf contains 0.005% by mass or more and 1.0% by mass or less in total, and the balance has a composition consisting of copper and unavoidable impurities. in the crystal orientation analysis by, the cube orientation {001} area ratio of <100> is not less than 5% greater than 50%, and preferably in addition to these is the average grain area of crystal grains having the cube orientation 1.8㎛ ² or more 45.0㎛ ² When satisfy | filling that the average grain area of the crystal grain of a base material is 50 micrometer <^2> or less, all of the characteristic of a bending, the characteristic of a bending coefficient, and a strength of bearing were favorable. In the characteristic of curvature, a crack did not generate | occur | produce in the front part of bending. Moreover, in the characteristic of a bending coefficient, the flexural coefficient anisotropy was less than 10 GPa, and in the characteristic of a bearing capacity, the stress anisotropy was less than 10 MPa, and all were small anisotropy.

Therefore, the copper alloy plate material of this invention can be provided as a copper alloy plate material suitable for connectors, terminal materials, relays, switches, etc. for automobile vehicle materials, such as lead frames, connectors, and terminal materials for electrical and electronic devices.

Moreover, as shown in Table 2, in the sample of the comparative example, some characteristics were inferior.

That is, in Comparative Examples 1, 2 and 4, the average grain area of the cube orientation grains was too large, resulting in inferior bending characteristics, bending coefficient anisotropy, and bearing anisotropy of BW. Since the cube orientation area ratio was too small, the comparative example 3 was inferior to the characteristic (BW), bending anisotropy, and bearing anisotropy of bending.

On the other hand, the electrical conductivity showed 30 to 45% IACS.

(Conventional example)

Copper was prepared in the same manner as in Example 1 except that the alloy composition (residue of copper (Cu)) shown in Table 3 was not subjected to heating in intermediate annealing [step 7] and intermediate warm rolling [step 8]. An alloy plate was produced. The test material of the copper alloy plate material obtained as a result was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[Table 3]

[Table 4]

As apparent from Tables 3 and 4, the conventional example 1 produced without satisfying the alloy composition specified in the present invention, without performing intermediate annealing [step 7], and without subsequent heating in intermediate warm rolling [step 8]. The copper alloy sheet material of 2 has a large average grain size of the cube orientation, a small number of cube particles per block, even if the manufacturing conditions (each process and condition) other than these two processes are adopted. And the anisotropy of the strength is increased.

In addition, although the alloy composition prescribed | regulated by this invention is satisfied, the copper alloy plate material of the prior art example 3 produced without performing intermediate annealing [step 7] and heating in subsequent intermediate warm rolling [step 8] is these 2 Even if the manufacturing conditions (each process and conditions) other than the two processes were adopted, the average grain size of the cube orientation is large, the number of cube particles per block is small, and the bending coefficient and the bending coefficient are inferior. Strength of anisotropy is increased.

Apart from these, in order to clarify the difference from the copper alloy plate material which concerns on this invention about the copper alloy plate material manufactured by conventional manufacturing conditions, a copper alloy plate material is produced by the said conventional manufacturing conditions, and the said characteristic The items were evaluated. In addition, unless otherwise indicated, the thickness of each board | plate material adjusted the processing rate so that it might become the same thickness as the said Example.

(Comparative Example 101) Japanese Laid-Open Patent Publication No. 2011-162848 Conditions of Example 1 of the present invention

Copper alloy of the composition which consists of 3.2 mass% Ni, 0.7 mass% Si, 1.0 mass% Zn, and 0.2 mass% Sn was melt-molded and cast. The obtained ingot was faced, hot-rolled so that the end temperature might be 550-850 degreeC after the homogenization heat processing, and after quenching by water cooling, the oxide layer of the surface layer was removed (faceted) by mechanical polishing. Subsequently, after rolling to a predetermined plate thickness by cold rolling, cold rolling was further performed at a processing rate of 90% or more, and heated to a temperature of 800 ° C to 900 ° C at a temperature increase rate of 0.1 ° C / s or less to perform a solution treatment.

Subsequently, an aging treatment was performed at 500 degreeC. The aging treatment time was adjusted to the time at which stiffness peaks at aging at a temperature of 460 ° C. depending on the composition of the copper alloy. On the other hand, about this aging treatment time, the optimum aging treatment time was calculated | required by the preliminary experiment according to the composition of the alloy of Example 1 of this invention.

Subsequently, finish cold rolling was further performed at the rolling rate of 40% with respect to the board | plate material after the said aging treatment. Furthermore, low temperature annealing was performed at 480 degreeC for 30 second. On the other hand, grinding | polishing and face-grinding were performed along the way as needed, and plate | board thickness was made into 0.10 mm.

This was set as sample c01.

The obtained test body c01 was compared with the example which concerns on the said invention on manufacture conditions, and also intermediate-temperature rolling [step 8] is performed under the heating temperature before solution heat treatment [step 9], without performing intermediate annealing [step 7]. It wasn't. In addition, since the temperature increase rate of the solution heat treatment was slow, grain growth became remarkable near the achieved temperature, and the grain size was coarsened. In the obtained structure, the area of the cube orientation grains was larger than 150 µm ² . In addition, the anisotropy of the bending coefficient and the strength was also larger than 10 GPa and larger than 15 MPa, respectively, resulting in not satisfying the required characteristics in the present invention.

(Comparative Example 102) Japanese Patent Application Laid-Open No. 2011-12321 Examples 1 and 4

Copper alloy of the composition consisting of 2.8 mass% Ni, 0.9 mass% Si (Example 1 of the said publication), and 2.8 mass% Ni, 0.9 mass% Si, 0.1 mass% Zn, 0.1 mass% Mg , Each alloy of a copper alloy (Example 4 of the publication) composed of 0.1% by mass of Sn was air-melted with a coreless furnace (high frequency induction melting furnace) under charcoal coating, and surrounded by four sides of a copper mold. Casting was carried out with a mold to produce an ingot having a thickness of 250 mm, a width of 620 mm, and a length of 2500 mm.

Next, the SUS rod of diameter 3mm was inserted in the perpendicular direction from the tap surface of the mold upper end part to the intersection position of the width 155mm position and the thickness 125mm position of the mold, and the depth of the unsolidified part was measured. The value which reduced mold length (copper mold length) from the depth of the obtained non-solidified part was defined as the distance from the mold bottom depth to the solidification end depth. Specifically, 300 mm (Example 1 of the said publication) and 260 mm ( Example 4 of this publication. The casting speed was adjusted in the range of 50-200 mm / min so that this distance might be 250 mm or more, casting was performed, and the ingot was obtained.

250x620x300mm block of the top part was cut out and taken out from the obtained ingot, and the slice (250x15x300mm) of the cross section parallel to the casting direction was extract | collected from the center part of width 620mm. This was immersed in nitric acid for 0.5 to 1 hour, and the direction of the columnar tablet [100] axis was obtained from the macrostructure obtained by etching. The angle at which the plane perpendicular to the casting direction and the direction of the [100] axis of the columnar crystal intersect was measured. Specifically, it was 13 degrees (Example 1 of the said publication) and 11 degrees (Example 4 of the said publication).

Moreover, after homogenizing, the ingot was temperature-controlled at 500-1000 degreeC, 60-96% of rolling was performed by the total work rate, and the obtained rolling material was directly water-cooled to make a coil of about 10 mm in thickness. The surface of this rolled material was milled to remove the oxidation scale. The ratio of the cube orientation of the rolling material at this point was 5 to 95%. After that, cold rolling with a work rate of 85 to 99.8%, solution heat treatment for 5 seconds to 1 hour at 700 to 1020 ° C., finish cold rolling with a work rate of 1 to 60%, and 5 seconds to 10 hours at 200 to 600 ° C. The crude annealing was performed in the order described to obtain a test material having a thickness of 0.15 mm.

These were taken as sample d01 (Example 1 of the said publication) and d02 (Example 4 of the said publication), respectively.

The obtained test bodies d01 and d02 were subjected to intermediate temperature annealing at the heating temperature before solution heat treatment [step 9] without performing intermediate annealing [step 7], compared with the manufacturing conditions of the present invention. Also not carried out. In the obtained structure, the area ratio of the cube orientation grains was 35% in the sample d01 (Example 1 of the publication) and 7% in the sample d02 (Example 4 of the publication), but the grain growth became remarkable, the average crystal grain size of the base material including crystal grains was in a coarse to 201㎛ ² (example 4 of the publication) 254㎛ ² and d02 in the sample (example 1 of the Publication), each sample d01. In addition, the anisotropy of the bending coefficient and the strength was also larger than 10 GPa and larger than 15 MPa, respectively, resulting in not satisfying the required characteristics in the present invention.

While the invention has been described in conjunction with the embodiments thereof, it is to be understood that the invention is not to be limited by any specific details of this description, but is to be accorded the widest scope consistent with the spirit and scope of the invention as set forth in the appended claims. I think it is natural to be interpreted.

This application claims the priority based on Japanese Patent Application No. 2011-102996 by which the patent application was carried out in Japan on May 2, 2011, This content is taken in here as a part of description of this specification.

Claims (6)

It contains 1.0 mass% or more and 5.0 mass% or less of Ni, 0.1 mass% or more and 2.0 mass% or less, and the remainder has the composition which consists of copper and an unavoidable impurity,
In the crystal orientation analysis by the electron backscattering diffraction method, the area ratio of crystal grains having an orientation in which the deviation from the cube orientation {001} <100> is within 15 ° is 5%. It is more than 50% or less, and 40 or more crystal grains are disperse | distributed to 60 or less in 60 micrometer square in which the crystal | crystallization which has an orientation with a deviation from a cube orientation {001} <100> within 15 degrees is characterized by the above-mentioned. Copper alloy sheet material. 1.0 mass% or more and 5.0 mass% or less, Ni 0.1 mass% or more and 2.0 mass% or less, at least 1 selected from the group consisting of Sn, Zn, Ag, Mn, B, P, Mg, Cr, Zr, Fe, and Hf It contains 0.005 mass% or more and 1.0 mass% or less in total, and the remainder has the composition which consists of copper and an unavoidable impurity,
In the crystal orientation analysis by the electron backscattering diffraction method, the area ratio of crystal grains having an orientation in which the deviation from the cube orientation {001} <100> is within 15 ° is 5% or more and 50% or less, and the cube orientation {001} The copper alloy plate material characterized by the dispersion | distribution to 40 or more and 100 or less crystal grains which have a deviation from <100> within 15 degrees in 60 micrometer square. 3. The method according to claim 1 or 2,
Cube orientation {001}, the average grain area of crystal grains having an orientation deviation of less than 15 ° from the <100> 1.8㎛ ² or more than ² 45.0㎛ copper alloy plate. The method according to any one of claims 1 to 3,
A copper alloy sheet material, wherein the average grain area of the grains of the base material is 50 µm ² or less. 5. The method according to any one of claims 1 to 4,
A copper alloy sheet material in which the difference between the bending coefficient in the rolling parallel direction and the bending coefficient in the rolling vertical direction is 10 GPa or less in absolute value, and the difference in the strength in the rolling parallel direction and the strength in the rolling vertical direction is 10 MPa or less in absolute value. The ingot obtained by casting a copper alloy material is subjected to homogenization heat treatment and hot rolling, and further formed into a thin plate by cold rolling, and then subjected to an intermediate solution heat treatment for resolving the solute atoms in the thin plate. As a method for producing an alloy sheet,
The copper alloy material is made of an alloy composition of the copper alloy sheet material according to claim 1,
Performing the homogenization heat treatment at 800 ° C. or higher and 1020 ° C. or lower for 3 minutes to 10 hours,
After performing the cold rolling at a rolling rate of 80% or more and 99.8% or less
Intermediate annealing is carried out for 5 seconds to 20 hours at a temperature of 400 ° C or more and 700 ° C or less which is less than the recrystallization temperature,
After heating to 100 degreeC or more and 400 degrees C or less, after carrying out the intermediate warm rolling of 5% or more and 50% or less under the temperature,
The intermediate solution heat treatment is performed at 600 ° C. or higher and 1000 ° C. or lower for 5 seconds to 1 hour,
The manufacturing method of the copper alloy plate material which includes each process which performs aging precipitation heat treatment for 5 minutes-10 hours at 400 degreeC or more and 700 degrees C or less in this order.

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