JP5468423B2 - High strength and high heat resistance copper alloy material - Google Patents

Description

  The present invention is suitable as a material for an electrical / electronic component, particularly a lead frame for a semiconductor device such as a QFP (Quad Flat Package) package or a QFN (Quad Flat no Lead Package) package. The present invention relates to a high-strength, high-heat-resistant copper alloy material with excellent oxide film adhesion.

  Conventionally, a copper alloy plate made of a Cu—Ni—Si based copper alloy containing Ni and Si is often used as a high strength lead frame material. Among the Cu—Ni—Si copper alloys, for example, Ni: 2.2 to 4.2 mass%, Si: 0.25 to 1.2 mass%, Mg :: 0.05 to 0.30 A copper alloy containing a mass (C70250 copper alloy) is widely used as a general-purpose alloy because of its excellent strength and heat resistance.

  In recent years, with increasing capacity, miniaturization, and higher functionality of semiconductor devices, lead frames have become finer, and in order to facilitate this miniaturization, the thickness of the copper alloy plate used for the lead frame is increased. Is getting thinner and thinner. Along with this, copper alloy plates used in these lead frames for semiconductor devices are required to have higher strength and higher heat resistance. Increasing the strength of the copper alloy plate is necessary for ensuring the handling property that decreases as the plate is thinned and for ensuring the strength as the final component. Further, the improvement in heat resistance is necessary for preventing softening by heat treatment for removing distortion after press punching for forming a lead frame, and for preventing softening when receiving a heat history in an assembly process of a semiconductor component. These correspond not only to lead frames but also to other electrical / electronic components such as copper alloy plates used for conductive components such as connectors, terminals, switches, and relays. In addition, the etching process, which is a suitable processing method for fine wiring, has no smut, and the smoothness of the etched surface of the copper alloy sheet is an important factor required for the copper alloy sheet. Attention has been paid.

  Note that semiconductor components that are packaged by sealing a semiconductor chip with a thermosetting resin have become mainstream from the viewpoint of low cost, and it is important to maintain the reliability of the package. The reliability of the package depends on the adhesion between the mold resin and the lead frame. If an oxide film with poor adhesion is formed on the surface of the lead frame due to the thermal history during the assembly process of the semiconductor component, the mold resin and Adhesion with the lead frame is reduced, package cracks and peeling occur due to heat during mounting on the printed circuit board, and the reliability of the package is reduced. Therefore, in order to maintain the reliability of the package, it is important to maintain the adhesion of the oxide film in the lead frame.

  From such a background, a copper alloy plate made of a Cu—Ni—Si based copper alloy (C70250 alloy) is excellent in strength and heat resistance, but in etching processing which is a suitable processing method for fine wiring processing, it is smut. Occurs, and the smoothness of the etched surface is inferior.

  Therefore, in order to improve the smoothness of such an etched surface, the applicant of the present application consists of a Cu-Ni-Fe-P-based copper alloy to which Ni is added based on a Cu-Fe-P-based copper alloy, A copper alloy plate in which a Ni—Fe—P compound was precipitated in the metal structure was proposed (Patent Document 1).

JP 2001-335864 A

  However, the Cu—Ni—Fe—P-based copper alloy sheet disclosed in Patent Document 1 achieves its intended purpose, but has a tensile strength of only about 700 MPa and obtains a higher strength than that. There is a problem that it is difficult to cope with the further thinning of the lead frame more recently. In addition, this conventional Cu-Ni-Fe-P-based copper alloy sheet can be strengthened by performing finish rolling (final cold rolling) at a high processing rate. Even if it is changed, the heat resistance is lowered and it is not suitable for practical use.

  The present invention has been made in view of such problems, and can achieve both high strength and high heat resistance with a tensile strength of 750 MPa or more and a hardness of Hv 220 or more, as well as press punching, Etching, which is a suitable processing method for wiring, has no smut, excellent smoothness of the etched surface, and excellent oxide film adhesion to maintain package reliability. An object is to provide a high-strength and heat-resistant copper alloy material.

The high-strength, high-heat-resistant copper alloy material according to the present invention is at least one element M selected from the group consisting of Ni: 0.4 to 1.0% by mass and Fe and Co: 0.03 to 0 in total amount .3% by mass, P: 0.05 to 0.2% by mass, Sn: 0.1 to 3% by mass, Zn: 0.05 to 2.5% by mass, Cr: 0.0005 to 0.05% by mass The ratio of Ni and M to the content of P (Ni + M) / P is 4 to 12, the ratio Ni / M of Ni to M is 3 to 12, and the balance is Cu and Having a composition consisting of inevitable impurities,
In the metal structure, the number of fine P precipitate particles having a particle size of 1 to 20 nm is 300 / μm ² or more, and the number of coarse crystal / precipitate particles having a particle size exceeding 100 nm is 0.5 / μm ² or less,
The Sn content in the P-compound-precipitated particles is 0.01 or more by mass% ratio by Sn / (Ni + M + P + Sn) by EDX analysis,
The elongation at break in a tensile test in a direction parallel to the rolling direction is 5% or more.
The EDX analysis is energy dispersive fluorescent X-ray analysis.

  In the present invention, the symbol M represents at least one element selected from the group consisting of Fe and Co, and is Fe and / or Co. In the present invention, the Fe and / or Co is contained in an amount of 0.03 to 0.3% by mass in a total amount (the total amount when both Fe and Co are included, and the content of the element in the case of being alone). The present invention satisfies the inequalities of 4 ≦ (Ni + M) / P ≦ 12 and 3 ≦ Ni / M ≦ 12, where the contents of Ni, elements M, and P are Ni, M, and P, respectively.

  Furthermore, the copper alloy material of the present invention is not limited to a copper alloy plate, but can be configured as a copper alloy material of various shapes such as a copper alloy block, and must have excellent adhesion with an oxide film. Can be used for applications.

  In the present invention, a predetermined number or more of P-compound-precipitated particles containing a predetermined amount of Ni, element M, P, and Sn and having a predetermined particle size are generated in the metal structure. When the Sn content of is not less than a predetermined value, the pinning force of the P precipitate precipitated particles that suppress the movement and disappearance of dislocations is increased, and the strength and heat resistance of the copper alloy plate are improved. In addition, in the etching process of the copper alloy plate, the P precipitate precipitate particles are suppressed from causing smut generation, so that the smoothness of the etched surface is improved.

Furthermore, by containing a predetermined amount of Zn, the thermal peeling of the plating and solder used to join the copper alloy is suppressed, the protection of the base material is increased, and the growth of the oxide film is suppressed. By improving the adhesion of the oxide film and containing a predetermined amount of Cr, Cr is concentrated in the crystal grain boundary of the ingot during the production of the copper alloy sheet, and the hot workability is improved. Furthermore, when the number of coarse crystal / precipitate particles having a particle size exceeding 100 nm is 0.5 / μm ² or less, the smoothness and plating properties of the etched surface are improved.

