CN111748713A - Copper alloy, copper-clad laminate and electronic device component - Google Patents

Copper alloy, copper-clad laminate and electronic device component Download PDF

Info

Publication number
CN111748713A
CN111748713A CN202010212628.3A CN202010212628A CN111748713A CN 111748713 A CN111748713 A CN 111748713A CN 202010212628 A CN202010212628 A CN 202010212628A CN 111748713 A CN111748713 A CN 111748713A
Authority
CN
China
Prior art keywords
copper alloy
copper
rolling
mass
gloss
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010212628.3A
Other languages
Chinese (zh)
Inventor
藤野慎平
野末贵裕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Nippon Mining and Metals Corp
Original Assignee
JX Nippon Mining and Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JX Nippon Mining and Metals Corp filed Critical JX Nippon Mining and Metals Corp
Priority to CN202211078499.9A priority Critical patent/CN115418525A/en
Publication of CN111748713A publication Critical patent/CN111748713A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/10—Alloys based on copper with silicon as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Metal Rolling (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Conductive Materials (AREA)

Abstract

The invention relates to a copper alloy, a copper alloy stretched article and an electronic device component. Specifically, the invention provides a copper alloy with high glossiness and good weldability, and a copper extending product and an electronic machine part using the copper alloy. The copper alloy of the present invention contains 0.5 to 5.0 mass% of Ni and 1 or more of Co in total, 0.1 to 1.2 mass% of Si in total, and the balance of Cu and unavoidable impuritiesThe rolled material comprising the impurity (b) has a surface roughness Rsk of-0.50 to 0.70 measured in a direction perpendicular to the rolling direction and a 60-degree gloss G60 measured in a direction parallel to the rolling directionRDIs more than 200.

