JP2012117123A - Rolled copper foil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rolled copper foil which can exert stable, excellent properties for a bending fatigue life even after application of heat treatment in the range of wide temperature conditions.SOLUTION: The rolled copper foil includes: copper (Cu) as the main component with inevitable impurities; boron (B); silver (Ag); and one or more kinds of additive elements selected from an elemental group excluding copper (Cu) and silver (Ag), which has a face-centered cubic crystal structure and also has the value of stacking fault energy higher than that of copper (Cu).

Description

  The present invention relates to a rolled copper foil, and more particularly to a rolled copper foil suitably used for a flexible printed wiring board and the like.

  A flexible printed circuit (FPC) is thin and excellent in flexibility, and thus has a high degree of freedom in a mounting form on an electronic device or the like. Therefore, folding parts of folding cellular phones, movable parts such as digital cameras and printer heads, and wiring of movable parts of disk-related equipment such as Hard Disk Drive (HDD), Digital Versatile Disc (DVD), Compact Disk (CD), etc. For example, FPC is used.

  In recent years, an FPC having excellent bending fatigue life characteristics has been demanded with downsizing and higher standardization of devices. In order to increase the bending fatigue life characteristics of the FPC, it is effective to increase the bending fatigue life characteristics of the rolled copper foil as the material.

  Tough pitch copper (oxygen content of 100 to 500 mass ppm) is mainly used as the material of the copper foil used for FPC. Moreover, in order to improve the bending fatigue life characteristic of FPC, invention which adds an alloy element to tough pitch copper is made | formed.

For example, in Patent Document 1, the tough pitch copper contains one or more of Ag, Au, Pd, Pt, Rh, Ir, Ru, and Os in a range where T defined by the following formula is 100 to 400, T = [Ag] +0.6 [Au] +0.6 [Pd] +0.4 [Rh] +0.3 [Ir] +0.3 [Ru] +0.3 [Os], S, As, Sb, Bi, The total amount of Se and Te is 0.003% by weight or less (30 ppm or less), the thickness is 5 to 50 μm, and the 200 surfaces obtained by X-ray diffraction of the rolled surface after annealing at 200 ° C. for 30 minutes. The strength (I) is I / I ₀ > 20 with respect to the strength (I ₀ ) of 200 planes determined by X-ray diffraction of fine powder copper, has a semi-softening temperature of 120 to 150 ° C., and continues at room temperature for a flexible printed circuit board holding the 300N / mm ² or more tensile strength and Nobedohaku have been described.

JP 2002-167632 A

  Since the rolled copper foil for flexible printed circuit boards described in Patent Document 1 has the above-described configuration, it exhibits excellent bending fatigue life characteristics. However, when an oxide is generated from oxygen contained in the copper foil, the oxide may be a starting point for fatigue failure, and there is a limit to improving the bending fatigue life characteristics.

  In addition, when oxygen-free copper containing almost no oxide is used, since the oxygen-free copper itself has a higher softening temperature than copper containing oxygen (containing 100 to 500 ppm), the minimum condition of the usable softening temperature is increased. End up. Furthermore, when an additive element such as Patent Document 1 is used for oxygen-free copper, the softening temperature of copper is further increased, which is convenient under high temperature conditions, but cannot be used under low temperature conditions.

  Further, in the state where nothing is added to the oxygen-free copper, there is no influence of the oxide, so the temperature is low (even if the temperature is low, the temperature is higher than when oxygen-containing copper is used). In, the progress of recrystallization properly proceeds in copper foil, and good bending fatigue life characteristics are obtained. In some cases, heat treatment over a wide temperature range is not possible.

  Accordingly, an object of the present invention is to provide a rolled copper foil that exhibits excellent bending fatigue life characteristics even after heat treatment in a wide temperature range.

  In order to solve the above problems, the present invention has a crystal structure other than copper (Cu) and inevitable impurities as main components, boron (B), silver (Ag), copper (Cu) and silver (Ag). A rolled copper foil characterized by comprising one or more additional elements selected from the group of elements having a face-centered cubic and stacking fault energy value greater than copper (Cu) To do.