  Since Sn is detected in the P compound precipitated particles, the Sn content of the P compound precipitated particles is defined in the present invention. Sn may be contained in a P compound comprising Ni-MP, or may be concentrated at the P compound and matrix interface. In the present invention, the Sn content including all these cases is defined.

  Further, the high strength and high heat resistance copper alloy material excellent in the adhesion of the oxide film in the present invention further contains at least one element selected from the group consisting of Al and Mn in a total amount of 0. .0005 to 0.05 mass%. By containing a predetermined amount of Al and / or Mn, the amount of S mixed as an inevitable impurity in the copper alloy is reduced, and the hot workability of the copper alloy plate is improved.

  Further, this high-strength, high heat-resistant copper alloy material has a C1s peak area value ratio C1s / Cu2p of 0.35 or less with respect to the Cu2p peak area value on the surface by XPS analysis after alkaline cathode electrolytic cleaning. The area ratio of fine crystal grains having an equivalent circle diameter of less than 0.5 μm to the observed area when the surface is observed by EBSD analysis is preferably 0.90 or less.

  In this configuration, by reducing the amount of C and crystal grain boundaries on the surface, defects due to C or crystal grain boundaries are prevented from being introduced into the oxide film, and an oxide film with few defects is formed. This improves the adhesion of the oxide film. In addition, the formation of an oxide film with few defects improves the protection of the base material by the oxide film, and the suppression of the growth of the oxide film also contributes to the improvement of the adhesion of the oxide film.

  Furthermore, the high strength and high heat resistance copper alloy material of the present invention preferably has an elongation at break in a tensile test in a direction parallel to the rolling direction of 5% or more.

  According to this configuration, by having an appropriate breaking elongation, it is possible to maintain an appropriate bending workability required for the lead frame material, and therefore, as a material for electrical and electronic parts, particularly as a lead frame material for semiconductor devices. It becomes a suitable copper alloy plate.

  According to the copper alloy material according to the present invention, strength (tensile strength and hardness) and heat resistance are increased, and not only in stamping, but also in etching which is a processing method suitable for fine wiring processing, There is no generation of smut, and the smoothness and plating properties of the etched surface are excellent. Moreover, according to the copper alloy material which concerns on this invention, the thermal peeling of plating and a solder does not generate | occur | produce at the time of joining of a copper alloy material. Furthermore, according to the copper alloy material which concerns on this invention, the hot workability in the case of manufacture of a copper alloy material improves. Furthermore, the copper alloy material of the present invention has an excellent oxide film adhesion.

  Hereinafter, the high-strength, high-heat-resistant copper alloy plate excellent in the adhesion of the oxide film according to the present invention will be described in detail. The following description applies not only to the case where the copper alloy material is a plate-shaped material but also to a block-shaped material or the like.

  First, the reasons for component addition and the composition range limitation in the copper alloy sheet and the reasons for the numerical limitation of the number and number of Sn precipitate particles, the coarse crystals, and the number of precipitate particles will be described.

“Ni: 0.4 to 1.0 mass%”
Ni is an element necessary for improving the strength and heat resistance of a copper alloy sheet by precipitating P-compound precipitated particles containing fine Sn in the alloy structure. When the Ni content is less than 0.4% by mass, fine P compound precipitate particles containing Sn are insufficient. For this reason, in order to exhibit the effect of high strength and high heat resistance effectively, it is necessary to contain 0.4 mass% or more of Ni. However, if Ni is contained excessively exceeding 1.0% by mass, coarse crystal / precipitate particles are generated in the alloy structure, the smoothness of the etched surface of the copper alloy plate is lowered, and Inter-workability is also reduced. Therefore, the Ni content is in the range of 0.4 to 1.0 mass%. In this range, the preferable range of Ni is 0.5 to 0.9% by mass.

“At least one element M selected from the group consisting of Fe and Co: 0.03 to 0.3 mass%”
By containing one or more of Fe and Co, the heat resistance of the copper alloy plate is improved, and it is effective in suppressing softening due to heat history in the lead frame punching and heat history in the semiconductor assembly process. Like Ni, Fe or Co is an element necessary for precipitating fine P precipitate particles containing Sn in the alloy structure and improving the strength and heat resistance of the copper alloy sheet. If the content of one or more of Fe and Co is less than 0.03% by mass, the fine P precipitate particles containing Sn are insufficient, and the P precipitate particles become precipitate particles mainly composed of Ni and P. In addition, since the effects of increasing the strength and increasing the heat resistance cannot be effectively exhibited, the content of 0.03% by mass or more is necessary. However, if it is excessively contained in excess of 0.3% by mass, coarse crystal / precipitate particles are formed in the alloy structure, the smoothness of the etched surface of the copper alloy plate is lowered, and hot workability is increased. Also decreases. Accordingly, the copper alloy plate has a content of one or more of Fe and Co in the range of 0.03 to 0.3% by mass. Moreover, a preferable range in this range is 0.05-0.2 mass%.

“P: 0.05 to 0.2 mass%”
In addition to deoxidizing action, P combines with Ni and M (Fe and / or Co) to form fine P-compound precipitated particles containing Sn in the alloy structure. It is an element necessary for improving the properties. When the P content is less than 0.05% by mass, fine P precipitate precipitate particles containing Sn are insufficient, so that the effects of increasing the strength and heat resistance cannot be exhibited effectively. For this reason, P needs to contain 0.05 mass% or more. However, when P is contained excessively exceeding 0.2 mass%, coarse crystal / precipitate particles are generated in the alloy structure, the smoothness of the etched surface of the copper alloy plate is lowered, and hot Workability also decreases. On the other hand, when P exceeds 0.2% by mass, the solid solution amount of P increases and the adhesion of the oxide film decreases. Therefore, the P content is in the range of 0.05 to 0.2 mass%. Moreover, in this range, the preferable range of P is 0.07 to 0.18 mass%.

“Sn: 0.1 to 3% by mass”
The addition of Sn contributes to the improvement of the strength of the copper alloy plate in the solid solution state. In the present invention, when the precipitated particles mainly composed of Ni-M (Fe and / or Co) -P are analyzed by EDX, Sn is added. Is detected. The reason why Sn is detected in the portion of the precipitated particles is not clear, but is detected because Sn is contained in the precipitated particles mainly composed of Ni-M (Fe and / or Co) -P. A mechanism is conceivable in which Ni-M (Fe and / or Co) -P particles are preferentially precipitated and detected in the Sn-enriched portion of the matrix. In any case, it is conceivable that Sn promotes precipitation of Ni—M (Fe and / or Co) —P particles. By such a mechanism, it is presumed that the strength and heat resistance of the copper alloy plate of the present invention are further improved as compared with the effect of only Sn solid solution. When the Sn content is less than 0.1% by mass, fine precipitated particles containing Ni-M (Fe and / or Co) -P as a main component and containing Sn as in the present invention are not formed. For this reason, in order to exhibit the effect of high strength and high heat resistance effectively, Sn needs to contain 0.1 mass% or more. However, if Sn is contained in excess of 3% by mass, the effect is saturated. On the other hand, a large amount of Sn segregation and coarse crystal / precipitate particles are produced during melt casting in the production of copper alloy sheets. In addition, hot workability also decreases. In addition, the conductivity of the copper alloy plate is lowered, and the adhesion of the oxide film is also lowered. Therefore, the Sn content is in the range of 0.1 to 3% by mass. Moreover, the range of Sn preferable in this range is 0.2 to 2.5 mass%.