Description

Copper alloy, copper-clad laminate and electronic device component
Technical Field
The present invention relates to a copper alloy, a copper alloy stretched article and an electronic device component.
Background
In the production of copper and copper alloy strips and foils, it is known that the surface gloss is adjusted in cold rolling. The conditions to be controlled in the cold rolling are rolling speed, viscosity of rolling oil, temperature of rolling oil, degree of working, surface roughness of work rolls, diameter of work rolls, and the like.
For example, japanese patent application laid-open No. 2006-281249 (patent document 1) discloses the following: a rolled copper foil of pure copper is used as a flexible printed circuit board (FPC) using a copper-clad laminate, and an oil film equivalent specified by the following formula (1) is adjusted in cold rolling:
(oil film equivalent) { (rolling oil viscosity, dynamic viscosity at 40 ℃; cSt) × (rolling speed; m/min) }/{ (yield stress of material; kg/mm)2) × (roll nip angle; rad) } … (1).
According to patent document 1, the glossiness of a rolled copper foil made of pure copper can be adjusted by controlling the oil film equivalent by using a low viscosity rolling oil, reducing the rolling speed, or the like based on the above formula (1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2006-281249.
Disclosure of Invention
[ problems to be solved by the invention ]
The thickness of the oil film present between the rolling roll and the rolled copper foil is not strictly uniform, but a thick portion and a thin portion are mixed. The plastic deformation of the surface differs between portions where the oil film is thick and portions where the oil film is thin.
The pressing force acting on the surface is greater in the portion where the oil film is thin than in the portion where the oil film is thick, and the binding of the irregularities formed on the surface of the rolling roll is strong. Therefore, the oxide film on the surface of the thin oil film is broken by the irregularities formed on the surface of the rolling roll, and a new surface appears. On the other hand, in a portion having a thick oil film, the pressing force acting on the surface is small compared to a portion having a thin oil film, and the irregularities formed on the surface of the rolling roll are less restrained. Therefore, the oxide film on the surface is preserved in the portion having the oil film thickness due to the fluid oil film interposed therebetween.
The rolled copper foil forms local depressions from the metallic structure, which are called oil pits (oil pits). The oil pits are portions where the oil film is locally thickened in the surface of the rolled copper foil. The oil pits remain on the oxide film to form pits, which inhibit light reflection and prevent the gloss from being improved. Therefore, in the case of a rolled copper foil composed of pure copper, if the oil film equivalent is small, the oil film existing between the rolling roll and the rolled copper foil becomes thin, and as a result, the occurrence of oil pits is suppressed, and a rolled copper foil with high glossiness can be obtained.
However, it is known that even if the oil film equivalent is controlled to be small for the Corson alloy (Corson alloy), only a significantly lower gloss than that expected from the performance of pure copper can be obtained. In particular, this tendency is strong in a Carson alloy foil having a thickness of 0.1mm or less.
Further, in the study of improving the glossiness by controlling the oil film equivalent, it is known that a copper alloy having poor weldability is widely seen. In particular, the tendency is strong in the case of a low-gloss casson alloy foil, and there is a copper alloy having poor weldability also in the case of a high-gloss alloy foil.
Accordingly, the present invention provides a copper alloy having high glossiness and excellent weldability, and a copper alloy and an electronic device component using the same.
[ means for solving the problems ]
The copper alloy according to the embodiment of the present invention is a copper alloy which is a rolled material containing 0.5 to 5.0 mass% in total of 1 or more of Ni and Co, 0.1 to 1.2 mass% of Si, and the balance of copper and inevitable impurities, and has a surface roughness Rsk of-0.50 to 0.70 measured in a direction perpendicular to a rolling direction, and a 60-degree gloss G60 measured in a direction parallel to the rolling directionRDIs more than 200.
Copper alloy of an embodiment of the present invention in one example, the 60 degree gloss G60 of the surface measured at right angles to the rolling directionTDIs more than 150.
In another example, the surface roughness Ra of the copper alloy according to the embodiment of the present invention measured in a direction perpendicular to the rolling direction is 0.03 to 0.20.
Copper alloy according to the embodiment of the present invention in still another embodiment, a surface of a rolled material is provided withPreparing a plating layer, and measuring the 60-degree glossiness G60 of the surface of the plating layer along the direction perpendicular to the rolling direction of the rolled materialTDIs more than 250.
In still another example, the copper alloy according to the embodiment of the present invention contains 0.005 to 3.0 mass% of 1 or more of Sn, Zn, Mg, Cr, Mn, Fe, Ti, Zr, P, Ag, and B in total.
In another aspect, the present invention provides a copper alloy for a copper alloy.
In still another aspect, the present invention is an electronic device component including a copper alloy, the electronic device component including a camera component.
[ Effect of the invention ]
According to the present invention, a copper alloy having high glossiness and excellent weldability, and a copper-extended product and an electronic device component using the same can be provided.
Detailed Description
Hereinafter, embodiments of the present invention will be described. The copper alloy according to the embodiment of the present invention is a rolled material containing 0.5 to 5.0 mass% in total of 1 or more of Ni and Co, 0.1 to 1.2 mass% of Si, and the balance of copper and inevitable impurities, and has a 60-degree gloss G60 on the surface measured in a direction parallel to the rolling directionRDIs more than 200.
(amounts of Ni, Co and Si added)
Ni, Co and Si are precipitated as intermetallic compounds such as Ni-Si, Co-Si and Ni-Co-Si by an appropriate aging treatment. The precipitates act to improve the strength, and Ni, Co, and Si that are dissolved in the Cu base material by precipitation are reduced, thereby improving the conductivity. However, if the total amount of Ni and Co is less than 0.5 mass% or Si is less than 0.1 mass%, it is difficult to obtain a high-strength copper alloy. If the total amount of Ni and Co exceeds 5.0 mass% or Si exceeds 1.2 mass%, the alloy is difficult to produce due to hot rolling cracking or the like.
Therefore, in the copper alloy according to the embodiment of the present invention, the total of 1 or more of Ni and Co is 0.5 to 5.0 mass%, and Si is 0.1 to 1.2 mass%. The amount of 1 or more of Ni and Co added is more preferably 0.8 mass% or more, and still more preferably 1.2 mass% or more. The amount of 1 or more of Ni and Co added is more preferably 4.0 mass% or less, and still more preferably 3.0 mass% or less. The amount of Si added is more preferably 0.35 mass% or more, and still more preferably 0.40 mass% or more. The amount of Si added is preferably 0.90 mass% or less, and more preferably 0.80 mass% or more.
(other additional elements)
