EP2088215A1 - Copper alloy material for electrical/electronic part and process for producing the same - Google Patents

Copper alloy material for electrical/electronic part and process for producing the same Download PDF

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Publication number
EP2088215A1
EP2088215A1 EP07829424A EP07829424A EP2088215A1 EP 2088215 A1 EP2088215 A1 EP 2088215A1 EP 07829424 A EP07829424 A EP 07829424A EP 07829424 A EP07829424 A EP 07829424A EP 2088215 A1 EP2088215 A1 EP 2088215A1
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EP
European Patent Office
Prior art keywords
copper alloy
mass
electric
electronic parts
alloy material
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.)
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Application number
EP07829424A
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German (de)
French (fr)
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EP2088215A4 (en
Inventor
Junsuke Nakano
Keisuke Kitazato
Takao Hirai
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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Publication date
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Publication of EP2088215A1 publication Critical patent/EP2088215A1/en
Publication of EP2088215A4 publication Critical patent/EP2088215A4/en
Withdrawn legal-status Critical Current

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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
    • 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
    • B21B1/22—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 plates, strips, bands or sheets of indefinite length
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals

Definitions

  • the present invention relates to a copper alloy material for electric/electronic parts and to a method of producing the same.
  • Sheet and strip materials of copper-based alloys that can be used for electric/electronic parts, such as lead frames, terminals, connectors, relays and switches, are required to be compatible between high strength and high electric conductivity as well as highly precise workability.
  • the lead frame that can be used for a circuit board in an integrated circuit is produced as a frame body having the required number of leads, by press-punching of the sheet and strip materials of the copper-based alloy.
  • the conventional materials for electric/electronic parts have such problems that high precession punching is difficult due to dimensional changes of the material before and after the above-mentioned strain relief annealing, and that automatic conveyance to a press machine becomes difficult due to deformation of the space between conveyance pilot pins.
  • a lead frame material having a contraction ratio of 0.03% or less as a ratio of the length of the material heated at 650°C for 10 minutes to the length of the original material is produced by strain relief annealing without applying a tensile strength or by strain relief annealing by suppressing the tensile strength to 5.0 kg/mm 2 or less, in the course of the production in which the alloy is subjected to cold rolling to a thickness of a desired product and then subjected to cutting into slits having a predetermined width followed by strain relief annealing.
  • the contraction ratio is defined by ⁇ (the length of the original material - the length of the material after heating)/the length of the original material ⁇ ⁇ 100 (for example, see JP-A-5-109960 ("JP-A" means unexamined published Japanese patent application)).
  • a lead frame material having a difference of the contraction ratio of 0.01 % or less before and after the heat treatment at a strain relief annealing temperature or at a recrystallization temperature in the course of working the material is produced by controlling the tensile strength in a furnace for allowing the frame sheet to pass through a continuous annealing furnace to be from 1.0 to 8.5% or less of the 0.2% yield strength of the material of the original sheet in the course of production of the material.
  • the contraction ratio is defined as a rate of change of the reference length in the longitudinal direction after heating (for example, see JP-A-2003-286527 ).
  • JP-A-5-109960 and JP-A-2003-286527 are insufficient for solving the above-mentioned problems, since only contraction ratios in the direction parallel to the rolling direction have been noticed and there are no descriptions on the rate of dimensional change in the direction perpendicular to the rolling direction.
  • JP-A-2003-286527 prescribes the tensile strength in a continuous annealing furnace. The temperature in the furnace is only described as the conditions in the examples, so that the method described in JP-A-2003-286527 is insufficient for solving the problems.
  • C194 alloy is used as the copper alloy in the examples of JP-A-2003-286527 , there are no descriptions or suggestions on whether the conditions in the examples are generally applicable to other copper alloys.
  • the present invention contemplates for providing a copper alloy material for electric/electronic parts in which the rates of dimensional changes before and after strain relief annealing after press-punching are simultaneously controlled in both directions parallel to and perpendicular to the rolling direction.
  • the inventors of the present invention have found the following facts as a result of investigations for simultaneously controlling the rates of dimensional changes in both directions parallel to and perpendicular to the rolling direction before and after strain relief annealing of the copper alloy material.
  • the rate of dimensional change in the direction perpendicular to the rolling direction is particularly important, and it was shown to be necessary to control the rates of dimensional changes in both directions parallel to and perpendicular to the rolling direction in the range from -0.02% to +0.02% in minimum, preferably in the range from -0.01 % to +0.01%.
  • the inventors of the present invention have noted (1) quenching (displacement) of lattice defects that have been introduced by rolling and (2) precipitating Ni 2 Si, and forming solid solution of Ni 2 Si in a matrix phase again, with respect to the phenomenon of dimensional changes before and after heat treatment.
  • dimensional changes in the matrix phase are presumed to occur as a result of changes of aggregate structures, which are caused by quenching (displacement) of lattice defects introduced by rolling, by heat hysteresis.
  • the behavior of the dimensional change is different between the directions parallel to and perpendicular to the rolling direction, since the arrangement of the lattice defects introduced by rolling is directional.
  • the behavior of the dimensional change was investigated in various manners, and it was found that the behavior largely contributes to the dimensional change in the direction parallel to the rolling direction. It was also presumed that the dimensional change of the matrix phase becomes large by preferential growth and precipitation of Ni 2 Si and by forming solid solution of the compound again. Since precipitation grows in a preferentially grown direction, the behavior of the dimensional change is different between the directions parallel to and perpendicular to the rolling direction. It was found from various studies that the contribution of the dimensional change caused by preferential growth and precipitation of Ni 2 Si and formation of solid solution of Ni 2 Si again is particularly large in the direction perpendicular to the rolling direction. The present invention has been accomplished based on the above-mentioned findings.