“Zn: 0.05 to 2.5 mass%”
Zn is an element necessary for suppressing thermal plating of Sn plating and solder used for bonding of copper alloy plates, improving heat-resistant peeling, and improving adhesion of an oxide film. In order to exhibit such an effect effectively, it is necessary to contain Zn by 0.05 mass% or more. However, if Zn is contained in excess of 2.5% by mass, coarse crystal / precipitate particles are easily generated and the effect of improving the adhesion of the oxide film is saturated. Therefore, the Zn content is in the range of 0.05 to 2.5 mass%. Moreover, in this range, the preferable range of Zn is 0.1 to 2.5 mass%.

“Cr: 0.0005 to 0.05 mass%”
Cr is an element necessary for improving the hot workability of the ingot during the production of the copper alloy sheet. Cr is concentrated at the crystal grain boundaries of the ingot to improve the strength of the grain boundaries at the hot working temperature and contribute to the improvement of hot workability. The copper alloy plate according to the present invention contains relatively high concentrations of P and Sn in order to achieve both high strength and high heat resistance, so that hot working is relatively difficult. For this reason, the element which has a grain-boundary reinforcement effect like Cr and improves hot workability is essential. In order to exhibit such an effect effectively, Cr needs to contain 0.0005 mass% or more.

  However, if Cr is contained in excess of 0.05% by mass, not only the effect of addition is saturated, but also coarse crystal / precipitate particles are easily generated in the alloy structure, The smoothness of the etched surface is reduced. Therefore, the Cr content is in the range of 0.0005 to 0.05 mass%. Further, a preferable Cr range in this range is 0.001 to 003 mass%.

“4 ≦ (Ni + M) / P ≦ 12 and 3 ≦ Ni / M ≦ 12”
By satisfying 4 ≦ (Ni + M) / P ≦ 12 and 3 ≦ Ni / M ≦ 12 in the relationship of mass% ratio of Ni, M (Fe and / or Co) and P, the strength of the copper alloy plate Heat resistance is greatly improved. Further, in order to precipitate the fine P-containing precipitated particles containing Sn of the present invention as described later, it is indispensable that the above two formulas are satisfied, and if these two formulas are not satisfied, the present invention It is impossible to achieve both high strength and high heat resistance. Therefore, the relationship between the mass% ratios of Ni, M, and P satisfies 4 ≦ (Ni + M) / P ≦ 12 and 3 ≦ Ni / M ≦ 12. Moreover, a preferable range among these ranges is 5 ≦ (Ni + M) / P ≦ 10 and 4 ≦ Ni / M ≦ 10.

"Inevitable impurities"
The inevitable impurities referred to in the present invention are elements such as Si, Ti, Zr, Be, V, Nb, Mo, W, and Mg. When these elements are contained, coarse crystal / precipitate particles are easily generated, and at the same time, both high strength and high heat resistance are inhibited. Therefore, it is preferable that the inevitable impurities have a total content of 0.5% by mass or less. In addition, elements such as B, C, Na, S, Ca, As, Se, Cd, In, Sb, Pb, Bi, and MM (Misch metal) contained in a minute amount in the copper alloy plate are unavoidable impurities. . When these elements are contained, coarse crystal / precipitate particles are likely to be generated and hot workability is reduced, so that the total amount can be suppressed to a minimum of 0.1% by mass or less. preferable.

“Number of P-oxide precipitation particles (particle size: 1 to 20 nm): 300 particles / μm ² or more, Sn content of P-oxide precipitation particles: Sn / (Ni + M + P + Sn) ratio of 0.01 or more”
The P-precipitate precipitated particles referred to in the present invention are particles detected by observing the copper alloy structure with a transmission electron microscope of 100,000 times or more, and are precipitated particles having a particle diameter of 1 to 20 nm. The number of the P compound precipitate particles is 300 / μm ² or more. These P-precipitate-precipitated particles are mainly composed of a P-compound composed of Ni-M (Fe and / or Co) -P, but the Sn content in the precipitate particles is a mass% ratio by EDX analysis. : Sn / (Ni + M + P + Sn) is 0.01 or more.

In the present invention, the particle size of the precipitated particles is the maximum diameter of each precipitated particle (the diameter of a circle circumscribing each precipitated particle). Similarly, the number of precipitated particles was determined by measuring the number of precipitated particles (particle size: 1 nm or more, 20 nm or less) in an observation field with a transmission electron microscope of 100,000 times or more, and converting the number as a measured number per 1 μm ² . This is the number referred to in the present invention. At least three arbitrary visual fields are observed, and the measurement results are averaged.

  Such fine P precipitate particles containing Sn are newly generated during the production of a copper alloy sheet, for example, during annealing after cold rolling. That is, such fine precipitated particles are compound phases that are finely precipitated from the parent phase by annealing. Therefore, it is not a coarse crystal / precipitate particle which is generated during casting or hot rolling and originally exists in the copper alloy structure. For this reason, such fine precipitate particles cannot be observed unless the copper alloy structure is observed with a transmission electron microscope of 100,000 times or more.

In the present invention, the number of such fine P oxide precipitate particles containing Sn is 300 / μm ² or more. Such fine P-precipitate precipitate particles containing Sn have a pinning force that suppresses the movement and disappearance of dislocations, which is much larger than coarser crystal / precipitate particles. For this reason, in the copper alloy sheet of the present invention, as many precipitated particles as a main component of a fine Ni-M (Fe and / or Co) -P-Sn compound having a particle size of 20 nm or less are present in the copper alloy structure as much as possible. Thereby, the said pinning force increases and it can attain high intensity | strength and high heat resistance.

  Furthermore, such fine P-precipitate-deposited particles containing Sn having a particle size of 20 nm or less do not become a cause of smut in the etching process, which is a suitable processing method for fine wiring processing, and the etched surface. It does not reduce the smoothness. On the other hand, coarse crystal / precipitate particles not only have a small contribution to high strength and high heat resistance, but also become a cause of smut in the etching process, and smoothness of the etched surface. It will also be a factor to reduce.