Sn, Zn, Mg, Cr, Mn, Fe, Ti, Zr, P, Ag, B as subcomponents contribute to the increase in strength. Further, Zn is effective for improving the thermal peeling resistance of Sn plating, Mg is effective for improving the stress relaxation property, and Cr and Mn are effective for improving the hot workability. If the total amount of Sn, Zn, Mg, Cr, Mn, Fe, Ti, Zr, P, Ag and B is less than 0.005 mass%, the above-mentioned effects cannot be obtained, and if it exceeds 3.0 mass%, the bending workability is remarkably lowered. Therefore, the copper alloy according to the embodiment of the present invention preferably contains these elements in an amount of 0.005 to 3.0 mass%, more preferably 0.01 to 1.0 mass%, based on the total amount.
(gloss degree)
The copper alloy according to the embodiment of the present invention has a 60 degree gloss G60 of the surface measured in a direction parallel to the rolling directionRDIs 200 or more, more preferably 250 or more, and still more preferably 300 or more. Thus, a copper alloy having a high metallic luster in which the crater-like irregularities are suppressed can be obtained.
60 degree gloss G60 of copper alloy surfaceRDThe higher the gloss, the more high gloss can be exhibited, so that although the product appearance becomes excellent, if the gloss G60 is obtainedRDIf it is too high, good solder wettability may not be obtained. The gloss G60 of the surface in the direction parallel to the rolling direction is not limited to the followingRDTypically, the concentration is preferably 200 to 500, and typically more preferably 250 to 250.
60 degree gloss G60RDCan be obtained by the following method: the Gloss at an incident angle of 60 ° in a direction parallel to the rolling direction was measured using various Gloss meters such as the Handy Gloss Meter PG-1 manufactured by JIS Z8741, for example, by the Nippon Denshoku industries Ltd.
Further, the copper alloy of the present invention has a 60-degree gloss G60 in the direction perpendicular to the rolling directionTDMore than 150, typically 150 to 450, more typically 200 to 400.
(glossiness of plating treatment layer)
The copper alloy of the present invention can maintain high glossiness even when a plating layer of about 0.1 to 20 μm is formed on the surface of the copper alloy by performing a predetermined plating treatment. That is, the copper alloy of the present invention has a plating layer on the surface of a rolled material, and the 60-degree gloss G60 on the surface of the plating layer when measured in a direction perpendicular to the rolling direction of the rolled materialTDIs more than 250. According to the present invention, a copper alloy having a plating layer excellent in oxidation resistance and high in metallic luster excellent in visual quality can be obtained.
Examples of the plating layer include: a copper-plated layer, a tin-plated layer, a Ni-plated layer, or a gold-plated layer, a combination of surface plating and under-plating, or a layer in which these plating layers are arranged in stripes or dots, or the like. In particular, by providing a Ni plating layer as a plating layer, a copper alloy having a high-gloss plating layer excellent in appearance and corrosion resistance can be obtained.
(surface roughness Rsk)
In an embodiment of the present invention, the surface roughness Rsk represents the geometrical specification (GPS) -surface properties based on the product made by JISB0601 ": profile curve mode-the result measured by the index defined by the wording, definition and surface property parameters "(2017). For example, the surface roughness distribution of the surface of the rolled material in a direction perpendicular to the rolling direction can be calculated based on JIS B0601(2013) using a non-contact laser type surface roughness meter, such as a confocal microscope manufactured by laser technologies and accompanying software.
The JISB0601 roughness curve has a shape in which peaks and valleys are alternately connected with each other with an average line therebetween. When the average line is taken as the symmetry axis, Rsk is an index indicating the symmetry between the mountain and the valley, and can be conceptually understood as follows according to its definition.
(1) When there are more hills with high height and narrow width and more valleys with shallow depth and wide width, Rsk takes a positive value. The more mountains that are high and narrow in height and the more valleys that are shallow in depth and wide in width, the larger the absolute value of Rsk.
(2) When there are many hills with low height and wide width and many valleys with deep depth and narrow width, Rsk takes a negative value. The more mountains that are low in height and wide in width and the more valleys that are deep in depth and narrow in width, the larger the absolute value of Rsk.
(3) When the height of the mountain is the same as the depth of the valley and the width of the mountain is the same as the width of the valley, Rsk shows 0.
On the surface of the copper alloy finished by cold rolling, local depressions due to treatment or working in steps other than cold rolling and cold rolling are present in many cases. If the density of the local depressions is high, the absolute value of Rsk shows a smaller value when Rsk is a positive value. Further, if the density of the local depressions is high, the absolute value of Rsk shows a large value when Rsk is a negative value.
Sometimes the treatment or machining does not have an effect on the local depressions due to the shape. Or the effect of treatment or processing may be small. Therefore, foreign matter is likely to remain in the local recess. Examples of the foreign matter include a pickling solution used in a pickling step, a rolling oil used in a cold rolling step, a degreasing solution used in a step of removing the rolling oil, and oxides generated by heat treatment such as aging treatment.
The presence of foreign matter in the local depressions is a cause of deterioration in weldability of the copper alloy. Therefore, it is preferable that the density of the local depressions is low. That is, when Rsk is a positive value, the absolute value of Rsk is preferably large. When Rsk is a negative value, the absolute value of Rsk is preferably small.
The local depressions present on the copper alloy surface have an influence on the reflection of light. That is, light incident on the local depression is absorbed by the local depression without being reflected. Or the incident angle and the reflection angle of the light incident to the local depression may not be the same. Therefore, the local dishing is a cause of lowering the glossiness.
In the case where Rsk is a positive value, the absolute value of Rsk is preferably large from the viewpoint of the glossiness of the copper alloy surface. When Rsk is a negative value, the absolute value of Rsk is preferably small. Specifically, the copper alloy according to the embodiment of the present invention has a surface roughness Rsk of-0.50 to 0.70. If Rsk is less than-0.50, the density of local depressions increases, which may result in reduced gloss and poor weldability. The upper limit of the preferable range is not determined depending on the purpose of metallic luster and weldability, but is not more than 0.7 in the case of the strips and foils of the casson alloy. The copper alloy according to the embodiment of the present invention has a surface roughness Rsk more typically in the range of-0.20 to 0.65, and still more typically in the range of-0.15 to 0.40.
(surface roughness Ra)
The surface roughness Ra can be calculated from the surface roughness distribution of the surface of the rolled material in a direction perpendicular to the rolling direction using a non-contact laser type surface roughness meter based on JIS specification B0601(2013), such as a confocal microscope manufactured by laser technologies and accompanying software. The surface roughness Ra of the copper alloy of the present embodiment is 0.03 to 0.20 μm, more typically 0.06 to 0.07. mu.m. If the surface roughness Ra is not in the range of 0.03 to 0.20 μm, it may not be suitable as a material for electronic parts. Further, the surface roughness Ra can be adjusted by controlling the surface roughness of the work rolls in the cold rolling.