  • the copper alloy material for electric/electronic parts of the present invention is produced by the steps comprising: finish rolling a copper alloy at a reduction ratio of 40% or less in a material producing process, subjecting the copper alloy finish-rolled to a heat treatment in the continuous annealing line (furnace) under the conditions at a temperature from 500°C to 800°C for a time period from 1 second to 100 seconds thereafter followed by further working the material in a material working process.
  • the material producing process in the present invention refers to the steps of producing the material for electric/electronic parts (such as sheet materials and strip materials) from an ingot, and includes a step of finish rolling and heat treatment in the continuous annealing furnace.
  • the material working process in the present invention refers to the steps before producing the electric/electronic parts by working the material (such as sheet materials and strip materials) for the electric/electronic parts, which material is produced in said material producing process.
  • the material working process includes, for example, pressing.
  • the reduction ratio by finish rolling in the material producing process is too large, many surface cracks may be formed or lattice defects are introduced in excess. Consequently, the rate of dimensional change in the direction parallel to the rolling direction before and after heat treatment in the steps thereafter (for example, the material working process) becomes so large that it is difficult to simultaneously control the rates of dimensional changes in the directions parallel to and perpendicular to the rolling direction within proper ranges.
  • the reduction ratio by finish rolling in the material producing process is 40% or less, preferably from 10% to 20%.
  • the continuous annealing temperature in the material producing process is from 500°C to 800°C, preferably from 600°C to 750°C.
  • the continuous annealing time in the material producing process is preferably 100 seconds or less, more preferably 60 seconds or less. Since a stable temperature distribution in the material is not obtained when the continuous annealing time is too short, stable solid solutions are not formed again and strain provided via rolling is not relieved to make it impossible to obtain desired mechanical characteristics. Therefore, the continuous annealing time is 1 second or more, preferably 10 seconds or more.
  • the thickness of the material produced in the material producing process is not particularly restricted, the thickness is preferably in the range from 0.25 to 0.05 mm.
  • the material in the present invention usually refers to those called as sheet materials and strip materials.
  • the material produced in the material producing process is formed into a processed material by the material working process including strain relief annealing at a temperature from 400°C to 600°C for a time period from 30 seconds to 1000 seconds.
  • the material working process is preferably a material working process for electric/electronic parts.
  • the material working process preferably includes a step of pressing. Strain provided via pressing is unable to be completely removed when the temperature of strain relief annealing in the material working process is too low. On the other hand, desired mechanical characteristics are not obtained due to advance of softening of the material when the strain relief annealing temperature is too high. Accordingly, the strain relief annealing temperature in the material working process is from 400°C to 600°C, preferably from 450°C to 550°C.
  • the strain relief annealing time in the material working process is a time period from 30 seconds to 1000 seconds, preferably a time period from 180 seconds to 600 seconds.
  • the rates of dimensional changes before and after heat treatment for strain relief annealing in both directions parallel to and perpendicular to the rolling direction is from -0.02% to +0.02% in the copper alloy material for electric/electronic parts of the present invention.
  • the preferable rates of dimensional changes before and after heat treatment for strain relief annealing in both directions parallel to and perpendicular to the rolling direction is also in the range from -0.01 % to +0.01%.
  • the preferable composition of the copper alloy of the copper alloy material for electric/electronic parts of the present invention will be described below.
  • An example of the copper alloy comprises Ni from 1.5 mass% to 4.5 mass% and Si from 0.35 mass% to 1.0 mass%, and further comprises any one or two or more elements selected from Mg from 0.05 mass% to 0.15 mass%, Sn from 0.05 mass% to 0.5 mass%, Zn from 0.05 mass% to 1 mass%, Ag from 0.01 % to 0.1 mass% and Cr from 0.05 mass% to 0.4 mass%, with the balance being made of copper and inevitable impurities.
  • Ni and Si have an effect for enhancing the strength of the alloy by forming a solid solution in the copper alloy, while the strength as well as electric conductivity of the alloy are remarkably improved by forming precipitates of a Ni 2 Si composition by applying appropriate aging treatment.
  • the alloy may fail in obtaining desired mechanical characteristics when the content of Ni is less than 1.5 mass% or the content of Si is less than 0.35%.
  • the content of Ni exceeds 4.5 mass% or the content of Si exceeds 1.0 mass% on the other hand, simultaneous control of the rates of dimensional changes in the direction parallel to and perpendicular to the rolling direction in proper ranges may be difficult since electric conductivity remarkably decreases and coarse Ni-Si particles are generated in the matrix phase.
  • the Ni content is further preferably from 2.0 mass% to 4.0 mass%, while the Si content is further preferably from 0.4 mass% to 0.90 mass%. It is desirable to allow the atomic ratio of the contents of Ni and Si in the alloy to be close to the atomic ratio of the stoichiometric composition of Ni 2 Si for simultaneously controlling the rate of dimensional change in the direction parallel to or perpendicular to the rolling direction. Accordingly, the ratio of the content of Si to the content of Ni (Ni content / Si content) is preferably in the range from 2 to 8, and a ratio of 4 is most preferable.
  • the copper alloy material comprises any one or two or more elements selected from Mg from 0.05 mass% to 0.15 mass%, Sn from 0.05 mass% to 0.5 mass%, Zn from 0.05 mass% to 1 mass%, Ag from 0.01 mass% to 0.1 mass%, and Cr from 0.05 mass% to 0.4 mass%, in addition to the above-mentioned components. Permitting these metals in the amounts described above may serve for enhancing the mechanical strength. More preferably, the alloy contains any one or two or more elements selected from Sn from 0.1 mass% to 0.125 mass% and Zn from 0.1 mass% to 0.5 mass%.
  • the rate of dimensional change in the present invention is defined as follows using the reference length before annealing and the reference length after annealing in the direction parallel to or perpendicular to the rolling direction: reference length after annealing ⁇ reference length before annealing / reference length before annealing ⁇ 100
  • a plus value of the rate of the dimensional change corresponds to expansion
  • a minus value of the rate of the dimensional change corresponds to contraction.
  • Usual production steps and treatment methods in the material producing process of the copper alloy material for electric/electronic parts and in the material working process may be directly applied except the above-mentioned items.
  • the reduction ratio by hot rolling applied before finish rolling is preferably from 90 to 99% in the present invention.
  • the reduction ratio by cold rolling applied before finish rolling is preferably from 90 to 99%.
  • the electric/electronic parts in the present invention may be lead frames, connectors, terminals, relays and switches, preferable parts are lead frames and connectors for which fine and precise working is necessary.
  • the copper alloy material of the present invention is able to simultaneously reduce or control the rates of dimensional changes in both directions of parallel to and perpendicular to the rolling direction before or after strain relief annealing in mid course of or after press-punching in the material producing process of electric/electronic parts.
  • the copper alloy material of the present invention is particularly suitable as a material for connectors that are necessary to apply fine and precise press-punching in accordance with miniaturization of lead frames and portable phones.
  • the method of the present invention enables the copper alloy material for electric/electronic parts having above-described excellent physical properties to be industrially produced.
  • Copper alloys having the chemical compositions shown in Table 1 were used as lead frame materials.
  • An ingot was obtained by melting and cooling each material by a usual method. The ingot was hot rolled and annealed, and cold rolled materials with a thickness from 0.05 mm to 0.25 mm were obtained by finish rolling at a reduction ratio of 3%, 10%, 20%, 40% or 45%, as shown in Table 2, after repeating cold rolling and annealing.
  • Materials No. 1 to 44 shown in Table 2 were obtained by heat treatment of the cold rolled materials obtained above by controlling the tensile strength in the continuous annealing furnace at 0.7 kg/mm 2 , the temperature in the furnace at 450, 500, 600, 700, 800 or 850°C, and the annealing time at 10, 60, 100 or 120 seconds.
  • the rates of dimensional changes before and after heat treatment are in the range from -0.02% to +0.02% in both directions parallel to and perpendicular to the rolling direction in Examples No. 1 to 32 according to the present invention.
  • the rates of dimensional changes before and after heat treatment in both directions parallel to and perpendicular to the rolling direction are particularly excellent, since they are in the range from -0.01 % to +0.01% in Examples No. 8, 9, 11, 12, 20, 21, 23 and 24 produced under particularly preferable conditions.
  • the rate of dimensional change in the direction parallel to the rolling direction is large in Comparative Examples No. 33 to 36 in which the reduction ratio by finish rolling is larger than the range according to the present invention.
  • the rate of dimensional change in the direction parallel to the rolling direction is large in Comparative Examples No. 37 and 39 in which the temperature in the furnace during continuous annealing is lower than the range according to the present invention.
  • the rate of dimensional change in the direction perpendicular to the rolling direction is particularly large in Comparative Examples No. 38 and 40 in which the temperature in the furnace during continuous annealing is higher than the range according to the present invention.
  • the rate of dimensional change in the direction perpendicular to the rolling direction is particularly large in Comparative Examples No. 41 to 44 in which the annealing time of continuous annealing is longer than the range according to the present invention.
  • the copper alloy material for electric/electronic parts of the present invention is subjected to strain relief annealing for fine working for producing the electric/electronic parts. Accordingly, the copper alloy material is favorable as a copper alloy material for electric/electronic parts in which the rates of dimensional changes in the direction parallel to and perpendicular to the rolling direction before and after heat treatment for strain relief annealing can be simultaneously controlled.
  • the method of producing a copper alloy material for electric/electronic parts of the present invention is able to favorably produce the copper alloy material for electric/electronic parts of the present invention.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
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Abstract

A copper alloy material for electric/electronic parts, which is produced by the steps containing: finish rolling a copper alloy at a reduction ratio of 40% or less, subjecting the copper alloy finish-rolled to a heat treatment under the conditions at a temperature from 500°C to 800°C for a time period from 1 second to 100 seconds by means of a continuous annealing line, and strain relief annealing the copper alloy heat-treated under the conditions at a temperature from 400°C to 600°C for a time period from 30 seconds to 1000 seconds,
wherein the copper alloy material for electric/electronic parts has rates of dimensional changes before and after the strain relief annealing in both directions parallel to and perpendicular to the rolling direction within the range from -0.02% to +0.02%.

Description

    [TECHNICAL FIELD]
  • The present invention relates to a copper alloy material for electric/electronic parts and to a method of producing the same.
  • [BACKGROUND ART]
  • Sheet and strip materials of copper-based alloys that can be used for electric/electronic parts, such as lead frames, terminals, connectors, relays and switches, are required to be compatible between high strength and high electric conductivity as well as highly precise workability.
    For example, the lead frame that can be used for a circuit board in an integrated circuit is produced as a frame body having the required number of leads, by press-punching of the sheet and strip materials of the copper-based alloy.
  • In accordance with high density integration of electric/electronic parts in recent years, fine and precise press-punching is necessary for connectors, while press-punching is applied at least twice in the course of working a complicated lead frame in which the number of leads is increased. In this case, a strain relief annealing is applied after the first press-punching step, and strain by working provided via press-punching is relieved, and then a final lead frame is produced by applying press-punching again.
  • However, the conventional materials for electric/electronic parts have such problems that high precession punching is difficult due to dimensional changes of the material before and after the above-mentioned strain relief annealing, and that automatic conveyance to a press machine becomes difficult due to deformation of the space between conveyance pilot pins.
  • Conventional techniques proposed by taking the dimensional change before and after the strain relief annealing in working the lead frame into consideration are as follows.
  • In an example of production methods of lead frames made of Fe-Ni based alloys or Fe-Ni-Co based alloys, a lead frame material having a contraction ratio of 0.03% or less as a ratio of the length of the material heated at 650°C for 10 minutes to the length of the original material is produced by strain relief annealing without applying a tensile strength or by strain relief annealing by suppressing the tensile strength to 5.0 kg/mm2 or less, in the course of the production in which the alloy is subjected to cold rolling to a thickness of a desired product and then subjected to cutting into slits having a predetermined width followed by strain relief annealing. Herein, the contraction ratio is defined by {(the length of the original material - the length of the material after heating)/the length of the original material} × 100 (for example, see JP-A-5-109960 ("JP-A" means unexamined published Japanese patent application)).
  • Further, in an example of production methods of lead frames made of copper or copper alloys, a lead frame material having a difference of the contraction ratio of 0.01 % or less before and after the heat treatment at a strain relief annealing temperature or at a recrystallization temperature in the course of working the material is produced by controlling the tensile strength in a furnace for allowing the frame sheet to pass through a continuous annealing furnace to be from 1.0 to 8.5% or less of the 0.2% yield strength of the material of the original sheet in the course of production of the material. Herein, the contraction ratio is defined as a rate of change of the reference length in the longitudinal direction after heating (for example, see JP-A-2003-286527 ).
  • [DISCLOSURE OF INVENTION]
  • It has been noticed to reduce the contraction ratio in metal materials for the electric/electronic parts for applying fine working, and the above-mentioned conventional measures were employed. However, the methods disclosed in JP-A-5-109960 and JP-A-2003-286527 are insufficient for solving the above-mentioned problems, since only contraction ratios in the direction parallel to the rolling direction have been noticed and there are no descriptions on the rate of dimensional change in the direction perpendicular to the rolling direction. Further, JP-A-2003-286527 prescribes the tensile strength in a continuous annealing furnace. The temperature in the furnace is only described as the conditions in the examples, so that the method described in JP-A-2003-286527 is insufficient for solving the problems. Furthermore, only C194 alloy is used as the copper alloy in the examples of JP-A-2003-286527 , there are no descriptions or suggestions on whether the conditions in the examples are generally applicable to other copper alloys.
  • In view of these problems, the present invention contemplates for providing a copper alloy material for electric/electronic parts in which the rates of dimensional changes before and after strain relief annealing after press-punching are simultaneously controlled in both directions parallel to and perpendicular to the rolling direction.
  • The inventors of the present invention have found the following facts as a result of investigations for simultaneously controlling the rates of dimensional changes in both directions parallel to and perpendicular to the rolling direction before and after strain relief annealing of the copper alloy material.
  • It was found from various experimental studies for simultaneously controlling the rates of dimensional changes in both directions parallel to and perpendicular to the rolling direction before and after strain relief annealing during or after press-punching that the rates of dimensional changes in both directions parallel to and perpendicular to the rolling direction is to be controlled in the range from -0.02% to +0.02% in minimum, preferably in the range from -0.01% to +0.01%, for stable automatic conveyance when the clearance between conveyance pins and pilot holes is, for example, about 5 µm in one side. In particular, when an outer lead portion of the lead frame having a narrow pitch is press-punched with high precision of about ±3 µm so as to protrude in four directions, the rate of dimensional change in the direction perpendicular to the rolling direction is particularly important, and it was shown to be necessary to control the rates of dimensional changes in both directions parallel to and perpendicular to the rolling direction in the range from -0.02% to +0.02% in minimum, preferably in the range from -0.01 % to +0.01%.
  • Further, the inventors of the present invention have noted (1) quenching (displacement) of lattice defects that have been introduced by rolling and (2) precipitating Ni2Si, and forming solid solution of Ni2Si in a matrix phase again, with respect to the phenomenon of dimensional changes before and after heat treatment. In other words, dimensional changes in the matrix phase are presumed to occur as a result of changes of aggregate structures, which are caused by quenching (displacement) of lattice defects introduced by rolling, by heat hysteresis. Thus, the behavior of the dimensional change is different between the directions parallel to and perpendicular to the rolling direction, since the arrangement of the lattice defects introduced by rolling is directional. The behavior of the dimensional change was investigated in various manners, and it was found that the behavior largely contributes to the dimensional change in the direction parallel to the rolling direction. It was also presumed that the dimensional change of the matrix phase becomes large by preferential growth and precipitation of Ni2Si and by forming solid solution of the compound again. Since precipitation grows in a preferentially grown direction, the behavior of the dimensional change is different between the directions parallel to and perpendicular to the rolling direction. It was found from various studies that the contribution of the dimensional change caused by preferential growth and precipitation of Ni2Si and formation of solid solution of Ni2Si again is particularly large in the direction perpendicular to the rolling direction. The present invention has been accomplished based on the above-mentioned findings.
  • According to the present invention, there is provided following means:
    1. (1) A copper alloy material for electric/electronic parts, which is produced by the steps comprising: finish rolling a copper alloy at a reduction ratio of 40% or less, subjecting the copper alloy finish-rolled to a heat treatment under the conditions at a temperature from 500°C to 800°C for a time period from 1 second to 100 seconds by means of a continuous annealing line, and strain relief annealing the copper alloy heat-treated under the conditions at a temperature from 400°C to 600°C for a time period from 30 seconds to 1000 seconds,
      wherein the copper alloy material for electric/electronic parts has rates of dimensional changes before and after the strain relief annealing in both directions parallel to and perpendicular to the rolling direction within the range from -0.02% to +0.02%;
    2. (2) The copper alloy material for electric/electronic parts according to the item (1), wherein the strain relief annealing is conducted in mid course of a material working process for electric/electronic parts;
    3. (3) The copper alloy material for electric/electronic parts according to the item (1) or (2), wherein the copper alloy material for electric/electronic parts is a lead frame material or a connector material;
    4. (4) The copper alloy material for electric/electronic parts according to any one of the items (1) to (3), wherein the copper alloy material for electric/electronic parts comprises Ni from 1.5 mass% to 4.5 mass% and Si from 0.35 mass% to 1.0 mass%, and further comprises at least one or plural elements selected from Mg from 0.05 mass% to 0.15 mass%, Sn from 0.05 mass% to 0.5 mass%, Zn from 0.05 mass% to 1 mass%, Ag from 0.01% to 0.1 mass%, and Cr from 0.05 mass% to 0.4 mass%, with the balance being made of copper and inevitable impurities;
    5. (5) A method of producing a copper alloy material for electric/electronic parts, comprising the steps of:
      • finish rolling a copper alloy at a reduction ratio of 40% or less;
      • subjecting the copper alloy finish-rolled to a heat treatment under the conditions at a temperature from 500°C to 800°C for a time period from 1 second to 100 seconds by means of a continuous annealing line; and
      • strain relief annealing the copper alloy heat-treated under the conditions at a temperature from 400°C to 600°C for a time period from 30 seconds to 1000 seconds,
      • to thereby produce the copper alloy material for electric/electronic parts having rates of dimensional changes before and after the strain relief annealing in both directions parallel to and perpendicular to the rolling direction within the range from -0.02% to +0.02%, and
    6. (6) The method of producing a copper alloy material for electric/electronic parts according to the item (5), wherein the strain relief annealing is conducted in mid course of a material working process for electric/electronic parts.
  • Other and further features and advantages of the invention will appear more fully from the following description.
  • [BEST MODE FOR CARRYING OUT THE INVENTION]
  • The copper alloy material for electric/electronic parts of the present invention is produced by the steps comprising: finish rolling a copper alloy at a reduction ratio of 40% or less in a material producing process, subjecting the copper alloy finish-rolled to a heat treatment in the continuous annealing line (furnace) under the conditions at a temperature from 500°C to 800°C for a time period from 1 second to 100 seconds thereafter followed by further working the material in a material working process. The material producing process in the present invention refers to the steps of producing the material for electric/electronic parts (such as sheet materials and strip materials) from an ingot, and includes a step of finish rolling and heat treatment in the continuous annealing furnace.
    The material working process in the present invention refers to the steps before producing the electric/electronic parts by working the material (such as sheet materials and strip materials) for the electric/electronic parts, which material is produced in said material producing process. The material working process includes, for example, pressing.
    When the reduction ratio by finish rolling in the material producing process is too large, many surface cracks may be formed or lattice defects are introduced in excess. Consequently, the rate of dimensional change in the direction parallel to the rolling direction before and after heat treatment in the steps thereafter (for example, the material working process) becomes so large that it is difficult to simultaneously control the rates of dimensional changes in the directions parallel to and perpendicular to the rolling direction within proper ranges. Accordingly, the reduction ratio by finish rolling in the material producing process is 40% or less, preferably from 10% to 20%.
  • When the temperature for continuous annealing in the material producing process is too low, lattice defects introduced by rolling are left behind to make the rate of dimensional change in the direction parallel to the rolling direction before and after heat treatment in the material producing process to be particularly large, and it may be difficult to simultaneously control the rates of dimensional changes in the directions parallel to and perpendicular to the rolling direction within proper ranges. Productivity may be also decreased when the continuous annealing temperature is too low since a long heat treatment time is necessary for quenching lattice defects. When the continuous annealing temperature is too high, on the contrary, the rate of dimensional change in the direction perpendicular to the rolling direction becomes particularly large since precipitation rapidly advances before and after the heat treatment in the steps (for example, the material working process) thereafter. Consequently, it is difficult to simultaneously control the rates of dimensional changes in the directions parallel to and perpendicular to the rolling direction within proper ranges. It may be also difficult to obtain desired mechanical characteristics when the continuous annealing temperature is too high since softening of the material advances. Accordingly, the continuous annealing temperature in the material producing process is from 500°C to 800°C, preferably from 600°C to 750°C.
  • Too long continuous annealing time in the material producing process makes it impossible to obtain desired mechanical characteristics since softening of the material advances to cause remarkable decrease of productivity. Accordingly, the continuous annealing time in the material producing process is preferably 100 seconds or less, more preferably 60 seconds or less. Since a stable temperature distribution in the material is not obtained when the continuous annealing time is too short, stable solid solutions are not formed again and strain provided via rolling is not relieved to make it impossible to obtain desired mechanical characteristics. Therefore, the continuous annealing time is 1 second or more, preferably 10 seconds or more.
  • While the thickness of the material produced in the material producing process is not particularly restricted, the thickness is preferably in the range from 0.25 to 0.05 mm. The material in the present invention usually refers to those called as sheet materials and strip materials.
  • The material produced in the material producing process is formed into a processed material by the material working process including strain relief annealing at a temperature from 400°C to 600°C for a time period from 30 seconds to 1000 seconds. The material working process is preferably a material working process for electric/electronic parts. Further, the material working process preferably includes a step of pressing.
    Strain provided via pressing is unable to be completely removed when the temperature of strain relief annealing in the material working process is too low. On the other hand, desired mechanical characteristics are not obtained due to advance of softening of the material when the strain relief annealing temperature is too high. Accordingly, the strain relief annealing temperature in the material working process is from 400°C to 600°C, preferably from 450°C to 550°C.
  • Strain provided via pressing is not sufficiently removed when the strain relief annealing time in the material working process is too short. Desired mechanical characteristics are not obtained due to the progress of softening of the material while productivity may be decreased when the strain relief annealing time is too long. Accordingly, the strain relief annealing time in the material working process is a time period from 30 seconds to 1000 seconds, preferably a time period from 180 seconds to 600 seconds.
  • The rates of dimensional changes before and after heat treatment for strain relief annealing in both directions parallel to and perpendicular to the rolling direction is from -0.02% to +0.02% in the copper alloy material for electric/electronic parts of the present invention. The preferable rates of dimensional changes before and after heat treatment for strain relief annealing in both directions parallel to and perpendicular to the rolling direction is also in the range from -0.01 % to +0.01%.
  • The preferable composition of the copper alloy of the copper alloy material for electric/electronic parts of the present invention will be described below.
    An example of the copper alloy comprises Ni from 1.5 mass% to 4.5 mass% and Si from 0.35 mass% to 1.0 mass%, and further comprises any one or two or more elements selected from Mg from 0.05 mass% to 0.15 mass%, Sn from 0.05 mass% to 0.5 mass%, Zn from 0.05 mass% to 1 mass%, Ag from 0.01 % to 0.1 mass% and Cr from 0.05 mass% to 0.4 mass%, with the balance being made of copper and inevitable impurities.
    Ni and Si have an effect for enhancing the strength of the alloy by forming a solid solution in the copper alloy, while the strength as well as electric conductivity of the alloy are remarkably improved by forming precipitates of a Ni2Si composition by applying appropriate aging treatment. However, the alloy may fail in obtaining desired mechanical characteristics when the content of Ni is less than 1.5 mass% or the content of Si is less than 0.35%. When the content of Ni exceeds 4.5 mass% or the content of Si exceeds 1.0 mass%, on the other hand, simultaneous control of the rates of dimensional changes in the direction parallel to and perpendicular to the rolling direction in proper ranges may be difficult since electric conductivity remarkably decreases and coarse Ni-Si particles are generated in the matrix phase. The Ni content is further preferably from 2.0 mass% to 4.0 mass%, while the Si content is further preferably from 0.4 mass% to 0.90 mass%. It is desirable to allow the atomic ratio of the contents of Ni and Si in the alloy to be close to the atomic ratio of the stoichiometric composition of Ni2Si for simultaneously controlling the rate of dimensional change in the direction parallel to or perpendicular to the rolling direction. Accordingly, the ratio of the content of Si to the content of Ni (Ni content / Si content) is preferably in the range from 2 to 8, and a ratio of 4 is most preferable.
  • Further, the copper alloy material comprises any one or two or more elements selected from Mg from 0.05 mass% to 0.15 mass%, Sn from 0.05 mass% to 0.5 mass%, Zn from 0.05 mass% to 1 mass%, Ag from 0.01 mass% to 0.1 mass%, and Cr from 0.05 mass% to 0.4 mass%, in addition to the above-mentioned components. Permitting these metals in the amounts described above may serve for enhancing the mechanical strength. More preferably, the alloy contains any one or two or more elements selected from Sn from 0.1 mass% to 0.125 mass% and Zn from 0.1 mass% to 0.5 mass%.
  • The rate of dimensional change in the present invention is defined as follows using the reference length before annealing and the reference length after annealing in the direction parallel to or perpendicular to the rolling direction: reference length after annealing − reference length before annealing / reference length before annealing × 100
    Figure imgb0001

    Herein, a plus value of the rate of the dimensional change corresponds to expansion, while a minus value of the rate of the dimensional change corresponds to contraction.
  • Usual production steps and treatment methods in the material producing process of the copper alloy material for electric/electronic parts and in the material working process may be directly applied except the above-mentioned items. For example, the reduction ratio by hot rolling applied before finish rolling is preferably from 90 to 99% in the present invention. The reduction ratio by cold rolling applied before finish rolling is preferably from 90 to 99%.
    While the electric/electronic parts in the present invention may be lead frames, connectors, terminals, relays and switches, preferable parts are lead frames and connectors for which fine and precise working is necessary.
  • The copper alloy material of the present invention is able to simultaneously reduce or control the rates of dimensional changes in both directions of parallel to and perpendicular to the rolling direction before or after strain relief annealing in mid course of or after press-punching in the material producing process of electric/electronic parts. The copper alloy material of the present invention is particularly suitable as a material for connectors that are necessary to apply fine and precise press-punching in accordance with miniaturization of lead frames and portable phones.
    The method of the present invention enables the copper alloy material for electric/electronic parts having above-described excellent physical properties to be industrially produced.
  • [EXAMPLES]
  • The present invention will be described in more detail based on examples given below, but the invention is not meant to be limited by these.
  • [Examples (examples of the present invention) and comparative examples]
  • Copper alloys having the chemical compositions shown in Table 1 were used as lead frame materials. An ingot was obtained by melting and cooling each material by a usual method. The ingot was hot rolled and annealed, and cold rolled materials with a thickness from 0.05 mm to 0.25 mm were obtained by finish rolling at a reduction ratio of 3%, 10%, 20%, 40% or 45%, as shown in Table 2, after repeating cold rolling and annealing.
  • Materials No. 1 to 44 shown in Table 2 were obtained by heat treatment of the cold rolled materials obtained above by controlling the tensile strength in the continuous annealing furnace at 0.7 kg/mm2, the temperature in the furnace at 450, 500, 600, 700, 800 or 850°C, and the annealing time at 10, 60, 100 or 120 seconds.
  • Then, the above-mentioned materials with a width of 55 mm were subjected to heat treatment in argon atmosphere at 500°C for 180 seconds as a simulation of strain relief annealing in mid course of or after press-punching in the working process of the lead frame. The rates of dimensional changes were calculated by measuring, after the heat treatment, the dimensional changes of a reference length 100 mm in the direction parallel to the rolling direction and a reference length 50 mm in the direction perpendicular to the rolling direction marked on the material, respectively, before the heat treatment. The results are shown in Table 2. Nos. 1 to 32 correspond to the examples according to the present invention, while Nos. 33 to 44 correspond to comparative examples.
  • [Table 1]
  • (Table 1)
    Kind of copper alloy Component (mass%)
    Ni Si Mg Sn Zn Ag Cr Cu
    A 3.0 0.65 0.15 - - - - Balance
    B 2.6 0.55 - - 0.5 0.05 - Balance
    C 2.3 0.50 0.10 0.15 0.5 - - Balance
    D 3.7 0.90 0.10 0.15 0.5 - 0.2 Balance
  • [Table 2]
  • (Table 2)
    No Thickness (mm) Kind of copper alloy Finish rolling Continuous annealing Rate (%) of dimensional change before and after heating (500°C × 180sec)
    Reduction ratio(%) Temperature in the furnace(°C) Heat treatment time (sec) Direction parallel to the rolling direction Direction perpendicular to the rolling
    1 0.050 A 3 500 10 0.0131 -0.0094
    2 0.100 B 3 500 100 0.0128 -0.0101
    3 0.150 C 3 800 10 -0.0041 -0.0182
    4 0.200 D 3 800 100 -0.0054 -0.0185
    5 0.250 A 10 500 10 0.0135 -0.0058
    6 0.050 B 10 500 60 0.0137 -0.0061
    7 0.100 C 10 500 100 0.0129 -0.0074
    8 0.150 D 10 600 10 0.0047 -0.0088
    9 0.200 A 10 600 50 0.0044 -0.0078
    10 0.250 B 10 600 100 0.0034 -0.0095
    11 0.050 C 10 700 10 0.0031 -0.0085
    12 0.100 D 10 700 50 0.0025 -0.0091
    13 0.150 A 10 700 100 0.0014 -0.0108
    14 0.200 B 10 800 10 0.0004 -0.0154
    15 0.250 C 10 800 60 -0.0025 -0.0165
    Example of this invention 16 0.050 D 10 800 100 -0.0027 -0.0177
    17 0.100 A 20 500 10 0.0157 -0.0049
    18 0.150 B 20 500 60 0.0154 -0.0052
    19 0.200 C 20 500 100 0.0154 -0.0068
    20 0.250 D 20 600 10 0.0068 -0.0074
    21 0.050 A 20 600 60 0.0061 -0.0069
    22 0.100 B 20 600 100 0.0049 -0.0082
    23 0.150 C 20 700 10 0.0044 -0.0072
    24 0.200 D 20 700 60 0.0041 -0.0079
    25 0.250 A 20 700 100 0.0031 -0.0091
    26 0.050 B 20 800 10 0.0024 -0.0142
    27 0.100 C 20 800 60 0.0010 -0.0148
    28 0.150 D 20 800 100 0.0015 -0.0161
    29 0.200 A 40 500 10 0.0184 -0.0014
    30 0.250 B 40 500 100 0.0171 -0.0031
    31 0.050 C 40 800 10 0.0048 -0.0141
    32 0.100 D 40 800 100 0.0031 -0.0151
    33 0.150 A 45 500 60 0.0274 0.0021
    34 0.200 B 45 600 60 0.0232 -0.0008
    35 0.250 C 45 700 60 0.0225 -0.0014
    36 0.050 D 45 800 60 0.0221 -0.0021
    37 0.100 A 10 450 60 0.0219 -0.0049
    Comparative example 38 0.150 B 10 850 60 -0.0005 -0.0231
    39 0.200 C 20 450 60 0.0232 -0.0051
    40 0.250 D 20 850 60 0.0021 -0.0215
    41 0.050 A 10 600 120 0.0023 -0.0211
    42 0.100 B 10 D 700 120 0.0024 -0.0231
    43 0.150 C 20 600 120 0.0028 -0.0214
    44 0.200 D 20 700 120 0.0032 -0.0227
  • As is apparent from Table 2, the rates of dimensional changes before and after heat treatment are in the range from -0.02% to +0.02% in both directions parallel to and perpendicular to the rolling direction in Examples No. 1 to 32 according to the present invention. This shows that the present invention exhibits such an advantageous action that stable automatic conveyance is possible even when, for example, the clearance between the conveyance pins and pilot holes is about 5 µm at one side.
    The rates of dimensional changes before and after heat treatment in both directions parallel to and perpendicular to the rolling direction are particularly excellent, since they are in the range from -0.01 % to +0.01% in Examples No. 8, 9, 11, 12, 20, 21, 23 and 24 produced under particularly preferable conditions.
  • On the other hand, the rate of dimensional change in the direction parallel to the rolling direction is large in Comparative Examples No. 33 to 36 in which the reduction ratio by finish rolling is larger than the range according to the present invention. The rate of dimensional change in the direction parallel to the rolling direction is large in Comparative Examples No. 37 and 39 in which the temperature in the furnace during continuous annealing is lower than the range according to the present invention. The rate of dimensional change in the direction perpendicular to the rolling direction is particularly large in Comparative Examples No. 38 and 40 in which the temperature in the furnace during continuous annealing is higher than the range according to the present invention. The rate of dimensional change in the direction perpendicular to the rolling direction is particularly large in Comparative Examples No. 41 to 44 in which the annealing time of continuous annealing is longer than the range according to the present invention.
  • [INDUSTRIAL APPLICABILITY]
  • The copper alloy material for electric/electronic parts of the present invention is subjected to strain relief annealing for fine working for producing the electric/electronic parts. Accordingly, the copper alloy material is favorable as a copper alloy material for electric/electronic parts in which the rates of dimensional changes in the direction parallel to and perpendicular to the rolling direction before and after heat treatment for strain relief annealing can be simultaneously controlled. The method of producing a copper alloy material for electric/electronic parts of the present invention is able to favorably produce the copper alloy material for electric/electronic parts of the present invention.
  • Having described our present invention as related to the present embodiments, it is our intention that the present invention not be limited by any of the details of the description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.
  • This application claims priority on Patent Application No. 2006-276808 filed in Japan on October 10, 2006, and Patent Application No. 2007-260386 filed in Japan on October 3, 2007, each of which is entirely herein incorporated by reference.

Claims (6)

  1. A copper alloy material for electric/electronic parts, which is produced by the steps comprising: finish rolling a copper alloy at a reduction ratio of 40% or less, subjecting the copper alloy finish-rolled to a heat treatment under the conditions at a temperature from 500°C to 800°C for a time period from 1 second to 100 seconds by means of a continuous annealing line, and strain relief annealing the copper alloy heat-treated under the conditions at a temperature from 400°C to 600°C for a time period from 30 seconds to 1000 seconds,
    wherein the copper alloy material for electric/electronic parts has rates of dimensional changes before and after the strain relief annealing in both directions parallel to and perpendicular to the rolling direction within the range from -0.02% to +0.02%.
  2. The copper alloy material for electric/electronic parts according to Claim 1, wherein the strain relief annealing is conducted in mid course of a material working process for electric/electronic parts.
  3. The copper alloy material for electric/electronic parts according to Claim 1 or 2, wherein the copper alloy material for electric/electronic parts is a lead frame material or a connector material.
  4. The copper alloy material for electric/electronic parts according to any one of Claims 1 to 3, wherein the copper alloy material for electric/electronic parts comprises Ni from 1.5 mass% to 4.5 mass% and Si from 0.35 mass% to 1.0 mass%, and further comprises at least one or plural elements selected from Mg from 0.05 mass% to 0.15 mass%, Sn from 0.05 mass% to 0.5 mass%, Zn from 0.05 mass% to 1 mass%, Ag from 0.01% to 0.1 mass%, and Cr from 0.05 mass% to 0.4 mass%, with the balance being made of copper and inevitable impurities.
  5. A method of producing a copper alloy material for electric/electronic parts, comprising the steps of:
    finish rolling a copper alloy at a reduction ratio of 40% or less;
    subjecting the copper alloy finish-rolled to a heat treatment under the conditions at a temperature from 500°C to 800°C for a time period from 1 second to 100 seconds by means of a continuous annealing line; and
    strain relief annealing the copper alloy heat-treated under the conditions at a temperature from 400°C to 600°C for a time period from 30 seconds to 1000 seconds,
    to thereby produce the copper alloy material for electric/electronic parts having rates of dimensional changes before and after the strain relief annealing in both directions parallel to and perpendicular to the rolling direction within the range from -0.02% to +0.02%.
  6. The method of producing a copper alloy material for electric/electronic parts according to Claim 5, wherein the strain relief annealing is conducted in mid course of a material working process for electric/electronic parts.
EP07829424A 2006-10-10 2007-10-09 Copper alloy material for electrical/electronic part and process for producing the same Withdrawn EP2088215A4 (en)

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JP2007260386A JP5170866B2 (en) 2006-10-10 2007-10-03 Copper alloy material for electric and electronic parts and method for producing the same
PCT/JP2007/069686 WO2008044680A1 (en) 2006-10-10 2007-10-09 Copper alloy material for electrical/electronic part and process for producing the same

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Publication number Priority date Publication date Assignee Title
US1A (en) * 1836-07-13 John Ruggles Locomotive steam-engine for rail and other roads
US4656003A (en) * 1984-10-20 1987-04-07 Kabushiki Kaisha Kobe Seiko Sho Copper alloy and production of the same
JPH0815170B2 (en) * 1987-07-07 1996-02-14 株式会社ジャパエナジー Method of manufacturing film carrier
US4908275A (en) * 1987-03-04 1990-03-13 Nippon Mining Co., Ltd. Film carrier and method of manufacturing same
JPH02221344A (en) * 1989-02-21 1990-09-04 Mitsubishi Shindoh Co Ltd High strength cu alloy having hot rollability and heating adhesiveness in plating
JP2902830B2 (en) 1991-10-15 1999-06-07 日立金属株式会社 Lead frame material and manufacturing method thereof
JP3479470B2 (en) * 1999-03-31 2003-12-15 日鉱金属株式会社 Copper alloy foil for hard disk drive suspension and method of manufacturing the same
JP3521074B2 (en) * 2000-01-06 2004-04-19 三井金属鉱業株式会社 Method for testing physical properties of electrolytic copper foil
EP1134730A3 (en) * 2000-03-14 2002-08-14 Nippon Mining & Metals Co., Ltd. Copper-Alloy foil to be used for suspension member of hard-disc drive
JP3539685B2 (en) * 2000-03-14 2004-07-07 日鉱金属加工株式会社 Copper alloy foil for hard disk drive suspension
JP2003286527A (en) 2002-03-29 2003-10-10 Dowa Mining Co Ltd Low shrinkage copper or copper alloy and method for producing the same
JP4386236B2 (en) * 2002-10-11 2009-12-16 日鉱金属株式会社 Cu-Ni-Si alloy
JP2004149873A (en) * 2002-10-31 2004-05-27 Nikko Metal Manufacturing Co Ltd Corson copper alloy with die abrasion resistance
JP2006276808A (en) 2005-03-01 2006-10-12 Olympus Corp Zoom optical system and electronic imaging apparatus having the same
US20070185464A1 (en) 2006-02-03 2007-08-09 Bristol-Myers Squibb Company Ostomy appliance with recovery resistant moldable adhesive

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