  As described above, the coarse crystal / precipitate particles having a particle diameter of more than 20 nm have a weak pinning force. Therefore, in this invention, the upper limit of the average particle diameter of the fine P compound precipitation particle | grains containing Sn shall be 20 nm. On the other hand, fine precipitates having a particle size of less than 1 nm are difficult to detect and measure even with a transmission electron microscope of 100,000 times or more, and the pinning force is weakened. Therefore, in the present invention, the number of P-oxide precipitate particles containing Sn is defined for P-oxide precipitates having a particle size of 1 nm or more.

If the number of such fine P precipitate precipitate particles containing Sn is less than 300 / μm ² , the number of particles to exhibit the effect is insufficient, and the tensile strength is 750 MPa (hardness Hv220) or higher. It cannot be obtained, and heat resistance is also lowered.

  In addition, if the Sn content of the P oxide precipitate particles containing fine Sn is less than 0.01 in terms of mass%, a high strength with a tensile strength of 750 MPa (hardness Hv220) or more cannot be obtained, and the heat resistance also decreases. To do. The composition analysis (Sn content) of the precipitated particles is performed by EDX analysis, and the mass% is calculated from the peak intensity of each component (Ni, Fe, Co, P, Sn). Each mass% is calculated by assuming Ni + Fe + Co + P + Sn as 100%, and the mass% ratio of Sn is calculated from this mass% by the formula of Sn / (Ni + Fe + Co + P + Sn). Moreover, at least 5 or more of the deposited particles of 1 nm or more and 20 nm or less in the observation visual field are analyzed, and the measurement results are averaged. In addition, the typical composition of the P precipitate particles is mass% by EDX analysis, Ni: 30 to 70%, M (Fe and / or Co): 5 to 60%, P: 5 to 35%, Sn: It consists of a range of about 1 to 30%.

“Number of coarse crystal / precipitate particles (particle size is 100 nm or more): 0.5 / μm ² or less”
In the present invention, the amount of fine P precipitate particles containing Sn having a particle size of 1 nm or more and 20 nm or less is defined. If this requirement is satisfied, the crystal / precipitate particle size is 20 nm. It is permissible for coarse crystal / precipitate particles exceeding 1 to exist in an appropriate amount in the copper alloy structure. However, when the copper alloy structure is observed with a scanning electron microscope of 10,000 times or more, the number of crystal / precipitate particles having a particle size exceeding 100 nm needs to be 0.5 / μm ² or less. It is. If the number of coarse crystal / precipitate particles having a particle size exceeding 100 nm exceeds 0.5 / μm ^{2, it} may cause smut during etching processing, decrease in smoothness of the etched surface, and plating. It becomes a factor causing problems such as deterioration of the property (generation of protrusions). Moreover, the production | generation of the P compound precipitation particle | grains containing the above-mentioned fine Sn is also inhibited.

  Coarse crystal / precipitate particles having a particle size exceeding 100 nm are produced during casting or hot rolling during the production of a copper alloy sheet. Here, the crystal / precipitate particles refer to crystal particles that separate as a crystal phase in a copper alloy structure, precipitate particles that separate as a solid phase that does not form a clear crystal phase, or a mixture thereof. The coarse crystal / precipitate particles having a particle diameter exceeding 100 nm include P-based (Ni—Fe—P, Ni—Co—P, Ni—P) and Ni—Sn based particles. Things exist.

In the present invention, the particle size of coarse crystal / precipitate particles is the maximum diameter of each crystal / precipitate particle (the diameter of a circle circumscribing each crystal / precipitate particle). Similarly, the number of coarse dispersoids is 10,000 times or more dispersoids number in the observation field of view with a scanning electron microscope (particle size: greater than 100 nm) was measured, 1 [mu] m ² per It is converted as the number of measurements. In this case, at least three arbitrary visual fields are observed, and the measurement result is averaged as a measurement value. Although observation is possible with a transmission electron microscope, the scanning electron microscope is easier because the particle size is large.

“Elongation at break in tensile test parallel to rolling direction: 5% or more”
The copper alloy sheet according to the present invention further has a breaking elongation of 5% or more in a tensile test parallel to the rolling direction. As a result, by having an appropriate elongation at break, it is possible to maintain an appropriate bending workability required for the lead frame material, which is suitable as a material for a lead frame for a semiconductor device, etc. It becomes a copper alloy plate. On the other hand, if the elongation at break in the tensile test parallel to the rolling direction is less than 5%, the appropriate bending workability required for the lead frame material cannot be maintained. A copper alloy plate suitable as a material, particularly as a lead frame material for a semiconductor device cannot be obtained. Therefore, the elongation at break in the tensile test parallel to the rolling direction is 5% or more. More preferably, the content is 6% or more.

“At least one selected from the group consisting of Al and Mn: 0.0005 to 0.05 mass% in total”
Al and / or Mn is an element mixed as an impurity in the copper alloy, but is an effective element for reducing the amount of S that reduces hot workability. Therefore, Al and / or Mn may be contained as long as they are not more than a predetermined amount. In order to exhibit the above-mentioned effects effectively, it is necessary to contain Al and / or Mn in a total amount of 0.0005% by mass or more. However, if Al and / or Mn is contained in excess of 0.05% by mass, not only the effect is saturated, but coarse crystal / precipitate particles are easily generated, and the copper alloy sheet is etched. Surface smoothness decreases. Accordingly, the copper alloy plate has a content of Al and / or Mn in the range of 0.0005 to 0.05 mass%. Moreover, in this range, the preferable range of Al and / or Mn is 0.001 to 0.03% by mass.

“Ratio of C1s peak area value to Cu2p peak area value on the copper alloy plate surface by XPS analysis after alkaline cathode electrolytic cleaning C1s / Cu2p: 0.35 or less”
In the copper alloy plate according to the present invention, the ratio of the peak area value of C1s to the peak area value of Cu2p on the surface of the copper alloy plate by XPS analysis after alkaline cathode electrolytic cleaning is 0.35 or less, and When the copper alloy plate surface is observed by EBSD analysis, the area ratio of fine crystal grains (equivalent circle diameter is less than 0.5 μm) to the observed area is preferably 0.90 or less.

  The ratio of the peak area value of C1s to the peak area value of Cu2p on the surface by XPS analysis after performing alkaline cathode electrolytic cleaning is, in other words, relative to the copper alloy plate surface after performing alkaline cathode electrolytic cleaning. Means an amount of C. Further, XPS analysis is X-ray photoelectron spectroscopy analysis, which is also called ESCA analysis, and is an analysis method that excels at composition and state analysis of a very thin layer on the surface. C detected from the surface of the copper alloy plate is usually derived from various contaminants (organic matter, inorganic matter) and treated to prevent discoloration of the copper alloy plate (benzotriazole, etc.) Derived from. Any of these substances present on the surface adversely affects the adhesion of the oxide film. This is probably because defects caused by these substances are introduced into the oxide film to generate an oxide film having many defects.

  A copper alloy plate used for a lead frame of a semiconductor device is subjected to a pretreatment such as electrolytic cleaning, and then partially subjected to a plating process, which is used for an assembly process, and is generated by a thermal history in the assembly process. The adhesion of the oxide film determines the reliability of the package. Therefore, C that affects the adhesion of the oxide film is C after the copper alloy plate is subjected to a pretreatment such as electrolytic cleaning, which must be captured. Therefore, in the present invention, attention has been paid to C on the surface by XPS analysis after alkaline cathode electrolytic cleaning, which is most commonly used as a pretreatment such as electrolytic cleaning. In addition, since the organic rust preventive film (benzotriazole etc.) for preventing discoloration of a copper alloy plate is easily removed by alkaline cathode electrolytic cleaning, there is no problem.

  Here, the alkaline cathode electrolytic cleaning is a cleaning method in which electrolysis is performed with an object as a cathode side in an alkaline aqueous solution and the detergency is enhanced by a mechanical stirring action by hydrogen gas generated from the surface of the object. The alkaline aqueous solution used in this method is generally composed of an alkali salt such as sodium hydroxide, sodium silicate, sodium phosphate, sodium carbonate, and the like, with an organic substance such as a surfactant or a chelate compound added. In addition, since electrolysis is performed using the object as a cathode, the surface of the copper alloy plate is not oxidized or dissolved, and the surface of the material itself is not damaged at all. Therefore, with alkaline cathode electrolytic cleaning, normal contaminants and organic rust preventive films can be easily removed, but abnormal contaminants (such as organic substances (resinous) having a strong adhesive force) cannot be removed. If such contaminants that cannot be removed by alkaline cathodic electrolysis are adhered to the surface of the copper alloy plate, the adhesion of the oxide film is greatly reduced, and the reliability of the package is lowered. Therefore, the ratio C1s / Cu2p of the peak area value of C1s to the peak area value of Cu2p on the surface by XPS analysis after alkaline cathode electrolytic cleaning is desirably smaller, and is 0.35 or less. C1s / Cu2p is more preferably set to 0.30 or less.

“The area ratio of fine crystal grains with an equivalent circle diameter of less than 0.5 μm to the observed area when the surface is observed by EBSD analysis is 0.90 or less.”
On the other hand, the area ratio of fine crystal grains (equivalent circle diameter is less than 0.5 μm) to the observed area when the surface of the copper alloy plate is observed by EBSD analysis is, so to speak, the occupation ratio of fine crystal grains on the surface of the copper alloy plate Means. Here, the EBSD analysis is a backscattered electron diffraction analysis, and is an analysis method that excels at analyzing the size, distribution, orientation, etc. of crystal grains. Further, the term “crystal grain” as used herein is regarded as a grain boundary when the orientation difference between adjacent measurement points is 5 ° or more by EBSD analysis, and a region completely surrounded by the grain boundary is defined as a crystal grain.

  The large area ratio of fine crystal grains on the surface of the copper alloy plate means that there are many fine crystal grains and that there are many crystal grain boundaries, and defects due to so many crystal grain boundaries are oxidized. It will be introduced into the film, and the adhesion of the oxide film will decrease. Therefore, it is desirable that the area ratio of fine crystal grains on the surface of the copper alloy plate is smaller, and it is set to 0.90 or less. More desirably, it is set to 0.85 or less.

"Copper alloy sheet manufacturing method"
Next, the manufacturing method of the copper alloy plate of this invention is demonstrated. In order to make the alloy structure of the copper alloy plate to be manufactured the above-described structure, it is not necessary to greatly change the conventionally known manufacturing process itself, and it can be manufactured in the same process as a conventional method. That is, a molten copper alloy adjusted to the above component composition is cast. Then, after chamfering the ingot, heating or homogenizing heat treatment, hot rolling, and water-cooling the copper alloy plate after hot rolling. Then, cold rolling, annealing, and washing are repeated several times, and finish (final) cold rolling is performed to obtain a copper alloy plate having a product plate thickness.

  Note that it is desirable to perform low-temperature annealing (also referred to as strain relief annealing) after the final cold rolling. With the miniaturization and high integration of semiconductor devices, the demand for quality regarding the flatness of the plate and the reduction of internal stress is increasing with the miniaturization of the lead frame, and low temperature annealing is effective in improving these quality. Furthermore, low temperature annealing is effective for restoring the ductility of the material, and is an effective means for controlling the elongation at break in a tensile test parallel to the rolling direction to 5% or more. Low temperature annealing may be performed in a temperature range of about 200 to 500 ° C. and a time range of about 1 to 300 seconds so that the elongation at break in a tensile test parallel to the rolling direction is 5% or more.

Here, in order to control so that the number of P-oxide precipitation particles containing Sn having a particle diameter of 1 nm or more and 20 nm or less is 300 particles / μm ² or more, annealing is performed under the following conditions in manufacturing. It is effective to do. In addition, in order to control Sn content of P compound precipitation particle | grains so that it may become 0.01 or more by mass% ratio by EDX analysis, content of Ni, Fe and / or Co, P, and Sn in a copper alloy It is effective to perform this adjustment.

  In other words, as described above, the fine P-containing precipitate particles containing Sn in the present invention are compound phases newly newly precipitated from the parent phase by annealing. In order to precipitate such fine P precipitate particles containing Sn, annealing is performed after cold rolling in the above-described manufacturing process of the copper alloy sheet.

  However, it is difficult to precipitate a large number of such fine P-containing precipitate particles containing Sn by only one annealing. When the annealing temperature is increased, the number of precipitated particles increases as the number of precipitated particles increases. Moreover, it causes coarsening. Therefore, annealing is performed in a plurality of times, and the annealing temperature per time is controlled to 430 ° C. or less, the growth and coarsening of the precipitated particles are controlled, and the fine precipitation form described above can be controlled. preferable. The annealing time may be in the range of about 5 minutes to 20 hours.

  Further, when cold rolling is performed between these annealings, lattice defects are increased by cold rolling and precipitation nuclei are formed in the subsequent annealing, so that the above-described fine precipitation form is easily obtained.

Therefore, in consideration of these conditions, in the above-described copper alloy sheet manufacturing process, after hot rolling to finish (final) cold rolling, a process of repeatedly performing cold and annealing twice, This is preferable in that the precipitation form of the fine P precipitate particles containing Sn is easily obtained. Further, by controlling the casting conditions and the hot rolling conditions so that the number of coarse crystal / precipitate particles having a particle diameter exceeding 100 nm is 0.5 particles / μm ² or less, fine P containing Sn is contained. It is preferable to promote the formation of the oxide precipitate particles.

As casting conditions and hot rolling conditions for controlling the number of coarse crystal / precipitate particles having a particle size exceeding 100 nm to 0.5 / μm ² or less, the cooling rate during casting is increased and hot rolling is performed. It is effective to increase the heating temperature and end temperature of the steel and to increase the cooling rate after hot rolling. The conditions for increasing the cooling rate during casting are that the cooling rate during solidification for suppressing coarse crystals and the cooling rate up to 500 ° C. after solidification for suppressing coarse precipitates are both set to 0. It should be 1 ° C./second or more, preferably 0.5 ° C./second or more. For this purpose, for example, cooling with water cooling is preferable. The conditions for increasing the heating temperature and the end temperature of hot rolling are that the heating temperature is 850 ° C. or higher and the end temperature is 650 ° C. or higher. The condition for increasing the cooling rate after hot rolling is that the cooling rate up to 300 ° C. after completion of hot rolling is 1 ° C./second or more, preferably 5 ° C./second or more. For this purpose, for example, water cooling is performed. If the cooling rate during casting is too slow, a large number of coarse crystal / precipitate particles are generated. In addition, when the heating temperature of hot rolling is low, the coarse crystals / precipitate particles generated during casting are not sufficiently dissolved, and the end temperature of hot rolling is lowered, so that the coarse crystals / precipitates are reduced. Many particles are formed. Even when the cooling rate after hot rolling is slow, a large number of coarse crystal / precipitate particles are generated.

  The ratio of the peak area value of C1s to the peak area value of Cu2p on the surface of the copper alloy plate by XPS analysis after the alkaline cathode electrolytic cleaning described above is 0.35 or less, and the surface of the copper alloy plate is analyzed by EBSD. In order that the area ratio of the fine crystal grains (equivalent circle diameter is less than 0.5 μm) to the observation area when observed with the above is 0.90 or less, the following steps may be performed.

  First, in order for the ratio of the peak area value of C1s to the peak area value of Cu2p on the surface of the copper alloy plate by XPS analysis after alkaline cathode electrolytic cleaning to be 0.35 or less, cleaning treatment before and after annealing is performed. This is very important. In general, after annealing, various cleaning treatments (acid cleaning, polishing, etc.) are performed in order to remove the oil residue resulting from the oxide film and rolling oil generated by annealing. It is difficult to effectively clean C such as oil residue, resulting in a loss such as a long cleaning time. Therefore, in order to effectively clean the oil residue that causes C, it is effective to perform a cleaning process before annealing, particularly before the low-temperature annealing, which is the final process. It is essential to perform an oxide film removal treatment by acid cleaning or the like after low-temperature annealing. As such cleaning treatment before annealing, there are various cleaning treatments such as solvent washing, alkali washing, and alkaline electrolytic washing, and an appropriate washing method may be used as necessary.

Next, since the area ratio of fine crystal grains (equivalent circle diameter is less than 0.5 μm) to the observed area when the copper alloy plate surface is observed by EBSD analysis is 0.90 or less, mechanical polishing after annealing is performed. It is important to reduce the grain size of the abrasive and keep the crystal grains of the surface layer as large as possible by not performing the process or by increasing the number of mechanical polishing. Further, even if mechanical polishing is performed, it is also an effective means to remove the fine crystal layer generated by the mechanical polishing by chemical dissolution treatment, electrochemical dissolution treatment, or the like. Conventionally, mechanical polishing is often performed after annealing. This is because the oxide film formed by annealing is strong and difficult to remove by acid cleaning alone. Therefore, in order not to perform mechanical polishing or to keep the area ratio of fine crystal grains small by reducing the load of mechanical polishing, the annealing atmosphere is sufficiently managed and a strong oxide film is not generated. It is important to do so. Specifically, the annealing atmosphere is a reducing atmosphere (atmosphere containing reducing components such as H ₂ and CO), and the oxidizing components (O ₂ and H ₂ O, etc.) are controlled to a concentration as low as possible to achieve strong oxidation. It is important not to produce a film. In particular, in the low-temperature annealing process, which is the final process, the oxide film can be removed only by acid cleaning by sufficiently controlling the annealing atmosphere and controlling it so as not to generate a strong oxide film, and without mechanical polishing. It is preferable to perform surface adjustment.

  Next, test results of examples and comparative examples for demonstrating the effects of the present invention will be described. As a method for producing a copper alloy plate, a molten copper alloy having the composition shown in Table 1 below is melted in a high-frequency furnace, and then cast into a graphite book mold by tilting, having a thickness of 50 mm, a width of 200 mm, and a long length. An ingot with a length of 200 mm was obtained. After the ingot was solidified in the mold, it was cooled with water at a temperature of 700 to 800 ° C. The graphite mold had a sufficient heat capacity and thermal conductivity, and the cooling rate during solidification obtained from the secondary branch spacing of the dendrite arm spacing was 1 ° C./second or more. In addition, the copper alloy shown in Table 1 contains elements such as Si, Ti, Zr, Be, V, Nb, Mo, W, and Mg as inevitable impurities in a total amount of 0.01% by mass or less, B, C, Na , S, Ca, As, Se, Cd, In, Sb, Pb, Bi, MM (Misch metal) and the like were included in a total amount of 0.005% by mass or less. In Table 1, compositions or component ratios deviating from claim 1 of the present invention are underlined.

  Then, from each ingot, a block having a thickness of 50 mm, a width of 180 mm, and a length of 80 mm was cut out, the rolled surface was chamfered and heated, and after reaching 900 ° C., held for 0.5 to 1 hour. Then, it hot-rolled until thickness became 16 mm, and water-cooled from the temperature of 700 degreeC or more. After chamfering the surface of the rolled plate to remove the oxide scale, cold rolling and annealing are repeated twice each (the number of cold rolling is the same as the number of annealing), and then the final cold rolling is performed. And a copper alloy plate having a thickness of 0.2 mm was obtained. At this time, the annealing temperature was controlled to 430 ° C. or less, and the annealing time was controlled in the range of about 5 minutes to 20 hours, so that the growth and coarsening of the precipitated particles were suppressed, and the fine precipitation form was controlled. And low temperature annealing was performed after the last cold rolling. The processing rate of final cold rolling was 50%. Low temperature annealing was performed in a temperature range of about 200 to 500 ° C. and a time range of about 1 to 300 seconds so that the elongation at break in a tensile test parallel to the rolling direction was 5% or more.

Here, annealing is performed in an N ₂ + 10% H ₂ atmosphere (dew point: −20 ° C. or lower, O ₂ concentration: 50 ppm or lower) together with two annealings and low temperature annealing, and the cleaning treatment before and after annealing is as follows. I went there. For annealing twice, solvent cleaning (ultrasonic cleaning with hexane: 20 kHz) is performed before annealing, acid cleaning (10% sulfuric acid) is performed after annealing, and then mechanical polishing (# 600 water resistant abrasive paper) is performed. went. Regarding low-temperature annealing, solvent cleaning (ultrasonic cleaning with hexane: 20 kHz) was performed before annealing, and only acid cleaning (10% sulfuric acid) was performed after annealing, and mechanical polishing was not performed.

  With respect to the copper alloy plate thus obtained, in each of the examples and comparative examples, a sample was cut out from the copper alloy plate, subjected to structure observation and surface analysis, and Sn-containing P-precipitate precipitated particles (hereinafter referred to as fine particles). The number of precipitated particles) was measured, and a composition analysis (Sn content) was performed. Further, the number of coarse crystal / precipitate particles (hereinafter referred to as coarse crystal / precipitate particles) was measured, and C1s / Cu2p (hereinafter referred to as relative C) by XPS analysis after alkaline cathode electrolytic cleaning of the surface of the copper alloy plate. And the area ratio of the fine crystal grains (equivalent circle diameter is less than 0.5 μm) to the observation area by the EBSD analysis of the copper alloy plate surface (hereinafter referred to as the area ratio of the fine crystal grains), The elongation at break and tensile strength were measured by a tensile test, the hardness was measured, the electrical conductivity and the heat resistance were measured, and the etching processability (etching property) and the adhesion holding temperature of the oxide film were evaluated. These results are shown in Tables 2 and 3. In Table 2, items that fall outside the scope of claim 1 are underlined. In Table 3, those with insufficient characteristics are underlined.

Observation of fine precipitated particles is by the above-mentioned measurement method, the particle size of observing a copper alloy structure at 300,000 times transmission electron microscope to measure the number of less deposited particles 20nm or 1 nm, pieces / [mu] m ² Calculated as The composition analysis (Sn content) of the finely precipitated particles was calculated as a mass% ratio by measuring mass% (Ni + M + P + Sn = 100%) by EDX analysis (beam diameter: 1 nm).

Coarse crystal / precipitate particles are observed by measuring the number of coarse crystal / precipitate particles with a particle size exceeding 100 nm when the copper alloy structure is observed with a scanning electron microscope of 10,000 times. And calculated as pieces / μm ² .

The relative amount of C is measured by measuring the peak area value of Cu2p and the peak area value of C1s on the surface by XPS analysis after performing alkaline cathode electrolytic cleaning on the surface of the copper alloy plate by the measurement method described above. Calculated as C1s / Cu2p. Here, the alkaline cathode electrolytic cleaning is a typical commercially available alkaline cathode electrolytic cleaning agent containing sodium hydroxide as a main component (40%) and containing other phosphates, silicates, carbonates and surfactants. Was dissolved in an aqueous solution at a concentration of 50 g / L under the conditions of liquid temperature: 60 ° C., cathode current density: 5 A / dm ² , and time: 30 seconds.

  The area ratio of the fine crystal grains is determined by measuring the observation area when the copper alloy plate surface is observed by EBSD analysis and the occupied area of the fine crystal grains (equivalent circle diameter is less than 0.5 μm) by the measurement method described above. The area ratio of crystal grains was calculated.

  In the tensile test, a JIS No. 5 test piece cut out in parallel with the rolling direction was prepared, and the elongation at break and the tensile strength were measured. The hardness test was performed by applying a load of 4.9 N with a micro Vickers hardness tester. The tensile strength was 750 MPa or more and the hardness was 220 Hv or more.

  The electrical conductivity was calculated by an average cross-sectional area method by processing a strip-shaped test piece having a width of 10 mm and a length of 300 mm by milling, measuring an electrical resistance with a double bridge resistance measuring device. The case where the electrical conductivity was 25% or more was considered good.

  The heat resistance was measured by measuring the hardness after heating at 450 ° C. for 1 minute by the above hardness test, and the hardness retention rate (%) = (hardness after heating / hardness before heating) × 100. The case where the hardness retention was 90% or more was considered good.

The etching processability (etchability) is determined by etching using a ferric chloride aqueous solution (specific gravity 1.4) at a liquid temperature of 45 ° C. and a spray pressure of 1.5 kgf / mm ^2. The etched surface was observed with a scanning electron microscope, and the smoothness was evaluated in three stages: A: good, B: rough skin, and C: large rough skin.

The oxide film adhesion holding temperature is obtained by performing alkaline cathodic electrolytic cleaning on the surface of the copper alloy plate, followed by washing with water → acid washing (10% sulfuric acid) → water washing → drying, and then heating at a predetermined temperature in the atmosphere for 10 minutes. Then, it evaluated by the peeling test by a tape. Alkaline cathode electrolytic cleaning is 50 g of a typical commercially available alkaline cathode electrolytic cleaning agent containing sodium hydroxide as the main component (40%) and containing phosphate, silicate, carbonate and surfactant. In an aqueous solution dissolved at a concentration of / L, the temperature was 60 ° C., the cathode current density was 5 A / dm ² , and the time was 30 seconds. The peeling test using a tape was performed by applying a commercially available tape (mending tape manufactured by Sumitomo 3M) and peeling it off. At this time, the heating temperature was changed in increments of 10 ° C., and the highest temperature at which the oxide film did not peel was evaluated as the oxide film adhesion holding temperature.

  As shown in Table 1, Examples 1 to 8 satisfy the composition range of Claim 1, and Examples 9 and 10 further satisfy the composition range of Claim 2. As shown in Table 2, Examples 1 to 10 satisfy the matrix structure defined in claim 1 and the surface properties defined in claim 3. Therefore, as shown in Table 3, the copper alloy plates of Examples 1 to 10 have mechanical properties such that the tensile strength is 750 MPa or more, the hardness is Hv 220 or more, and the conductivity is 25% IACS or more. there were. Further, the heat resistance has a hardness retention of 90% or more, and both high strength and high heat resistance can be achieved. The etching processability was also good, and the oxide film adhesion holding temperature was good at 240 ° C. or higher.

On the other hand, in Comparative Example 11, the Ni content, (Ni + M) / P and Ni / M ratio are below the lower limit, and therefore the number of finely precipitated particles is below the lower limit of 300 / μm ² . , Tensile strength, hardness, heat resistance (hardness retention) was low. Moreover, since (Ni + M) / P was below the lower limit value, the solid solution amount of P was increased, so that the adhesion holding temperature of the oxide film was lowered.

  In Comparative Example 12, the number of finely precipitated particles satisfies Claim 1, and the tensile strength, hardness, and heat resistance are all good, but the Ni content exceeds the upper limit value, so it is coarse. Crystalline / precipitate particles increased and the etching property decreased.

In Comparative Example 13, the Fe content was 0.02% by mass, lower than the lower limit, and Ni / M exceeded the upper limit. Therefore, the number of fine precipitated particles was lower than the lower limit of 300 / μm ² , The strength, hardness, and heat resistance (hardness retention) were low.