(thickness)
The copper alloy according to the embodiment of the present invention includes a strip or foil of a casson alloy, and the thickness thereof may be set to be typically 0.030mm to 0.15mm, more typically 0.030mm to 0.120mm, and still more typically 0.050 mm to 0.010 mm.
(use)
The copper alloy according to the embodiment of the present invention can be suitably used for electronic equipment parts including terminals, connectors, relays, switches, sockets, bus bars, lead frames, heat radiating plates, electromagnetic shielding plates, camera parts, and the like used in electric/electronic equipment, automobiles, and the like.
The copper alloy according to the embodiment of the present invention can be processed into the form of a copper alloy strip, a copper alloy sheet, or a copper foil by being finished to a predetermined thickness according to the purpose of use. When the copper alloy according to the embodiment of the present invention is processed into a copper foil, a high-gloss copper foil excellent in surface appearance can be obtained by subjecting the material subjected to the final cold rolling to acid pickling and polishing treatment.
(production method)
The copper alloy according to the embodiment of the present invention can be produced by a general manufacturing method of a casson alloy. In a general method for producing a casson alloy, first, raw materials such as electrolytic copper, Ni, Co, and Si are melted in a furnace to obtain a melt having a desired composition. Then, the melt was cast into an ingot. Then, the steel sheet is hot-rolled and cold-rolled to obtain a rolled material, and then subjected to solution treatment and aging treatment in this order to finish the rolled material into a copper alloy strip, a copper alloy sheet, or a copper foil having a desired thickness and properties. For increasing the strength, cold rolling may be performed between the solution treatment and the aging treatment or after the aging treatment.
(thickness of oxide film in aging treatment)
The copper alloy according to the embodiment of the present invention preferably has a surface oxide film thickness of 15 to 35nm after aging treatment. If the thickness of the surface oxide film is less than the lower limit of the preferable range, a portion having a thick surface oxide film, a thin portion, and a portion substantially not having an oxide film are mixed, and thus the oxidation state becomes uneven. If the oxidation state is not uniform, local corrosion, pitting corrosion, or so-called pitting corrosion may easily occur in the case of pickling after aging treatment, and local dishing may occur in the surface. Further, if the oxidation state is not uniform, the polishing effect tends to be non-uniform in the polishing treatment after pickling, and local dishing may occur on the surface. Further, if the oxidation state is not uniform, the film thickness of the rolling oil may be not uniform during cold rolling, and a local dent called an oil pit may be generated. The generation of such local depressions may cause the surface roughness Rsk to easily exhibit a negative value.
If the thickness of the oxide film exceeds the upper limit of the preferable range, the oxide film is brittle, so cracks are likely to be generated, and the same phenomenon as described above may occur due to cracks. The reason why the oxide film thickness portion, the thin portion, and the portion substantially not having the oxide film are mixed is that: in the casson alloy, a Co-Si-based or Ni-Si-based compound phase exists inside copper as a matrix phase, and the oxidation rates of these compound phases are different, so that a local difference is likely to occur in the generation of an oxide film in an initial stage of the oxide film being thin. The reason why the Co-Si-based or Ni-Si-based compound phase is contained is that: in the production of the casson alloy, there is a cooling process from a high temperature, and a Co — Si-based or Ni — Si-based compound phase is precipitated or crystallized. The surface oxide film formed on the rolled surface of the copper alloy after the aging treatment is more preferably 25nm or less, and still more preferably 20nm or less.
(method of measuring thickness of oxide film)
The thickness of the oxide film can be measured by, for example, Auger Electron Spectroscopy (AES). In the AES analysis, measurement of the oxygen concentration and sputtering with Ar were alternately performed to prepare an oxygen concentration curve. The horizontal axis of the concentration curve represents the integrated value of the sputtering time, and the vertical axis represents the oxygen concentration. The oxygen concentration of the surface layer of the aged casson alloy is high. When Ar sputtering and measurement of the oxygen concentration are further alternately performed at a position where the oxygen concentration is maximum, the oxygen concentration decreases as the cumulative value of the sputtering time increases. Then, the oxygen concentration showed a constant value regardless of the cumulative value of the sputtering time. The thickness of the oxide film was determined by obtaining the cumulative value of the Ar sputtering time, which is a value half the maximum value of the oxygen concentration, from the oxygen concentration curve and converting the Ar sputtering time into a length.
The length of the obtained product is calculated by the cumulative value of Ar sputtering time and is SiO2The sputtering rate of (2) is used as a reference. For example, when SiO2The sputtering rate of (2) is 1 nm/min, and the cumulative value of the Ar sputtering time is 12 minutes, the conversion is 1 × 12-12 nm, which is a method generally performed by Auger Electron Spectroscopy (AES), and the preferred sputtering rate is, for example, 1 to 2 nm/min, and the sputtering time of 1 time is 1 to 2 minutes.
(method of controlling thickness of oxide film)
The thickness of the oxide film in the aging treatment can be controlled by adjusting the atmosphere in the heating apparatus. The preferable atmosphere is a reducing gas used industrially, and the composition and the water concentration may be adjusted. For example, a mixture of a non-oxidizing gas such as argon or nitrogen and hydrogen or carbon monoxide may be used. For example, a gas having an argon gas content of 70 to 90 mass%, a hydrogen gas content of 10 to 30 mass%, and a dew point of-40 to-20 ℃ can be used.
Further, the thickness of the oxide film is not always preferable as long as it is within the range shown in the above example, and the composition of the gas must be adjusted according to the composition of the casson alloy because the casson alloy needs to contain Si which is easily reacted with oxygen. However, if the type of gas to be mixed is set to a minimum, the preferred composition can be adjusted by simple preliminary experiments.
In order to obtain a copper alloy having high glossiness and good weldability, it is preferable that the surface roughness Ra of the Carson alloy measured in a direction perpendicular to the rolling direction after the aging treatment is 0.04 to 0.06. If the surface roughness Ra of the surface measured in the direction perpendicular to the rolling direction after the aging treatment exceeds the upper limit of the preferable range, the cold rolling after the aging treatment causes unevenness in the film thickness of the rolling oil, and irregularities due to oil pits are generated, and Rsk in the product state easily shows a negative value. If Ra is less than the lower limit of the preferred range, cold rolling after aging treatment is preferred for the purpose of adjusting Rsk in the product state, but rolling oil is less likely to flow between the rolling rolls and the casson alloy, and cold rolling may become difficult. The surface roughness Ra can be adjusted by controlling the surface roughness of the work rolls in the cold rolling for adjusting the copper alloy subjected to the aging treatment to a predetermined thickness.