  Further, the rolled copper foil may contain 0.002% by weight or less (20 ppm or less) of oxygen.

  In the rolled copper foil, the thickness is preferably 20 μm or less.

  Further, the boron (B) is 0.003% to 0.05% by weight (30 ppm to 500 ppm), and the silver (Ag) is 0.002% to 0.025% by weight (20 ppm to 250 ppm). The following are preferable:

  Furthermore, the additive element is preferably nickel (Ni) and / or aluminum (Al).

  Further, the nickel (Ni) and / or aluminum (Al) is preferably contained in a total amount of at least one of 0.003% by weight or more and 0.03% by weight or less (30 ppm or more and 300 ppm or less).

  The rolled copper foil of the present invention can stably exhibit excellent bending fatigue life characteristics even after heat treatment in a wide temperature range.

It is a figure which shows the flow of manufacture of the rolled copper foil which concerns on embodiment of this invention. It is a figure which shows the outline | summary of the test method of a bending fatigue life test (sliding bending test).

(Outline of rolled copper foil)
The rolled copper foil which concerns on this Embodiment is a rolled copper foil used for flexible wiring members, such as a flexible printed wiring board, for example. Specifically, the rolled copper foil according to the present embodiment includes copper (Cu) and inevitable impurities as main components, boron (B), silver (Ag), copper (Cu), and silver (Ag). Other than the above, it is configured to include one or more additive elements and elements selected from the group of elements having a crystal structure of face-centered cubic and a stacking fault energy value larger than copper (Cu). . And as an example, the rolled copper foil which concerns on this Embodiment is the rolled copper foil obtained after passing through the final cold rolling process of the manufacturing process of the rolled copper foil mentioned later, and before going through recrystallization annealing. For example, it is formed to have a thickness of 50 μm or less, preferably 20 μm or less for the purpose of use in a rolled copper foil for FPC.

(Copper (Cu))
The rolled copper foil according to the present embodiment is formed using, for example, oxygen-free copper or a copper material equivalent to oxygen-free copper as a base material. Here, “oxygen-free copper” according to the present embodiment is, for example, oxygen-free copper specified by JIS C1020 and having a purity of 99.96% or more, but the oxygen content is not completely zero. It is not excluded that oxygen of several ppm (0.000 several percent) is contained in oxygen-free copper. Therefore, the rolled copper foil according to the present embodiment is formed by containing 0.002% by weight or less (that is, 20 ppm or less) of oxygen as an example. In addition, in order to suppress that an oxide produces | generates in rolled copper foil, it is preferable to further reduce oxygen content.

  Further, the inevitable impurities such as sulfur (S) are dissolved in the oxygen-free copper, so that the softening temperature of the oxygen-free copper tends to increase. On the other hand, if the inevitable impurities (for example, S) react with a predetermined additive element to form a compound to eliminate the solid solution in the oxygen-free copper, the softening temperature of the oxygen-free copper tends to decrease. .

(Boron (B))
Boron (B) serves to lower the softening temperature of the produced rolled copper foil, that is, to start recrystallization from a lower temperature. Here, the reason why the upper limit of the addition amount of boron (B) is set to 0.05 wt% (500 ppm) is that boron in copper as a base material in the manufacturing equipment for rolled copper foil according to the present embodiment ( This is because the maximum solid solution amount of B) is about 0.05% by weight. Moreover, the reason for setting the lower limit of the addition amount of boron (B) to 0.003% by weight (30 ppm) is to reduce the softening temperature of the rolled copper foil produced from a practical viewpoint to an appropriate temperature, This is because of the minimum amount that can be controlled in mass production.

Moreover, the knowledge which the inventor acquired regarding boron (B) is as follows.
The rolled copper foil according to the present embodiment is formed using oxygen-free copper or copper equivalent to oxygen-free copper as a base material. First, boron (B) forms a compound with inevitable impurities such as sulfur (S). Here, when S or the like is dissolved in the base material, the softening temperature of the base material may be increased. However, S or the like and boron generate a compound to suppress the solid solution of S or the like in the base material. it can. Thereby, it can suppress that the softening temperature of a base material rises. The reason why the softening temperature of ordinary oxygen-free copper is high is considered that one of the major factors is that S, which is an inevitable impurity, is dissolved in the base material. However, the reason why the softening temperature of ordinary oxygen-free copper is high cannot be completely explained. In other words, there are other major factors, but it is not clear at present. However, it is an experimental fact that the softening temperature of oxygen-free copper to which B is added is lower than that of normal oxygen-free copper to which B is not added.

(Silver (Ag))
Silver (Ag) has an effect of suppressing the growth rate of crystal grains in recrystallization of a rolled copper foil to be produced.

(Nickel (Ni) and / or Aluminum (Al))
Other than copper (Cu) and silver (Ag), nickel (Ni) and / or aluminum (Al) can be considered as an element having a crystal structure of face-centered cubic and a stacking fault energy value larger than Cu.

  Table 1 shows the value of stacking fault energy (Hiroshi Kimura, “Concept of Material Strength”, Agne Technology Center Co., Ltd., February 10, 2004, revised edition 2nd edition, p.134) Than).

  Here, the inventors considered the stacking fault energy and the bending life characteristics as follows from the viewpoint of the metal material and the knowledge obtained through experiments so far. The copper foil with higher stacking fault energy, the easier it is for dislocations in the copper crystal to move during the bending operation (dislocations can jump over the crystal grain boundaries of copper), so the accumulation of dislocations at the crystal grain boundaries That is, the accumulation of metal fatigue is delayed. That is, it is considered that the bending life characteristics of a copper alloy foil manufactured using a copper alloy having a reduced stacking fault energy will be reduced. Therefore, when copper is alloyed, the stacking fault energy must not be reduced due to the flex life characteristics.

  In general, it is known that the larger the stacking fault energy, the smaller the expansion of dislocations. Nickel (Ni) and aluminum (Al) used as alloy elements (additive elements) of the present embodiment are shown in Table 1. Since each stacking fault energy is large, the extension of dislocations is very small. It is also generally known that stacking fault energy is reduced by alloying Cu. Therefore, by adding an alloying element with a large stacking fault energy to Cu and dissolving it, it was thought that the decrease in stacking fault energy could be suppressed and the expansion of dislocations could be suppressed. As a result, excellent bending life characteristics were obtained, and the present invention was achieved. The stacking fault energy of the copper alloy obtained in the examples described later has not been measured because it is very difficult to measure, but since excellent flex life characteristics have been obtained, the decrease in stacking fault energy is suppressed. The inventor believes that

  Here, nickel (Ni) and aluminum (Al) are involved not only in stacking fault energy but also in the growth rate of crystal grains in recrystallization of the manufactured Cu alloy. However, since it cannot be applied universally to CCL processes with various temperature conditions (150 ° C. to 400 ° C., 1 minute to 120 minutes) using only Al and Ni as described later, Ag is also added. Then, it can be applied universally under a wide range of temperature conditions. Note that the effect of suppressing the growth rate of crystal grains during recrystallization is higher for Ag than for Ni or Al.

(Method for producing rolled copper foil)
FIG. 1 is a flowchart showing a flow of manufacturing a rolled copper foil according to an embodiment of the present invention. Hereinafter, the manufacturing method of rolled copper foil is demonstrated, referring the flowchart shown in FIG.

  First, an ingot (that is, an ingot) of a copper alloy material is prepared as a raw material (ingot preparation step: step 10, hereinafter, “step” is expressed as “S”). For example, oxygen-free copper (for example, JIS H3100, JIS C1020, etc.) having an oxygen (O) content of 2 ppm or less as a base material, and a predetermined amount of nickel (Ni) and / or aluminum (Al) in total An ingot of copper alloy material containing boron (B) and a predetermined amount of silver (Ag) is prepared.

  Next, the ingot is hot rolled to produce a plate material (hot rolling step: S20). Subsequent to the hot rolling step, a step of cold rolling the plate material (cold rolling step: S32) and a step of annealing the cold rolled plate material (intermediate annealing step: S34) are repeated a predetermined number of times. Implement (S30: Loop). In addition, an intermediate annealing process (S34) is a process of relieving work hardening of the board | plate material in which cold rolling was given. Thereby, a copper strip called “dough” (hereinafter, sometimes referred to as “copper strip before the final cold rolling process”) is manufactured.