  In Comparative Example 14, the number of finely precipitated particles satisfies Claim 1 and the tensile strength and hardness are good, but the Fe content exceeds the upper limit value, and Ni / M is below the lower limit value. In addition to low heat resistance (hardness retention), coarse crystal / precipitate particles were formed, and etching properties were reduced.

  In Comparative Example 15, since the P content is below the lower limit and (Ni + M) / P exceeds the upper limit, the number of finely precipitated particles is lower than the lower limit, and the tensile strength, hardness, and heat resistance are increased. Was also low.

  In Comparative Example 16, the number of finely precipitated particles satisfied Claim 1, and the tensile strength, hardness and heat resistance were all good, but the P content exceeded the upper limit, and (Ni + M) / P was Since it was below the lower limit, coarse crystal / precipitate particles were generated, and the etching property was lowered. Further, since the P content exceeded the upper limit value and (Ni + M) / P was below the lower limit value, the solid solution amount of P increased and the oxide film adhesion holding temperature was low.

  In Comparative Example 17, the number of finely precipitated particles satisfies Claim 1, but since the Sn content is below the lower limit, the Sn content of the finely precipitated particles is also below the lower limit, and the tensile strength and The hardness was insufficient.

  In Comparative Example 18, the number of finely precipitated particles satisfies Claim 1 and the tensile strength and hardness are good, but the Sn content exceeds the upper limit value. As a result, the heat resistance (hardness retention) and the etching property were lowered, and the conductivity was also greatly lowered. Moreover, since Sn content exceeded the upper limit, the oxide film adhesion holding temperature was also low.

  In Comparative Example 19, the number of finely precipitated particles satisfies Claim 1, and the tensile strength, hardness, and heat resistance (hardness retention) are good, but the Zn content is below the lower limit. The oxide film adhesion holding temperature decreased.

  In Comparative Example 20, the number of finely precipitated particles satisfies Claim 1, and the tensile strength, hardness, and heat resistance (hardness retention) are good, but the Zn content exceeds the upper limit. As a result, coarse crystal / precipitate particles were formed, and the etching property decreased. Further, it can be seen from the comparison with Examples 7 and 8 that the effect of improving the oxide film adhesion holding temperature is saturated in Comparative Example 20.

  Next, test results regarding the relationship between the surface properties and the oxide film adhesion holding temperature will be described. In Example 2, a copper alloy plate having a thickness of 0.2 mm was obtained from the ingot of Example 2 in Table 1 by the same method and conditions as in Example 1. Therefore, the properties of composition, component ratio, base material structure, tensile strength, elongation at break, hardness, electrical conductivity, heat resistance and etching processability were equivalent to those in Example 2 in Table 3.

However, annealing is performed in N ₂ + 10% H ₂ atmosphere (dew point: −20 ° C. or lower, O ₂ concentration: 50 ppm or lower) together with two annealings and low temperature annealing, and by changing the cleaning treatment before and after annealing, The surface properties (relative C amount, area ratio of fine crystal grains) of the copper alloy plate were changed, and the oxide film adhesion holding temperature was evaluated. In this case, the cleaning process before and after the two annealings was performed under the same method and conditions.

  These processing conditions are shown in Tables 4 and 5. However, in Tables 4 and 5, alkali dipping cleaning and alkali cathodic electrolysis cleaning are representative of sodium hydroxide as the main component and other phosphates, silicates, carbonates, and surfactants, respectively. Commercially available alkaline immersion cleaning solution and alkaline cathode electrolytic cleaning agent were used. In addition, a typical commercially available aqueous solution mainly composed of sulfuric acid and hydrogen peroxide was used for the chemical dissolution treatment partially performed in the post-treatment of the two annealings. Table 6 shows the obtained surface properties and characteristics. In Table 6, items deviating from claim 3 are underlined, and items with insufficient characteristics are underlined.

  As shown in Tables 4 and 5, in Examples 1 to 10, since appropriate cleaning treatment was performed before and after each annealing as well as two annealings and low-temperature annealing, an alkali cathode was formed on the surface of the copper alloy plate. Surface C1s / Cu2p (relative C content) by XPS analysis after electrolytic cleaning is good at 0.35 or less, and fine crystal grains (equivalent circle diameter) relative to the observation area by EBSD analysis of the copper alloy plate surface Is less than 0.50m, it is good at 0.90 or less.

  As a result, the oxide film adhesion retention temperature of the copper alloy plates of Examples 1 to 10 was good at 240 ° C. or higher. Further, it is recognized that the oxide film adhesion holding temperature tends to be improved (increased) as the relative C amount and the area ratio of the fine crystal grains become smaller.

  On the other hand, in Comparative Examples 11 to 13, since both the annealing and the low-temperature annealing are performed only by immersion cleaning with ethanol, the relative C amount exceeds the upper limit, and the oxide film The adhesion holding temperature was low.

  Further, in Comparative Examples 14 to 16, by polishing after low-temperature annealing, the area ratio of fine crystal grains was increased to 0.90 or more, and the oxide film adhesion holding temperature was lowered.

  The copper alloy material according to the present invention has excellent oxide film adhesion, and according to the copper alloy plate according to the present invention, it has an appropriate bending workability required for a lead frame material. Thereby, the copper alloy material according to the present invention is not limited to use as a lead frame material, but can be suitably used for other materials for electric / electronic parts in general.

Claims (3)

Ni: 0.4 to 1.0 mass%, at least one element selected from the group consisting of Fe and Co M: 0.03 to 0.3 mass% in total, P: 0.05 to 0.2 Containing mass%, Sn: 0.1 to 3 mass%, Zn: 0.05 to 2.5 mass%, Cr: 0.0005 to 0.05 mass%, Ni and M content and P content The ratio (Ni + M) / P to the amount is 4 to 12, the ratio Ni / M of Ni to M is 3 to 12, and the balance is composed of Cu and inevitable impurities,
In the metal structure, the number of fine P precipitate particles having a particle size of 1 to 20 nm is 300 / μm ² or more, and the number of coarse crystal / precipitate particles having a particle size exceeding 100 nm is 0.5 / μm ² or less,
The Sn content in the P-compound-precipitated particles is 0.01 or more by mass% ratio by Sn / (Ni + M + P + Sn) by EDX analysis,
A high-strength, high-heat-resistant copper alloy material having a breaking elongation of 5% or more in a tensile test in a direction parallel to the rolling direction. The high-strength, high-heat-resistant copper alloy material according to claim 1, further comprising 0.0005 to 0.05 mass% in total of at least one element selected from the group consisting of Al and Mn. . The ratio C1s / Cu2p of the peak area value of C1s to the peak area value of Cu2p on the surface by XPS analysis after alkaline cathode electrolytic cleaning is 0.35 or less, and the observation area when the surface is observed by EBSD analysis The high-strength, high-heat-resistant copper alloy material according to claim 1 or 2, wherein an area ratio of fine crystal grains having an equivalent circle diameter of less than 0.5 µm is 0.90 or less.