The surface roughness Ra after aging treatment can be calculated from the surface roughness distribution of the surface of the rolled material in the direction perpendicular to the rolling direction, using a non-contact laser type surface roughness meter, for example, a confocal microscope manufactured by laser technologies and accompanying software, based on JIS B0601(2013), as in the measurement of the surface roughness Ra of the product surface.
In order to obtain a high-gloss copper alloy having excellent surface appearance, it is preferable to control the temperature of the rolling oil in the final cold rolling step to an appropriate range. In the present embodiment, the rolling temperature is preferably set to 30 to 70 ℃, more preferably 40 to 60 ℃.
According to the copper alloy of the embodiment of the present invention, and the copper alloy, the copper alloy stretch product, the electronic device component, and the method for producing the copper alloy using the same, a high metallic luster can be produced on the surface, and a good surface appearance can be realized. Further, according to the copper alloy of the embodiment of the present invention, and the copper-clad article and the electronic device component using the same, the solderability is good regardless of the presence or absence of Pb, and even when a plating layer is formed on the copper alloy after acid pickling and polishing, a copper alloy having high gloss and excellent surface appearance can be obtained.
[ examples ]
Examples of the present invention and comparative examples are disclosed below, but these examples are provided for better understanding of the present invention and advantages thereof, and are not intended to limit the present invention.
The electrolytic copper is melted in a vacuum furnace, and Ni, Co, Si, and additive elements (subcomponents) are added so as to obtain a predetermined composition, thereby casting an ingot. The ingot is hot rolled and cold rolled in sequence to obtain a cold rolled strip. The cold rolled strip is subjected to solution treatment, then cold rolling and aging treatment are carried out, and finally acid pickling and grinding are carried out to prepare the product. In the acid-washing grinding step, acid-washing and polishing grinding using a mixed acid of hydrogen peroxide and sulfuric acid are performed.
The following evaluations were performed on each material after acid pickling and polishing.
< surface roughness Ra, Rsk >
The surface roughness Rsk of each material after acid pickling and polishing was measured. The surface roughness Rsk is a result calculated from a surface roughness distribution of the surface of the rolled material in a direction perpendicular to the rolling direction using a confocal microscope manufactured by laser technology corporation and accompanying software in accordance with JIS standard B0601 (2013). The surface roughness Ra after acid cleaning and polishing and the surface roughness Ra after aging treatment were evaluated using the same measuring apparatus as the surface roughness Rsk.
< gloss >
A gloss meter Handy gloss Meter manufactured by Nippon Denshoku industries Ltd was used in accordance with JIS Z8741PG-1 measurement of 60 degree gloss G60 in the parallel to the Rolling and in the Right Angle to the RollingRD、G60TD。
< weldability >
A solder test was carried out using a Pb-free solder M705-based solder made of Pb-doped solder (60 mass% Sn-40 mass% Pb) and heavy metal. In the evaluation of solder wettability, the solder was soldered in accordance with jis c60068-2-54 by a solderability tester (SAT-2000 manufactured by RHESCA corporation) in the same procedure as in the case of the submerged arc soldering method (meniscograph method), and the appearance of the soldered portion was observed. The measurement conditions were as follows. As pretreatment of the sample, degreasing was performed using acetone. Next, pickling was performed using a 10 vol% sulfuric acid aqueous solution. The test temperature of the solder was set at 245 + -5 deg.C. 25 percent by mass of rosin and 75 percent by mass of ethanol are used as the soldering flux. The immersion depth was 12mm, the immersion time was 10 seconds, the immersion speed was 25 mm/sec, and the width of the sample was 10 mm. As evaluation criteria, visual observation was performed with a 50-fold stereomicroscope, and a case where the entire surface of the welded portion was covered with solder was regarded as good (o), and a case where a part (pinhole) or the entire surface of the welded portion was not covered with solder was regarded as bad (x).
< plating treatment >
The acid-washed and ground material is subjected to alkaline electrolytic degreasing as a pretreatment, and is subjected to Ni plating after acid washing. The nickel plating includes normal gloss plating, semi-gloss plating, and the gloss plating is performed by using a commercially available plating solution. The results are shown in tables 1 and 2.
[ Table 1]
Figure BDA0002423336010000111
[ Table 2]
Figure BDA0002423336010000121
In examples 1 to 32 in which the surface roughness Ra, the oxide film thickness, and the rolling oil temperature after the aging treatment were in the preferable ranges, the 60-degree gloss of the surface measured in the direction parallel to the rolling directionG60RDA 60 degree gloss G60 of 200 or more measured in a direction perpendicular to the rolling directionTDA copper alloy having a high degree of gloss and a good surface appearance, a good weldability and a high degree of gloss after plating, of 150 or more.
Comparative example 1 the surface roughness Rsk of the product was low and the 60-degree gloss G60 in the direction perpendicular to the rolling direction was low because the oxide film thickness after aging treatment was thinTDLow. As a result, the weldability was poor and a sufficient metallic luster was not exhibited after 1 μm plating.
In comparative example 2, the oxide film after aging treatment was thin, and therefore the surface roughness Rsk of the product was low, and the gloss in both the rolling parallel direction and the rolling perpendicular direction was low. As a result, the weldability was poor and a sufficient metallic luster was not exhibited after 1 μm plating.
In comparative example 3, the temperature of the rolling oil was increased, but the surface roughness Rsk of the product could not be controlled within an appropriate range, and the gloss in both the parallel rolling direction and the perpendicular rolling direction was high. Although the plating of 1 μm showed metallic luster, the weldability was poor.
The rolling oil temperature of comparative example 4 was low. Therefore, the gloss in both the rolling parallel direction and the rolling orthogonal direction is low. As a result, although the weldability was good, the plating film did not exhibit sufficient metallic luster after 1 μm plating.
The surface roughness Ra after aging treatment of comparative example 5 was large. Therefore, the surface roughness Rsk of the product and the gloss in the rolling parallel direction and the rolling orthogonal direction are both low. As a result, the weldability was poor, and the 1 μm plating did not exhibit sufficient metallic luster.
The oxide film thickness after aging treatment of comparative examples 6 and 7. Therefore, the surface roughness Rsk of the product and the gloss in the rolling parallel direction and the rolling orthogonal direction are both low. As a result, the weldability was poor, and the 1 μm plating did not exhibit sufficient metallic luster.