  Subsequently, the copper strip is subjected to a predetermined annealing treatment (dough annealing step: S40). In the dough annealing step, it is preferable to carry out a heat treatment that can sufficiently relieve the processing strain caused by each step before the dough annealing step, for example, a substantially complete annealing treatment. Subsequently, the “fabric” subjected to the annealing treatment (hereinafter referred to as “annealed fabric”) is subjected to cold rolling (final cold rolling step (also referred to as finish rolling step): S50). Thereby, the rolled copper foil which has the predetermined thickness which concerns on this Embodiment is manufactured.

  In addition, when using the rolled copper foil which concerns on this Embodiment obtained as mentioned above for manufacture of FPC, the rolled copper foil which concerns on this Embodiment is thrown into the manufacturing process of FPC mentioned later continuously can do. In this case, first, surface treatment etc. are performed with respect to the rolled copper foil which passed through the last cold rolling process (surface treatment etc. process: S60). Next, the rolled copper foil subjected to the surface treatment or the like is supplied to the FPC manufacturing process (FPC manufacturing process: S70). By passing through the FPC manufacturing process (S70), it is possible to manufacture an FPC including the surface-treated rolled copper foil obtained by subjecting the rolled copper foil according to the present embodiment to a surface treatment.

(FPC manufacturing process)
The outline of the FPC manufacturing process will be described below. The FPC manufacturing process includes, for example, a process of forming a copper clad laminate (CCL) by bonding a copper foil for FPC and a base film (base material) made of a resin such as polyimide, and etching into the CCL. A step of forming circuit wiring by a technique such as the above (wiring forming step) and a step of performing surface treatment (surface treatment step) for the purpose of protecting the wiring on the circuit wiring. As a CCL process, after laminating a copper foil and a substrate via an adhesive, the adhesive is cured and adhered by heat treatment to form a laminated structure (copper foil / adhesive / base film: 3-layer CCL). And a laminated structure (copper foil / base film: two-layer CCL) by directly bonding the surface-treated copper foil directly to the base material without using an adhesive, followed by heating and pressing There are two types of methods, and a method of forming each of which can be used.

  Here, in the FPC manufacturing process, a copper foil that has been cold-rolled from the viewpoint of ease of manufacture, that is, a work-hardened copper foil may be used. This is because the copper foil softened by annealing is likely to be deformed (for example, deformation such as elongation, wrinkle, fold, etc.) when the copper foil is cut or laminated on a base material, resulting in a defective product. This is because there are cases in which

  On the other hand, when the copper foil is subjected to recrystallization annealing, the bending fatigue life characteristics of the copper foil are remarkably improved as compared with the case where the copper foil is rolled. Therefore, it is preferable to employ a manufacturing method that also serves as recrystallization annealing of the copper foil in the heat treatment for closely attaching and integrating the base material and the copper foil in the CCL process described above.

  In addition, although the heat treatment conditions for the recrystallization annealing can be changed according to the contents of the CCL process, as an example, the heat treatment is performed at a temperature of 150 ° C. or higher and 400 ° C. or lower for a time of 1 minute or longer and 120 minutes or shorter. . Further, the recrystallization annealing can be performed in a separate process instead of the heat treatment performed in the CCL process. A copper foil having a recrystallized structure can be produced by heat treatment within the range of such temperature conditions. Here, in FPC, the bending fatigue life of a base film made of a resin such as polyimide is remarkably longer than the bending fatigue life of a copper foil. Therefore, the bending fatigue life of the entire FPC greatly depends on the bending fatigue life of the copper foil.

(Effect of embodiment)
The rolled copper foil according to the embodiment of the present invention includes a predetermined amount of boron (B), a predetermined amount of silver (Ag), a predetermined amount of nickel (Ni), and / or oxygen-free copper as a base material. By containing aluminum (Al), the softening temperature (recrystallization temperature) can be lowered, and the growth rate of crystal grains after recrystallization can be moderated. Therefore, this copper foil is suitable in a wide temperature condition range from a CCL manufacturing process under low temperature conditions (for example, 150 ° C. × 120 minutes) to a CCL manufacturing process under high temperature conditions (for example, 400 ° C. × 5 minutes). Recrystallization can be obtained and excellent bending fatigue life characteristics can be exhibited. Thereby, the rolled copper foil which concerns on this Embodiment can respond | correspond to the heat processing of various conditions in a CCL manufacturing process (FPC manufacturing process), for example.

  Hereinafter, the rolled copper foil of this invention is demonstrated more concretely using an Example. Note that the present invention is not limited in any way by the following examples.

  First, the component composition in each example was manufactured in such a manner that the concentration of each element was varied and the other elements were fixed in concentration. However, in the case of manufacturing a copper alloy, large and small variations occur depending on the scale of the manufacturing process with respect to the concentration to be manufactured (target concentration). As for the fixed concentrations, the target value of the fixed composition of Ni and / or Al is 120 ppm, the target value of the fixed composition of B is 120 ppm, and the target value of the fixed composition of Ag is 100 ppm. The numerical values shown in bold in Tables 2 to 4 described later are the analysis results of the fixed composition, but such variations are unavoidable. Moreover, since oxygen is stably produced at 2 to 3 ppm with normal oxygen-free copper, Examples 19, 20, 21, 40, 41, 42, 61, 62, 63 and Comparative Examples 7, 8, 15 , 16, 23, and 24 were manufactured with an increased oxygen concentration. Here, the manufacturing method in the case of increasing the oxygen concentration was manufactured by opening the lid of the melting furnace in the middle of casting and increasing the oxygen concentration during casting in a normal oxygen-free copper manufacturing facility. Therefore, there was no target concentration of oxygen for the oxygen concentration other than the usual 2-3 ppm, and the oxygen concentration was measured for the resulting product, and the concentration portion corresponding to the examples and comparative examples was collected as a result. .

(Examples 1-6)
First, after the main raw material having oxygen-free copper as a base material was melted in a melting furnace, nickel (Ni), boron (B), silver (Ag) was added to the melt, and the thickness was 150 mm, An ingot having a width of 500 mm was produced (ingot preparation step). Here, the concentration of Ni was varied between 30 to 300 ppm for 6 conditions, and the concentrations of B, Ag, and oxygen were fixed.

  Next, according to the rolled copper foil manufacturing method according to the embodiment, the ingot was hot-rolled to produce a 10 mm plate (hot rolling step). Subsequently, cold rolling (cold rolling process) and annealing treatment (intermediate annealing process) were repeated on the plate material to produce a “dough”. Then, the “fabric” was subjected to an annealing treatment (fabric annealing step). The annealing treatment in the dough annealing process was carried out by holding at a temperature of about 750 ° C. for about 1 minute. Next, the cold-rolled fabric subjected to the fabric annealing step was cold-rolled (final cold-rolling step). Thereby, the rolled copper foil which concerns on Examples 1-6 whose thickness is 0.012 mm (12 micrometers) was produced.

(Examples 7 to 12)
First, after the main raw material having oxygen-free copper as a base material was melted in a melting furnace, nickel (Ni), boron (B), silver (Ag) was added to the melt, and the thickness was 150 mm, An ingot having a width of 500 mm was produced (ingot preparation step). Here, the concentration of B was varied between 30 to 480 ppm for 6 conditions, and the concentrations of Ni, Ag and oxygen were fixed.

  Next, the rolled copper foil which concerns on Examples 7-12 whose thickness is 0.012 mm was produced according to the manufacturing method of the rolled copper foil which concerns on embodiment similarly to the above.

(Examples 13 to 18)
First, after the main raw material having oxygen-free copper as a base material was melted in a melting furnace, nickel (Ni), boron (B), silver (Ag) was added to the melt, and the thickness was 150 mm, An ingot having a width of 500 mm was produced (ingot preparation step). Here, the concentration of Ag was varied between 20 to 250 ppm for 6 conditions, and the concentrations of Ni, B, and oxygen were fixed.

  Next, the rolled copper foil which concerns on Examples 13-18 whose thickness is 0.012 mm was produced according to the manufacturing method of the rolled copper foil which concerns on embodiment similarly to the above.

(Examples 19 to 21 and Comparative Examples 7 and 8)
First, after the main raw material having oxygen-free copper as a base material was melted in a melting furnace, nickel (Ni), boron (B), silver (Ag) was added to the melt, and the thickness was 150 mm, An ingot having a width of 500 mm was produced (ingot preparation step). Here, as described above, the oxygen concentration was increased by opening the lid of the melting furnace in the middle of casting to mix air. Therefore, the oxygen concentration of the manufactured ingot produced a concentration gradient when the melting furnace was opened. In this concentration gradient, the portion of 20 ppm or less which is the oxygen concentration range of the present invention was sampled and used as Examples 19-21. Similarly, Comparative Examples 7 to 8 were collected from 20 ppm or more. The oxygen concentrations of Comparative Example 7 and Comparative Example 8 are considerably higher than 20 ppm, which is the upper limit of the oxygen concentration range of the present invention, and are 38 ppm and 68 ppm, respectively. This is because the concentration gradient of the portion was steep, and the sample was taken from a portion where a relatively stable material length could be obtained.

  Next, according to the rolled copper foil manufacturing method according to the embodiment, the rolled copper foils according to Examples 19 to 21 and Comparative Examples 7 and 8 having a thickness of 0.012 mm were produced in the same manner as in the above Examples. .

(Comparative Examples 1-6)
In Comparative Example 1 and Comparative Example 2, the Ni concentration was less than 30 ppm and more than 300 ppm, and the B, Ag, and oxygen concentrations were fixed. Further, in Comparative Example 3 and Comparative Example 4, the B concentration was less than 30 ppm and more than 500 ppm, and Ni, Ag, and oxygen concentrations were fixed. In Comparative Example 5 and Comparative Example 6, the concentration of Ni, B, and oxygen was fixed by setting the Ag concentration to less than 20 ppm and more than 250 ppm.

  The ingots of Comparative Examples 1 to 6 produced rolled copper foils according to Comparative Examples 1 to 6 having a thickness of 0.012 mm under the same conditions as the rolled copper foil manufacturing method according to the embodiment.

Table 2 is a table showing the component concentrations (analytical concentrations) of the above Examples and Comparative Examples. Component concentrations were quantified using ICP emission spectroscopy.

  Here, the numerical values in the table are displayed in units of 5 ppm. However, oxygen is expressed in units of 1 ppm (1 ppm = 0.0001%). The component composition in bold in the table is a fixed value. The target value of the fixed composition of Ni and / or Al is 120 ppm, the target value of the fixed composition of B is 120 ppm, the target value of the fixed composition of Ag is 100 ppm, and the target value of the fixed composition of oxygen is that of oxygen-free copper. The concentration is 2-3 ppm. Tables 3 and 4 below are also displayed in the same units, and the target values of the fixed composition of each element are the same.

  In the manufacture of copper alloys, apart from oxygen, the alloy elements Ni, Al, B, and Ag have the same fixed composition as described above, but actually, the degree shown in Table 2 varies. Since the experiment of the present invention was performed on a laboratory scale, it was suppressed with the variation of the degree shown in Table 2, but it should be added that when the mass production process is performed, the variation may become larger. .

(Examples 22 to 42 and Comparative Examples 9 to 16)
In Examples 22-42 and Comparative Examples 9-16, the Ni part in Examples 1-21 and Comparative Examples 1-8 was made into Al, and it manufactured on the same conditions. The manufacturing method and manufacturing conditions are the same except that Ni is changed to Al.

  Table 3 is a table showing the component concentrations (analytical concentrations) of the above Examples and Comparative Examples.

(Examples 43 to 63 and Comparative Examples 17 to 24)
In Examples 43 to 63 and Comparative Examples 17 to 24, the Ni portion in Examples 1 to 21 and Comparative Examples 1 to 8 was made Ni + Al and manufactured under the same conditions. The manufacturing method and manufacturing conditions are the same except that Ni is changed to Ni + Al.

Table 4 is a table showing the component concentrations (analytical concentrations) of the above Examples and Comparative Examples.

(Bending fatigue life test)
The bending fatigue life test was performed in accordance with the IPC standard using a sliding bending test apparatus (model: SEK-31B2S) manufactured by Shin-Etsu Engineering Co., Ltd.

  As shown in FIG. 2, the sliding bending test apparatus 2 is in contact with the sample fixing plate 20 that holds the rolled copper foil 10, the screw 20 a that fixes the rolled copper foil 10 to the sample fixing plate 20, and the rolled copper foil 10. The vibration transmission unit 30 that transmits vibration to the rolled copper foil 10 and the oscillation driver 40 that vibrates the vibration transmission unit 30 in the vertical direction are provided.

  Specifically, after producing a test piece having a width of 12.5 mm and a length of 220 mm from each of the rolled copper foils (thickness 0.012 mm, ie, 12 μm) according to Examples 1 to 63 and Comparative Examples 1 to 24 The test piece was subjected to recrystallization annealing at 160 ° C. for 120 minutes. Thereafter, a bending fatigue life test was performed.

  Moreover, after producing the test piece of width 12.5mm and length 220mm from each of the rolled copper foil (thickness 0.012mm, ie, 12 micrometers) which concerns on Examples 1-63 and Comparative Examples 1-24, this test The piece was subjected to recrystallization annealing at 400 ° C. for 5 minutes. Thereafter, a bending fatigue life test was conducted in the same manner.

  The test conditions of the bending fatigue life test are as follows: the curvature R of the rolled copper foil is 1.5 mm, the amplitude stroke of the vibration transmitting unit 30 is 10 mm, and the frequency of the oscillation driver 40 is 25 Hz (that is, the amplitude speed is 1500 times / minute). Was used. Further, the direction of the test piece length of 220 mm, that is, the longitudinal direction of the rolled copper foil 10 was set to be the rolling direction. The measurement was performed five times for each sample, and the average values (rounded off to the last three digits) of the five execution results were compared with each other. The results are shown in Table 5 and Table 6, respectively.

Table 5 shows the results of samples heat-treated at 160 ° C. for 120 minutes, and Table 6 shows the results of samples heat-treated at 400 ° C. for 5 minutes.

  Referring to Table 5 and Table 6, in the case of the rolled copper foils according to Examples 1 to 63, in both conditions of 160 ° C. × 120 minutes of low temperature conditions and 400 ° C. × 5 minutes of high temperature conditions, It was shown that the rolled copper foil has a very excellent flexion fatigue life, and is compatible with a wide range from a low temperature condition to a high temperature condition.

  On the other hand, in the comparative example, except for Comparative Examples 3, 6, 11, 14, 19, and 22, both the low temperature condition of 160 ° C. × 120 minutes and the high temperature condition of 400 ° C. × 5 minutes were used. The flex life was about half or less than that of the example. This is because one of the alloy elements is out of the predetermined amount range.

  In Comparative Examples 3, 6, 11, 14, 19, and 22, the number of flexing lives is 160 ° C. × 120 minutes under a low temperature condition, which is even shorter than the other comparative examples, but 400 ° C. × 5 minutes under a high temperature condition. Then, the bending life characteristics are as good as those of the examples. The reason for this is that, in Comparative Examples 3, 11, and 19, since boron (B) is less than a predetermined amount, the recrystallization temperature of the copper foil did not drop so much, so the recrystallization temperature was higher than 160 ° C. (× 120 minutes). This is because, since the recrystallization did not proceed due to the increase, the flex life characteristics were not exhibited.

  On the other hand, in Comparative Examples 6, 14, and 22, since the amount of silver (Ag) was larger than a predetermined amount, the recrystallization temperature of the copper foil increased, and recrystallization did not proceed at 160 ° C. (× 120 minutes). Therefore, the bending life characteristic was not exhibited. In Comparative Examples 3, 11, and 19 in which boron (B) is less than a predetermined amount and in Comparative Examples 6, 14, and 22 in which silver (Ag) is more than a predetermined amount, recrystallization occurs under low temperature conditions of 160 ° C. (× 120 minutes). However, the flex life characteristics were low because the recrystallization was performed properly at a high temperature condition of 400 ° C. for 5 minutes. It was. However, the applicable temperature range is narrow.

  Further, in Comparative Examples 7, 8, 15, 16, 23, and 24, the recrystallization progresses appropriately in both the low temperature condition of 160 ° C. × 120 minutes and the high temperature condition of 400 ° C. × 5 minutes. However, since the oxygen content was higher than 20 ppm, an oxide was formed and interposed in the copper, and this oxide caused metal fatigue, resulting in a decrease in flex life characteristics.

(Grounds for optimal conditions)
For oxygen, the smaller the amount, the less oxide is produced. That is, there are fewer factors that shorten the number of flexural fatigue lives. In the present invention, a result that there is no problem as long as it is less than 20 ppmm is obtained from the results of Examples, but it is preferably 10 ppm or less, and more preferably 5 ppm or less. However, as described above, in the production methods of Examples and Comparative Examples in the present invention, the oxygen concentration is considerably higher than 20 ppm (38 to 77 ppm), and therefore the oxygen concentration is unknown from 20 ppm to 37 ppm.

  About boron (B), although 30 ppm or more and 500 ppm or less were used, in order to stabilize the effect of the present invention, the lower limit is preferably 40 ppm or more, and more preferably 50 ppm or more. The upper limit is preferably 400 ppm or less, and more preferably 300 ppm or less.

About Ag, although it set to the range of 20 ppm or more and 250 ppm or less, in order to acquire the effect of this invention stably, 35 ppm or more is preferable and the lower limit is more preferable that it is 50 ppm or more. The upper limit is preferably 225 ppm or less, and more preferably 200 ppm or less.

  About Ni and / or Al, the total amount was set in the range of 30 ppm or more and 300 ppm or less, but in order to stably obtain the effects of the present invention, the lower limit is preferably 40 ppm or more, and more preferably 50 ppm or more. . Further, the upper limit is preferably 250 ppm or less, and more preferably 200 ppm or less.

  Although the embodiments and examples of the present invention have been described above, the embodiments and examples described above do not limit the present invention in any way. It should be noted that not all combinations of features described in the embodiments and examples are necessarily essential to the means for solving the problems of the invention.

  Moreover, since the rolled copper foil according to the present embodiment can stably exhibit excellent bending fatigue life characteristics even after being subjected to heat treatment in a wide temperature range as described above, this rolled copper foil Can be used suitably for flexible wiring of flexible printed wiring boards and other conductive members.

  Furthermore, the rolled copper foil according to the present embodiment is considered to have a certain degree of correlation between vibration resistance under no load, vibration resistance in an unfixed state, and bending fatigue life characteristics. It can also be applied to conductive members that require certain characteristics.

  DESCRIPTION OF SYMBOLS 2 ... Sliding bending test apparatus, 10 ... Rolled copper foil, 20 ... Sample fixing plate, 20a ... Screw, 30 ... Vibration transmission part, 40 ... Oscillation drive body.

Claims (6)

Other than copper (Cu) and inevitable impurities as main components, boron (B), silver (Ag), copper (Cu) and silver (Ag), the crystal structure is face-centered cubic, and stacking fault energy One or more additional elements selected from the group of elements having a value greater than copper (Cu). The rolled copper foil according to claim 1, wherein oxygen is contained in an amount of 0.002% by weight or less (20 ppm or less). The rolled copper foil according to claim 1 or 2, wherein the rolled copper foil has a thickness of 20 µm or less. The boron (B) is 0.003% to 0.05% by weight (30 ppm to 500 ppm) and the silver (Ag) is 0.002% to 0.025% by weight (20 ppm to 250 ppm). It contains. The rolled copper foil in any one of Claims 1-3 characterized by the above-mentioned. The rolled copper foil according to any one of claims 1 to 4, wherein the additive element is nickel (Ni) and / or aluminum (Al).   The rolling according to claim 5, wherein the nickel (Ni) and / or aluminum (Al) is contained in a total amount of at least one of 0.003% to 0.03% by weight (30 ppm to 300 ppm). Copper foil.

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