Claims (7)

1. A copper alloy comprising 0.5 to 5.0 mass% in total of 1 or more of Ni and Co, 0.1 to 1.2 mass% of Si, and the balance of copper and unavoidable impuritiesThe surface roughness Rsk of the surface of the rolled material composed of impurities measured in the direction perpendicular to the rolling direction is-0.50-0.70, and the 60-degree glossiness G60 of the surface measured in the direction parallel to the rolling directionRDIs more than 200.
2. The copper alloy according to claim 1, having a 60 degree gloss G60 of the surface measured at right angles to the rolling directionTDIs more than 150.
3. The copper alloy according to claim 1 or 2, wherein a surface roughness Ra of the surface measured in a direction perpendicular to a rolling direction is 0.03 to 0.20.
4. The copper alloy according to any one of claims 1 to 3, wherein a plating layer is provided on a surface of the rolled material,
the 60 degree gloss G60 of the surface of the plating layer measured in a direction perpendicular to the rolling direction of the rolled materialTDIs more than 250.
5. The copper alloy according to any one of claims 1 to 4, which contains 0.005 to 3.0 mass% of 1 or more of Sn, Zn, Mg, Cr, Mn, Fe, Ti, Zr, P, Ag, B in total.
6. A copper extended article provided with the copper alloy according to any one of claims 1 to 5.
7. An electronic device part comprising the copper alloy according to any one of claims 1 to 5.
CN202010212628.3A 2019-03-28 2020-03-24 Copper alloy, copper-clad laminate and electronic device component Pending CN111748713A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211078499.9A CN115418525A (en) 2019-03-28 2020-03-24 Copper alloy, copper-clad laminate and electronic device component

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019064873A JP7296757B2 (en) 2019-03-28 2019-03-28 Copper alloys, copper products and electronic equipment parts
JP2019-064873 2019-03-28

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN202211078499.9A Division CN115418525A (en) 2019-03-28 2020-03-24 Copper alloy, copper-clad laminate and electronic device component

Publications (1)

Publication Number Publication Date
CN111748713A true CN111748713A (en) 2020-10-09

Family

ID=72673140

Family Applications (2)

Application Number Title Priority Date Filing Date
CN202211078499.9A Pending CN115418525A (en) 2019-03-28 2020-03-24 Copper alloy, copper-clad laminate and electronic device component
CN202010212628.3A Pending CN111748713A (en) 2019-03-28 2020-03-24 Copper alloy, copper-clad laminate and electronic device component

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN202211078499.9A Pending CN115418525A (en) 2019-03-28 2020-03-24 Copper alloy, copper-clad laminate and electronic device component

Country Status (4)

Country Link
JP (2) JP7296757B2 (en)
KR (3) KR20200115265A (en)
CN (2) CN115418525A (en)
TW (1) TWI743689B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4413992B2 (en) * 2007-10-03 2010-02-10 古河電気工業株式会社 Copper alloy sheet for electrical and electronic parts
JP2012201963A (en) * 2011-03-28 2012-10-22 Jx Nippon Mining & Metals Corp Co-Si BASED COPPER ALLOY SHEET
JP2013119639A (en) * 2011-12-06 2013-06-17 Jx Nippon Mining & Metals Corp Co-Si-BASED COPPER ALLOY SHEET

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3465108B2 (en) * 2000-05-25 2003-11-10 株式会社神戸製鋼所 Copper alloy for electric and electronic parts
JP3520034B2 (en) * 2000-07-25 2004-04-19 古河電気工業株式会社 Copper alloy materials for electronic and electrical equipment parts
JP4401998B2 (en) 2005-03-31 2010-01-20 日鉱金属株式会社 High-gloss rolled copper foil for copper-clad laminate and method for producing the same
JP2007268596A (en) 2006-03-31 2007-10-18 Nikko Kinzoku Kk Copper alloy foil for roughening treatment
JP4986499B2 (en) * 2006-04-26 2012-07-25 Ｊｘ日鉱日石金属株式会社 Method for producing Cu-Ni-Si alloy tin plating strip
JP5362921B1 (en) * 2012-11-09 2013-12-11 Ｊｘ日鉱日石金属株式会社 Surface-treated copper foil and laminate using the same
JP2016036829A (en) 2014-08-07 2016-03-22 Jx日鉱日石金属株式会社 Rolled copper foil, and secondary battery power collector using the same
JP6788471B2 (en) 2016-10-14 2020-11-25 Ｄｏｗａメタルテック株式会社 Cu-Ni-Co-Si based copper alloy thin plate material and manufacturing method and conductive member

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4413992B2 (en) * 2007-10-03 2010-02-10 古河電気工業株式会社 Copper alloy sheet for electrical and electronic parts
JP2012201963A (en) * 2011-03-28 2012-10-22 Jx Nippon Mining & Metals Corp Co-Si BASED COPPER ALLOY SHEET
JP2013119639A (en) * 2011-12-06 2013-06-17 Jx Nippon Mining & Metals Corp Co-Si-BASED COPPER ALLOY SHEET

Also Published As

Publication number Publication date
KR20240046458A (en) 2024-04-09
TW202035725A (en) 2020-10-01
JP2022095903A (en) 2022-06-28
CN115418525A (en) 2022-12-02
JP2020164908A (en) 2020-10-08
KR20220070187A (en) 2022-05-30
KR20200115265A (en) 2020-10-07
TWI743689B (en) 2021-10-21
JP7296757B2 (en) 2023-06-23
JP7381644B2 (en) 2023-11-15

Similar Documents

Publication Publication Date Title
KR101419147B1 (en) Copper alloy sheet and process for producing same
KR101577877B1 (en) Process for producing copper alloy sheet material
JP6055242B2 (en) Cu-Mg-P-based copper alloy Sn plated plate and method for producing the same
JP6113674B2 (en) Copper alloy strip with surface coating layer with excellent heat resistance
JP3962751B2 (en) Copper alloy sheet for electric and electronic parts with bending workability
JP5851000B1 (en) Copper alloy strip for LED lead frame
JP4986499B2 (en) Method for producing Cu-Ni-Si alloy tin plating strip
EP2743381A1 (en) Tin-plated copper alloy terminal member with outstanding insertion and removal characteristics
US20110200480A1 (en) Copper alloy material for electric/electronic parts
KR20170032455A (en) Conductive material for connection parts which has excellent minute slide wear resistance
JP5144814B2 (en) Copper alloy material for electrical and electronic parts
TWI628407B (en) Copper alloy plate and coil for heat dissipation parts
JP5950499B2 (en) Copper alloy for electrical and electronic parts and copper alloy material with Sn plating
JP5393739B2 (en) Cu-Ni-Si alloy tin plating strip
US20220081738A1 (en) Copper alloy plate, plating film-attached copper alloy plate, and methods respectively for manufacturing these products
JP4688100B2 (en) Manufacturing method of Cu plated steel sheet for electrical contacts
JP5339995B2 (en) Cu-Zn-Sn alloy plate and Cu-Zn-Sn alloy Sn plating strip
JP2007031795A (en) Cu-Ni-Sn-P-BASED COPPER ALLOY
JP2011157607A (en) Conductor made of aluminum alloy and method for producing the same
CN111748713A (en) Copper alloy, copper-clad laminate and electronic device component
KR102247328B1 (en) Titanium clad material and method for manufacturing the same
JP2023032936A (en) Copper plate material and method for producing the same
JP2010236038A (en) Copper alloy sheet excellent in thermal peeling resistance of tin plating
JPH01177316A (en) Manufacture of steel sheet for lead frame excellent in rust resistance, formability, and platability

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination