CN108431256A - Electronic electric equipment copper alloy, electronic electric equipment copper alloy plate web, electronic electric equipment component, terminal, busbar and relay movable plate - Google Patents
Electronic electric equipment copper alloy, electronic electric equipment copper alloy plate web, electronic electric equipment component, terminal, busbar and relay movable plate Download PDFInfo
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- CN108431256A CN108431256A CN201780005496.3A CN201780005496A CN108431256A CN 108431256 A CN108431256 A CN 108431256A CN 201780005496 A CN201780005496 A CN 201780005496A CN 108431256 A CN108431256 A CN 108431256A
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 103
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- 229910052749 magnesium Inorganic materials 0.000 abstract description 21
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- 239000000463 material Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 19
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- 238000011156 evaluation Methods 0.000 description 17
- 230000007547 defect Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 16
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- 238000005266 casting Methods 0.000 description 9
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- 239000011159 matrix material Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000005482 strain hardening Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
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- 239000011800 void material Substances 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
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- 238000009749 continuous casting Methods 0.000 description 2
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- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
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- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
-
- 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
- H01B1/026—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/02—Single bars, rods, wires, or strips
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H50/00—Details of electromagnetic relays
- H01H50/14—Terminal arrangements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H50/00—Details of electromagnetic relays
- H01H50/54—Contact arrangements
- H01H50/56—Contact spring sets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/58—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation characterised by the form or material of the contacting members
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electromagnetism (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The present invention is characterized in that, containing 0.15 mass % less than within the scope of 0.35 mass % Mg and 0.0005 mass % less than the P within the scope of 0.01 mass %, remainder is made of Cu and inevitable impurity, conductivity is more than 75%IACS, and the content (Mg) (quality %) of Mg meets the relational expression of (Mg)+20 × (P) ＜ 0.5 with the content (P) (quality %) of P, the content of H is 10 mass ppm or less, the content of O is 100 mass ppm or less, the content of S is 50 mass ppm or less, the content of C is 10 mass ppm or less.
Description
Technical Field
The present invention relates to a copper alloy for electronic and electrical devices suitable for terminals such as connectors and press-fitted parts, movable pieces for relays, lead frames, and electronic components for electronic and electrical devices such as bus bars, and a copper alloy strip material for electronic and electrical devices, a component for electronic and electrical devices, a terminal, a bus bar, and a movable piece for relays, each of which is made of the copper alloy for electronic and electrical devices.
The present application claims priority based on patent application 2016-.
Background
Conventionally, copper or a copper alloy having high conductivity has been used for terminals such as connectors and press-fittings, movable pieces for relays, lead frames, and electronic/electrical equipment modules such as bus bars.
In accordance with the miniaturization of electronic devices, electric devices, and the like, there is a demand for miniaturization and thinning of electronic/electric device components used in these electronic devices, electric devices, and the like. Therefore, high strength and good bending workability are required as materials constituting the electronic and electrical device module. Further, a terminal of a connector or the like used in a high temperature environment such as an automobile engine room is also required to have stress relaxation resistance.
Here, as materials used for terminals such as connectors and press-fittings, movable pieces for relays, lead frames, and components for electronic and electrical devices such as bus bars, for example, Cu — Mg-based alloys have been proposed in patent documents 1 and 2.
Patent document 1: japanese laid-open patent publication No. 2007-056297 (A)
Patent document 2: japanese laid-open patent publication No. 2014-114464 (A)
However, the Cu — Mg alloy described in patent document 1 contains P in a relatively large amount of 0.08 to 0.35 mass%, and is insufficient in cold workability and bending workability, and it is difficult to mold a component for electronic and electrical equipment having a predetermined shape.
In the Cu — Mg alloy described in patent document 2, since the Mg content is 0.01 to 0.5 mass% and the P content is 0.01 to 0.5 mass%, coarse crystals are generated, and cold workability and bending workability are not sufficient.
In the above Cu — Mg alloy, Mg increases the viscosity of the copper alloy melt, and therefore, there is a problem that the castability is lowered if P is not added.
Further, in the above patent documents 1 and 2, the content of O and the content of S are not considered, and inclusions composed of Mg oxide, Mg sulfide, and the like are generated, which become defects at the time of working and deteriorate cold workability and bending workability. Further, since the content of H is not considered, a void defect is generated in the ingot, which causes a defect at the time of working and deteriorates cold workability and bending workability. Further, since the content of C is not considered, cold workability is deteriorated due to defects caused by inclusion of C during casting.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a copper alloy for electronic and electrical equipment, a copper alloy strip for electronic and electrical equipment, a module for electronic and electrical equipment, a terminal, a bus bar, and a movable piece for a relay, which are excellent in conductivity, cold workability, bending workability, and castability.
In order to solve the problem, the inventors of the present application have made intensive studies and have obtained the following findings: by setting the contents of Mg and P contained in the alloy within the range of the predetermined relational expression and defining the content of H, O, C, S, it is possible to reduce Mg and P-containing crystals and inclusions composed of Mg oxides, Mg sulfides, and the like, and to improve the strength, the stress relaxation resistance, and the castability without lowering the cold workability and the bending workability.
The present invention has been made in view of the above-mentioned findings, and a copper alloy for electrical and electronic equipment (hereinafter referred to as "copper alloy for electrical and electronic equipment of the present invention") according to an aspect of the present invention is characterized by containing 0.15 mass% or more and less than 0.35 mass% of Mg and 0.0005 mass% or more and less than 0.01 mass% of P, the remainder being composed of Cu and unavoidable impurities, having an electrical conductivity of more than 75% IACS, and having a content [ Mg ] (mass%) and a content [ P ] (mass%) of P satisfying a relational expression of [ Mg ] +20 × [ P ] < 0.5, and having a content of H of 10 mass ppm or less, a content of O of 100 mass ppm or less, a content of S of 50 mass ppm or less, and a content of C of 10 mass ppm or less.
According to the copper alloy for electronic and electrical equipment having the above-described structure, since the content of Mg is in the range of 0.15 mass% or more and less than 0.35 mass%, Mg is dissolved in the matrix phase of copper to improve the strength and the stress relaxation resistance without significantly lowering the electrical conductivity.
Further, since P is contained in a range of 0.0005 mass% or more and less than 0.01 mass%, castability can be improved.
Further, the content [ Mg ] of Mg and the content [ P ] of P satisfy the following relationship in terms of mass ratio:
〔Mg〕+20×〔P〕＜0.5，
therefore, the generation of coarse crystals containing Mg and P can be suppressed, and the reduction of cold workability and bending workability can be suppressed.
Further, since the content of O is 100 mass ppm or less and the content of S is 50 mass ppm or less, inclusions composed of Mg oxide, Mg sulfide, and the like can be reduced, and generation of defects at the time of processing can be suppressed. Further, by reacting with O and S, consumption of Mg can be prevented, and deterioration of mechanical properties can be suppressed.
Further, since the content of H is 10 mass ppm or less, generation of a void defect in the ingot can be suppressed, and generation of a defect at the time of processing can be suppressed.
Further, since the content of C is 10 mass ppm or less, cold workability can be ensured and the occurrence of defects during machining can be suppressed.
Further, since the conductivity exceeds 75% IACS, it can be applied to applications using pure copper.
In the copper alloy for electronic and electrical devices according to the present invention, it is preferable that the content [ Mg ] (% by mass) of Mg and the content [ P ] (% by mass) of P satisfy the following relationship: [ Mg ]/[ P ] ≦ 400.
In this case, the castability can be reliably improved by defining the ratio of the Mg content for lowering the castability and the P content for improving the castability as described above.
In the copper alloy for electronic and electrical devices according to the present invention, the 0.2% proof stress in a tensile test in a direction perpendicular to the rolling direction is preferably 300MPa or more.
In this case, since the 0.2% proof stress in the tensile test in the direction orthogonal to the rolling direction is defined as described above, the copper alloy is not easily deformed, and is particularly suitable as a copper alloy constituting a module for electronic and electrical devices such as a terminal of a connector, a press-fitting or the like, a movable piece for a relay, a lead frame, a bus bar or the like.
In the copper alloy for electronic and electrical devices according to the present invention, the residual stress ratio is preferably 50% or more under the conditions of 150 ℃ and 1000 hours.
In this case, since the residual stress ratio is defined as described above, the permanent deformation can be suppressed to a small level even when used in a high-temperature environment, and a drop in contact pressure of, for example, a connector terminal or the like can be suppressed. Therefore, the resin composition can be used as a material for electronic and electrical equipment modules used in high-temperature environments such as engine rooms.
A copper alloy strip for electrical and electronic equipment according to another aspect of the present invention (hereinafter referred to as "copper alloy strip for electrical and electronic equipment according to the present invention") is characterized by being composed of the above copper alloy for electrical and electronic equipment.
The copper alloy strip for electronic and electrical equipment having such a structure is excellent in conductivity, strength, cold workability, bending workability, and stress relaxation resistance because it is made of the above copper alloy for electronic and electrical equipment, and is particularly suitable as a material for a terminal such as a connector or a press-fitting, a movable piece for a relay, a lead frame, a bus bar, or other electronic and electrical equipment components.
The copper alloy strip for electronic and electrical equipment according to the present invention includes a plate material and a strip material formed by winding the plate material in a coil shape.
Here, the copper alloy strip for electronic and electrical equipment according to the present invention preferably has an Sn-plated layer or an Ag-plated layer on the surface.
In this case, since the surface has a Sn-plated layer or an Ag-plated layer, the surface is particularly suitable as a material for a terminal such as a connector or a press-fitting, a movable piece for a relay, a lead frame, a bus bar, or other electronic and electrical equipment module. In addition, in the invention of the present application, "Sn plating" includes pure Sn plating or Sn alloy plating, and "Ag plating" includes pure Ag plating or Ag alloy plating.
A module for an electrical and electronic device according to another aspect of the present invention (hereinafter referred to as "module for an electrical and electronic device according to the present invention") is characterized by being formed from the copper alloy strip for an electrical and electronic device. The module for an electrical and electronic device according to the present invention includes a terminal such as a connector or a press-fit, a movable piece for a relay, a lead frame, a bus bar, and the like.
The module for an electrical and electronic device having this structure is manufactured using the copper alloy strip for an electrical and electronic device, and therefore can exhibit excellent characteristics even when the module is downsized and thinned.
In the module for electronic and electrical equipment according to the present invention, the surface may have a Sn-plated layer or an Ag-plated layer. The Sn-plated layer and the Ag-plated layer may be formed in advance on the copper alloy strip for electrical and electronic equipment, or may be formed after molding the component for electrical and electronic equipment.
A terminal according to another aspect of the present invention (hereinafter referred to as "terminal of the present invention") is formed of the copper alloy strip for electronic/electrical equipment.
The terminal having this structure is manufactured using the copper alloy strip for electronic and electrical equipment, and therefore can exhibit excellent characteristics even when the terminal is reduced in size and thickness.
The terminal of the present invention may have a Sn plated layer or an Ag plated layer on the surface thereof. The Sn-plated layer and the Ag-plated layer may be formed in advance on the copper alloy strip for electronic/electrical equipment, or may be formed after the terminal is molded.
A bus bar according to another aspect of the present invention (hereinafter referred to as "bus bar of the present invention") is composed of the copper alloy plate bar material for electronic and electrical devices.
The bus bar having this structure is manufactured using the copper alloy strip material for electronic and electrical equipment, and therefore can exhibit excellent characteristics even when the bus bar is reduced in size and thickness.
The bus bar according to the present invention may have a Sn-plated layer or an Ag-plated layer on the surface thereof. The Sn-plated layer and the Ag-plated layer may be formed in advance on the copper alloy strip for electronic/electrical equipment, or may be formed after the bus bar is molded.
A relay movable piece according to another aspect of the present invention (hereinafter referred to as a "relay movable piece according to the present invention") is formed from the copper alloy strip for an electrical and electronic device.
The movable piece for a relay having this structure is manufactured using the copper alloy strip for an electric and electronic device, and therefore can exhibit excellent characteristics even when the movable piece is downsized and thinned.
The relay movable piece according to the present invention may have a Sn-plated layer or an Ag-plated layer on the surface thereof. The Sn-plated layer and the Ag-plated layer may be formed in advance on the copper alloy strip for electronic and electrical devices, or may be formed after the relay movable piece is molded.
According to the present invention, it is possible to provide a copper alloy for electronic and electrical equipment, a copper alloy strip for electronic and electrical equipment, a module for electronic and electrical equipment, a terminal, a bus bar, and a movable piece for a relay, which are excellent in conductivity, cold workability, bending workability, and castability.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a copper alloy for electronic and electrical devices according to the present embodiment.
Detailed Description
Hereinafter, a copper alloy for electronic and electrical equipment according to an embodiment of the present invention will be described.
The copper alloy for electronic and electrical equipment of the present embodiment has the following composition: contains Mg in the range of 0.15 to less than 0.35 mass% and P in the range of 0.0005 to less than 0.01 mass%, with the remainder being Cu and unavoidable impurities.
In the copper alloy for electronic and electrical devices according to the present embodiment, the electrical conductivity exceeds 75% IACS.
In the copper alloy for electronic and electrical equipment according to the present embodiment, the content of Mg [ Mg ] (mass%) and the content of P [ P ] (mass%) satisfy the following relational expression:
〔Mg〕+20×〔P〕＜0.5。
in the copper alloy for electronic and electrical equipment according to the present embodiment, the content of H is 10 mass ppm or less, the content of O is 100 mass ppm or less, the content of S is 50 mass ppm or less, and the content of C is 10 mass ppm or less.
In the copper alloy for electronic and electrical devices according to the present embodiment, the content of Mg [ Mg ] (mass%) and the content of P [ P ] (mass%) satisfy the following relational expression:
〔Mg〕/〔P〕≤400。
in the copper alloy for electronic and electrical equipment according to the present embodiment, the 0.2% proof stress in a tensile test in a direction perpendicular to the rolling direction is 300MPa or more. That is, in the present embodiment, the rolled material is a copper alloy for electrical equipment, and the 0.2% proof stress in the tensile test is defined in the direction orthogonal to the rolling direction in the final step of rolling as described above.
In the copper alloy for electronic and electrical equipment according to the present embodiment, the residual stress ratio is 50% or more under the conditions of 150 ℃ and 1000 hours.
The reason why the composition and various properties are defined as described above will be described below.
(Mg: 0.15 mass% or more and less than 0.35 mass%)
Mg is an element having an effect of improving strength and stress relaxation resistance without greatly lowering electrical conductivity by solid-dissolving in a mother phase of a copper alloy.
When the Mg content is less than 0.15 mass%, the effects may not be sufficiently exhibited. On the other hand, if the Mg content is 0.35 mass% or more, the conductivity may be greatly reduced, the viscosity of the copper alloy melt may be increased, and the castability may be reduced.
In view of the above, in the present embodiment, the content of Mg is set in a range of 0.15 mass% or more and less than 0.35 mass%.
In order to further improve the strength and the stress relaxation resistance, the Mg content is preferably 0.16 mass% or more, and more preferably 0.17 mass% or more. In order to reliably suppress the decrease in conductivity and the decrease in castability, the Mg content is preferably 0.30 mass% or less, and more preferably 0.28 mass% or less.
(P: 0.0005 mass% or more and less than 0.01 mass%)
P is an element having an action effect of improving castability.
When the content of P is less than 0.0005 mass%, the effects may not be sufficiently exhibited. On the other hand, when the content of P is 0.01 mass% or more, there is a possibility that crystals containing Mg and P are coarsened, and therefore, the crystals become starting points of fracture and fracture occurs at the time of cold working or bending.
In view of the above, in the present embodiment, the content of P is set in a range of 0.0005 mass% or more and less than 0.01 mass%.
In order to reliably improve castability, the content of P is preferably 0.0007 mass% or more, and more preferably 0.001 mass% or more. In order to reliably suppress the generation of coarse crystals, the content of P is preferably less than 0.009 mass%, more preferably less than 0.008 mass%, and still more preferably 0.0075 mass% or less. More preferably 0.0060 mass% or less, most preferably less than 0.0050 mass%.
(〔Mg〕+20×〔P〕＜0.5)
When P is added, Mg and P coexist as described above, and a crystal containing Mg and P is generated.
When the content [ Mg ] and the content [ P ] of P are set to mass%, and when the content [ Mg ] +20 × [ P ] is 0.5 or more, the total amount of Mg and P is large, crystals containing Mg and P may be coarsened and have a high density distribution, and cracks may be easily generated at cold working or bending working.
In view of the above, in the present embodiment, [ Mg ] +20 × [ P ] is set to less than 0.5. Further, in order to suppress the occurrence of cracking during cold working or bending by reliably suppressing the coarsening and densification of the crystal, it is preferable to set [ Mg ] +20 × [ P ] to less than 0.48, and more preferably to less than 0.46. Even more preferably less than 0.44 and most preferably less than 0.42.
(〔Mg〕/〔P〕≤400)
Since Mg is an element having an action of increasing the viscosity of the copper alloy melt and reducing castability, the ratio of the content of Mg to the content of P needs to be appropriately set in order to reliably improve castability.
When the content [ Mg ] of Mg and the content [ P ] of P are set to mass%, if [ Mg ]/[ P ] exceeds 400, the content of Mg relative to P increases, and the effect of improving castability by the addition of P may decrease.
In view of the above, in the present embodiment, when P is added, [ Mg ]/[ P ] is set to 400 or less. In order to further improve castability, [ Mg ]/[ P ] is preferably 350 or less, more preferably 300 or less.
If [ Mg ]/[ P ] is too low, Mg is consumed as a crystal, and the effect of solid solution of Mg may not be obtained. In order to suppress the formation of crystals containing Mg and P and to reliably improve the yield strength and the stress relaxation resistance by solid solution of Mg, the lower limit of [ Mg ]/[ P ] is preferably set to more than 20, more preferably more than 25.
(H: 10 ppm by mass or less)
H is an element which is bonded to O during casting to form water vapor and causes a void defect in the ingot. The porosity defect causes cracking during casting, and causes defects such as swelling and peeling during rolling. It is known that these defects such as cracking, bulging, and peeling become starting points of the failure due to stress concentration, and thus the strength and the stress corrosion cracking resistance are deteriorated. Therefore, if the content of H exceeds 10 mass ppm, the above-described pore defects are likely to occur.
Therefore, in the present embodiment, the content of H is defined to be 10 mass ppm or less. In order to further suppress the occurrence of the pore defects, the content of H is preferably 4 mass ppm or less, and more preferably 2 mass ppm or less.
The lower limit of the content of H is not particularly set, and excessively lowering the content of H causes an increase in manufacturing cost. Therefore, the content of H is usually 0.1 mass ppm or more.
(O: 100 ppm by mass or less)
O is an element that reacts with each constituent element in the copper alloy to form an oxide. These oxides act as starting points of fracture, and therefore, cold workability is lowered and bending workability is also deteriorated. When O exceeds 100 mass ppm, Mg is consumed by reaction with Mg, and the amount of Mg dissolved in the matrix phase of Cu decreases, possibly deteriorating mechanical properties.
Therefore, in the present embodiment, the content of O is defined to be 100 mass ppm or less. The content of O in the above range is particularly preferably 50 mass ppm or less, and more preferably 20 mass ppm or less.
The lower limit of the content of O is not particularly set, and excessively lowering the content of O causes an increase in production cost. Therefore, the content of O is usually 0.1 mass ppm or more.
(S: 50 ppm by mass or less)
S is an element present in the form of an intermetallic compound or a complex sulfide at crystal grain boundaries. These intermetallic compounds and complex sulfides present in the grain boundaries cause grain boundary fracture during hot working, and become a cause of the work fracture. Further, these elements act as starting points of fracture, and therefore, cold workability or bending workability deteriorates. Further, since S reacts with Mg, Mg is consumed, and the amount of Mg dissolved in the matrix phase of Cu is reduced, which may deteriorate mechanical properties.
Therefore, in the present embodiment, the content of S is defined to be 50 mass ppm or less. The content of S is particularly preferably 40 mass ppm or less, and more preferably 30 mass ppm or less within the above range.
The lower limit of the S content is not particularly set, and an excessive reduction in the S content leads to an increase in the production cost. Therefore, the S content is usually 1 mass ppm or more.
(C: 10 ppm by mass or less)
C is an element that may be inevitably mixed in, and is used to coat the surface of the melt in melting or casting for the purpose of deoxidation of the melt. If the content of C exceeds 10 mass ppm, the inclusion of C during casting is large. The segregation of solid solutions of these C, complex carbides, and C deteriorates cold workability.
Therefore, in the present embodiment, the content of C is defined to be 10 mass ppm or less. The content of C is preferably 5 mass ppm or less, more preferably 1 mass ppm or less, within the above range.
In addition, the lower limit of the content of C is not particularly set, and excessively lowering the content of C causes an increase in manufacturing cost. Therefore, the content of C is usually 0.1 mass ppm or more.
(unavoidable impurities: 0.1% by mass or less)
Examples of the other inevitable impurities include Ag, B, Ca, Sr, Ba, Sc, Y, rare earth elements, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Se, Te, Rh, Ir, Ni, Pd, Pt, Au, Zn, Cd, Hg, Al, Ga, In, Ge, Sn, As, Sb, Tl, Pb, Bi, Be, N, Si, Li, and the like. Since these inevitable impurities have an effect of lowering the conductivity, the total amount is set to 0.1 mass% or less.
Further, Ag, Zn, and Sn are easily mixed in copper to lower the conductivity, and the total amount is preferably less than 500 mass ppm. In particular, in order to greatly reduce the conductivity, it is preferable that Sn is less than 50 mass ppm by itself.
In addition, Si, Cr, Ti, Zr, Fe, and Co in particular greatly reduce the electric conductivity and deteriorate the bending workability due to the formation of inclusions, and therefore the total amount of these elements is preferably less than 500 mass ppm.
(conductivity: more than 75% IACS)
In the copper alloy for electronic and electrical equipment of the present embodiment, when the electrical conductivity is set to more than 75% IACS, the copper alloy can be suitably used as a terminal such as a connector or a press-fitting, a movable piece for a relay, a lead frame, a bus bar, or other electronic and electrical equipment module.
The conductivity is preferably more than 76% IACS, more preferably more than 77% IACS, even more preferably more than 78% IACS, and even more preferably more than 80% IACS.
(0.2% yield strength: 300MPa or more)
The copper alloy for electronic and electrical equipment according to the present embodiment is particularly suitable as a material for a component for electronic and electrical equipment, such as a terminal of a connector, a press-fitting, or the like, a movable piece for a relay, a lead frame, a bus bar, or the like, by setting the 0.2% proof stress to 300MPa or more. In the present embodiment, the 0.2% proof stress in the tensile test in the direction orthogonal to the rolling direction is 300MPa or more.
Here, the 0.2% yield strength is preferably 325MPa or more, and more preferably 350MPa or more.
(residual stress ratio: 50% or more)
As described above, the copper alloy for electronic and electrical equipment according to the present embodiment has a residual stress ratio of 50% or more at 150 ℃ for 1000 hours.
When the residual stress ratio under such conditions is high, the permanent strain can be suppressed to a small extent and the decrease in contact pressure can be suppressed even when the material is used under a high-temperature environment. Therefore, the copper alloy for electronic and electrical equipment according to the present embodiment can be applied to a terminal used in a high-temperature environment such as around an engine room of an automobile. In the present embodiment, the residual stress ratio in the stress relaxation test performed in the direction orthogonal to the rolling direction was 50% or more under the conditions of 150 ℃ and 1000 hours.
The residual stress ratio is preferably 60% or more under the conditions of 150 ℃ and 1000 hours, and more preferably 70% or more under the conditions of 150 ℃ and 1000 hours.
Next, a method for producing a copper alloy for electronic and electrical equipment according to the present embodiment having such a structure will be described with reference to a flowchart shown in fig. 1.
(melting and casting step S01)
First, the above elements are added to a copper melt obtained by melting a copper raw material to adjust the composition, thereby producing a copper alloy melt. When various elements are added, simple elements, mother alloys, or the like can be used. Further, the raw material containing the above-mentioned elements may be melted together with the copper raw material. Further, recycled materials and waste materials of the alloy may be used. Here, the molten copper is preferably 4NCu having a purity of 99.99 mass% or more or 5NCu having a purity of 99.999 mass% or more. In particular, in the present embodiment, since the content of H, O, S, C is defined as described above, raw materials having a small content of these elements are selected and used. Specifically, it is preferable to use a raw material having an H content of 0.5 mass ppm or less, an O content of 2.0 mass ppm or less, an S content of 5.0 mass ppm or less, and a C content of 1.0 mass ppm or less.
In the melting step, it is preferable to use H for suppressing the oxidation of Mg and for reducing the hydrogen concentration2The melting is performed in an inert gas atmosphere (for example, Ar gas) having a low vapor pressure of O, and the holding time during the melting is minimized.
Then, the copper alloy melt adjusted in composition is poured into a mold to produce an ingot. In addition, in view of mass production, it is preferable to use a continuous casting method or a semi-continuous casting method.
In this case, since crystals containing Mg and P are formed when the melt solidifies, the solidification rate can be increased to make the crystal size finer. Therefore, the cooling rate of the melt is preferably 0.1 ℃/sec or more, more preferably 0.5 ℃/sec or more, and most preferably 1 ℃/sec or more.
(homogenizing and solutionizing step S02)
Next, the obtained ingot is subjected to a heating treatment for homogenization and solutionizing. In the interior of the ingot, intermetallic compounds and the like which are generated by concentration due to Mg segregation during solidification and contain Cu and Mg as main components exist. Here, in order to eliminate or reduce these segregation and intermetallic compounds, the ingot is heated to 400 ℃ to 900 ℃ inclusive, and Mg is uniformly diffused in the ingot or dissolved in the matrix. The homogenization and solutionizing step S02 is performed in a non-acidic or reducing atmosphere. And, the copper material heated to 400 ℃ or higher and 900 ℃ or lower is cooled to 200 ℃ or lower at a cooling rate of 60 ℃/min or higher.
Here, when the heating temperature is less than 400 ℃, the solutionizing does not proceed completely, and a large amount of intermetallic compounds containing Cu and Mg as main components may remain in the matrix phase. On the other hand, if the heating temperature exceeds 900 ℃, a part of the copper material becomes a liquid phase, and there is a possibility that the structure or the surface state becomes uneven. Therefore, the heating temperature is set in the range of 400 ℃ to 900 ℃. More preferably, it is 500 ℃ to 850 ℃, and still more preferably 520 ℃ to 800 ℃.
(Hot working Process S03)
For the purpose of efficiency of rough machining and homogenization of the structure, hot machining may be performed. The temperature condition in the hot working step S03 is not particularly limited, and is preferably in the range of 400 ℃ to 900 ℃. The post-processing cooling method is preferably cooling to 200 ℃ or lower at a cooling rate of 60 ℃/min or more by water quenching or the like. The processing method is not particularly limited, and rolling, drawing, extrusion, groove rolling, forging, pressing, and the like can be used, for example.
(crude processing step S04)
Rough machining is performed to machine the workpiece into a predetermined shape. The temperature condition in the rough working step S04 is not particularly limited, but is preferably set in the range of-200 ℃ to 200 ℃ for cold working or warm working, and particularly preferably at room temperature, in order to suppress recrystallization or improve dimensional accuracy. The reduction ratio (rolling reduction) is preferably 20% or more, and more preferably 30% or more. The processing method is not particularly limited, and rolling, drawing, extrusion, groove rolling, forging, pressing, and the like can be used, for example.
(intermediate Heat treatment Process S05)
After the rough machining step S04, heat treatment is performed for the purpose of thorough solution, recrystallization texture, or softening for improving workability. The method of heat treatment is not particularly limited, but heat treatment is preferably performed in a non-oxidizing atmosphere or a reducing atmosphere under conditions of a holding temperature of 400 ℃ to 900 ℃ inclusive and a holding time of 10 seconds to 10 hours inclusive. The cooling method after heating is not particularly limited, but a method such as water quenching at a cooling rate of 200 ℃/min or more is preferably employed.
The rough processing step S04 and the intermediate heat treatment step S05 may be repeatedly performed.
(finishing step S06)
The copper material after the intermediate heat treatment step S05 is finished to be worked into a predetermined shape. The temperature conditions in the finishing step S06 are not particularly limited, but are preferably set in the range of-200 ℃ to 200 ℃ for cold working or warm working, and particularly preferably at room temperature, in order to suppress recrystallization or softening. The machining rate is appropriately selected so as to be similar to the final shape, but in order to improve the strength by the work hardening in the finishing step S06, the machining rate is preferably set to 20% or more. When further improvement in strength is desired, the reduction ratio is more preferably 30% or more, still more preferably 40% or more, and most preferably 60% or more. Further, the bending workability is deteriorated due to the increase in the working ratio, and therefore, it is preferably 99% or less.
(Final Heat treatment Process S07)
Next, the plate bar obtained in the finishing step S06 is subjected to a final heat treatment for the purpose of improving the stress relaxation resistance and low-temperature annealing/curing or for the purpose of removing residual strain.
The heat treatment temperature is preferably set in the range of 100 ℃ to 800 ℃. In the final heat treatment step S07, it is necessary to set heat treatment conditions (temperature, time, cooling rate) so as to avoid a significant decrease in strength due to recrystallization. For example, it is preferable to keep the temperature at 300 ℃ for about 1 second to 120 seconds. The heat treatment is performed in a non-oxidizing atmosphere or a reducing atmosphere.
The method of heat treatment is not particularly limited, and it is preferable to perform heat treatment in a short time by a continuous annealing furnace in view of the effect of reducing the production cost.
The finishing step S06 and the final heat treatment step S07 may be repeatedly performed.
Thus, the copper alloy sheet strip for electronic and electrical equipment of the present embodiment (the sheet material or the strip material having a coil shape) is produced, and the sheet thickness of the copper alloy sheet strip for electronic and electrical equipment is in a range exceeding 0.05mm and 3.0mm or less, preferably in a range exceeding 0.1mm and less than 3.0 mm. When the thickness of the copper alloy strip for electronic and electrical equipment is 0.05mm or less, it is not suitable for use as a conductor for large current applications, and when the thickness exceeds 3.0mm, it is difficult to perform press punching.
Here, the copper alloy strip for electronic and electrical equipment according to the present embodiment may be used as it is for a module for electronic and electrical equipment, or may be formed with an Sn-plated layer or an Ag-plated layer having a thickness of about 0.1 to 100 μm on one surface or both surfaces of the plate surface. In this case, the thickness of the copper alloy strip for electronic and electrical equipment is preferably 10 to 1000 times the thickness of the plating layer.
Further, the copper alloy for electronic and electrical equipment (copper alloy plate bar for electronic and electrical equipment) of the present embodiment is used as a raw material, and is subjected to punching, bending, or the like, to mold a terminal such as a connector or a press-fitting, a movable piece for a relay, a lead frame, a bus bar, or the like.
According to the copper alloy for electronic and electrical devices of the present embodiment configured as described above, since the content of Mg is in the range of 0.15 mass% or more and less than 0.35 mass%, Mg is dissolved in the matrix phase of copper, and strength and stress relaxation resistance can be improved without significantly decreasing electrical conductivity.
In the copper alloy for electronic and electrical equipment according to the present embodiment, the content of P is in the range of 0.0005 mass% or more and less than 0.01 mass%, and therefore the viscosity of the copper alloy melt can be reduced and the castability can be improved.
In addition, since the electrical conductivity of the copper alloy for electronic and electrical equipment of the present embodiment exceeds 75% IACS, the copper alloy can be applied to applications requiring high electrical conductivity.
Further, since the content [ Mg ] (% by mass) of Mg and the content [ P ] (% by mass) of P satisfy the relational expression of [ Mg ] +20 × [ P ] < 0.5, the formation of coarse crystals of Mg and P can be suppressed.
Further, since the content of O is 100 mass ppm or less and the content of S is 50 mass ppm or less, inclusions composed of Mg oxides, Mg sulfides, and the like can be reduced.
Further, since the content of H is 10 mass ppm or less, generation of a void defect in the ingot can be suppressed.
Further, the content of C is 10 mass ppm or less, and therefore, cold workability can be ensured.
According to the above features, occurrence of defects during machining can be suppressed, and cold workability and bending workability can be greatly improved.
Further, in the copper alloy for electronic and electrical equipment of the present embodiment, since the content [ Mg ] (% by mass) of Mg and the content [ P ] (% by mass) of P satisfy the relational expression of [ Mg ]/[ P ] < 400, the ratio of the content of Mg for lowering castability to the content of P for improving castability is rationalized, and the effect of adding P can reduce the viscosity of the copper alloy melt and reliably improve castability.
Further, in the copper alloy for electronic and electrical equipment according to the present embodiment, the 0.2% proof stress is 300MPa or more, and the residual stress ratio is 50% or more under the conditions of 150 ℃ and 1000 hours, and therefore, the copper alloy is excellent in strength and stress relaxation resistance, and is therefore particularly suitable as a material for terminals such as connectors and press fittings, movable pieces for relays, lead frames, bus bars, and other electronic and electrical equipment components.
Further, since the copper alloy strip for electrical and electronic equipment according to the present embodiment is made of the above copper alloy for electrical and electronic equipment, it is possible to manufacture a terminal such as a connector or a press-fitting, a module for electrical and electronic equipment such as a movable piece for a relay, a lead frame, and a bus bar by bending the copper alloy strip for electrical and electronic equipment.
When the Sn-plated layer or the Ag-plated layer is formed on the surface, the Sn-plated layer or the Ag-plated layer is particularly suitable as a material for terminals such as connectors and press-fittings, movable pieces for relays, lead frames, and modules for electronic and electrical devices such as bus bars.
Further, since the module for an electrical and electronic apparatus (a terminal such as a connector or a press-fitting, a movable piece for a relay, a lead frame, a bus bar, and the like) of the present embodiment is made of the above copper alloy for an electrical and electronic apparatus, excellent characteristics can be exhibited even if the module is downsized and thinned.
The above description has been made of the copper alloy for electronic and electrical equipment, the copper alloy plate bar material for electronic and electrical equipment, and the module for electronic and electrical equipment (terminal, bus bar, etc.) according to the embodiment of the present invention, but the present invention is not limited thereto, and can be modified as appropriate within a range not departing from the technical idea of the present invention.
For example, although the above embodiment describes an example of a method for producing a copper alloy for electrical and electronic equipment, the method for producing a copper alloy for electrical and electronic equipment is not limited to the method described in the embodiment, and a conventional production method may be appropriately selected for production.
Examples
The following describes the results of a confirmation experiment performed to confirm the effects of the present invention.
Copper to be screened, which has an H content of 0.1 mass ppm or less, an O content of 1.0 mass ppm or less, an S content of 1.0 mass ppm or less, a C content of 0.3 mass ppm or less, and a Cu purity of 99.99 mass% or more, is prepared as a raw material, and the copper is charged into a high-purity alumina crucible and melted in a high-purity Ar gas (dew point-80 ℃ or less) atmosphere using a high-frequency melting furnace. When H, O is introduced by adding various elements to the copper alloy melt, high-purity Ar gas (dew point-80 ℃ or lower) and high-purity N are used2Gas (dew point below-80 deg.C), high purity O2Gas (dew point below-80 deg.C), high purity H2Gas (dew point-80 ℃ C. or lower) Ar-N was used as an atmosphere at the time of melting2-H2And Ar-O2Mixed gas atmosphere. When introducing C, the surface of the melt is coated with C particles during melting and brought into contact with the melt. When S is introduced, S is added as it is. In addition, magnesium having a magnesium purity of 99.99 mass% or more is used as the Mg material. In this way, molten alloy having the composition shown in table 1 and table 2 was produced by melting, and a casting mold was filled with the molten alloy to produce an ingot. In addition, the carbon mold was used in invention example 11, the heat insulating material (isocool) mold was used in invention example 28, and the copper alloy mold having a water cooling function was used as the mold for casting in invention examples 1 to 10, 12 to 27, and 29 to 37 and comparative examples 1 to 11. The size of the ingot is set to be thickThe degree is about 20mm x the width about 200mm x the length about 300 mm.
From the obtained ingot, the vicinity of the surface skin of the cast piece was subjected to face cutting, and a block of 16 mm. times.200 mm. times.100 mm was cut out.
The block was heated under the temperature conditions shown in tables 3 and 4 for 4 hours in an Ar gas atmosphere, and was homogenized and solutionized.
In order to appropriately form the heat-treated copper material into a shape suitable for the final shape, surface grinding is performed simultaneously with cutting. Thereafter, rough rolling was performed at normal temperature at the rolling ratios shown in tables 3 and 4.
Then, the obtained strips were subjected to an intermediate heat treatment under an Ar gas atmosphere under the conditions shown in tables 3 and 4. Thereafter, water quenching was performed.
Subsequently, finish rolling was performed at the rolling ratios shown in tables 3 and 4 to produce a sheet having a thickness of 0.5mm and a width of about 200 mm. In the finish rolling, rolling oil is applied to the surface and cold rolling is performed.
After the finish rolling, a final heat treatment was performed in an Ar atmosphere under the conditions shown in tables 3 and 4, and then water quenching was performed to produce a sheet for property evaluation.
(composition of ingredients)
The composition analysis was performed using the sheet for property evaluation obtained as described above. At this time, analysis of Mg and P was performed by inductively coupled plasma emission spectroscopy. Further, analysis was performed by a heat conduction method, and analysis was performed by O, S, C using an infrared absorption method.
(castability)
As evaluation of castability, the presence or absence of surface cracking during casting was observed. The case where no surface cracks were completely or almost confirmed with the naked eye was evaluated as a, the case where small surface cracks having a depth of less than 1mm were generated was evaluated as B, and the case where surface cracks having a depth of 1mm or more and less than 2mm were generated was evaluated as C. Further, the occurrence of a large surface crack having a depth of 2mm or more was evaluated as D, and the evaluation was terminated halfway. The evaluation results are shown in tables 5 and 6.
The depth of the surface crack means the depth of the surface crack from the end portion of the ingot toward the center portion.
(mechanical Properties)
A test specimen No. 13B specified in JIS Z2241 was collected from the strip for characteristic evaluation, and the 0.2% yield strength was measured by the micro-residual elongation method according to JIS Z2241. In addition, test samples were taken in a direction orthogonal to the rolling direction. The evaluation results are shown in tables 5 and 6.
(number of breaks in tensile test)
The tensile test was performed 10 times using the test specimen No. 13B, and the number of times the tensile test specimen was broken in the elastic region before the specimen was subjected to 0.2% yield strength was determined as the number of times of breaking in the tensile test. The evaluation results are shown in tables 5 and 6.
The elastic region is a region satisfying a linear relationship in a stress-strain curve. The larger the number of fracture cycles, the lower the workability due to inclusions.
(conductivity)
Test samples having a width of 10mm × a length of 150mm were collected from the property evaluation strips, and the electric resistance was determined by a four-terminal method. Then, the measurement of the size of the test sample was performed using a micrometer, and the volume of the test sample was calculated. Then, the conductivity was calculated from the measured resistance value and the volume. Further, test samples were collected so that the longitudinal direction thereof was perpendicular to the rolling direction of the property evaluation strip. The evaluation results are shown in tables 5 and 6.
(stress relaxation resistance characteristics)
Regarding the stress relaxation resistance test, the test was carried out in compliance with the Japan copper elongation Association technical Standard JCBA-T309: the cantilever beam screw-type method of 2004 applies stress and the residual stress rate after 1000 hours of holding at a temperature of 150 c was measured.
As a test method, from each property evaluation strip, a test sample (width 10mm) was taken in a direction orthogonal to the rolling direction, and the span length was adjusted by setting the initial flexural displacement to 2mm so that the surface maximum stress of the test sample became 80% of the yield strength. The above surface maximum stress is determined by the following formula.
Surface maximum stress (MPa) 1.5Et delta0/Ls 2
Wherein,
e: young's modulus (MPa)
t: thickness of sample (t ═ 0.5mm)
δ0: initial deflection displacement (2mm)
Ls: span length (mm)
The residual stress rate was measured from the bending characteristics after holding at a temperature of 150 ℃ for 1000 hours, and the stress relaxation resistance was evaluated. In addition, the residual stress ratio was calculated by the following equation.
Residual stress ratio (%) - (1- δ)t/δ0)×100
Wherein,
δt: permanent deflection Displacement (mm) after 1000 hours at 150 ℃ to permanent deflection Displacement (mm) after 24 hours at ambient temperature
δ0: initial deflection displacement (mm).
(bending workability)
Complying with the technical standard JCBA-T307 of Japan copper elongation Association: test method 4 of 2007 performed a bending process. A plurality of test specimens each having a width of 10 mm. times.a length of 30mm were collected from the sheet for property evaluation so that the bending axis was perpendicular to the rolling direction. A W-bend test was performed using a W-type jig having a bend radius of 1.0mm (R/t 2) when the bend angle was 90 degrees and the finish rolling ratio exceeded 85%, and a bend radius of 0.5mm (R/t 1) when the finish rolling ratio was 85% or less.
The outer periphery of the bent portion was visually observed, and judged as "C" when cracking was observed, judged as B when large wrinkles were observed, and judged as a when cracking, fine cracking, and large wrinkles were not observed. Further, a and B were judged as allowable bendability. The evaluation results are shown in tables 5 and 6.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
[ Table 6]
The Mg content of comparative example 1 was less than the range of the present invention (the range of 0.15 mass% or more and less than 0.35 mass%), the 0.2% yield strength was low, and the strength was insufficient.
The Mg content of comparative example 2 is higher than the range of the present invention (the range of 0.15 mass% or more and less than 0.35 mass%), and the conductivity is low.
The content of P in comparative example 3 is more than the range of the present invention (the range of 0.0005 mass% or more and less than 0.01 mass%), and a large edge breakage occurs during rough rolling, and therefore, the subsequent evaluation is terminated.
In comparative examples 4 to 6, [ Mg ] +20 × [ P ] exceeded 0.5, and a large edge was formed during rough rolling, and the subsequent evaluation was terminated.
The content of H in comparative example 7 was higher than the range of the present invention (10 mass ppm or less), and large edge breakage occurred during rough rolling, and the subsequent evaluation was terminated.
The content of O in comparative example 8 was higher than the range of the present invention (100 mass ppm or less), and 10 times of tensile tests were conducted, and as a result, it was confirmed that fracture of the tensile test specimen in the elastic region and deterioration of workability due to inclusions occurred 8 times. The bending workability was not sufficient.
The content of S in comparative example 9 was higher than the range of the present invention (50 mass ppm or less), 10 times of tensile tests were conducted, and it was confirmed that fracture of the tensile test specimen in the elastic region and deterioration of workability due to inclusions occurred 8 times. The bending workability was not sufficient.
The content of C in comparative examples 10 and 11 was higher than the range of the present invention (10 mass ppm or less), and as a result of 10 times of tensile tests, it was confirmed that fracture of the tensile test specimens and deterioration of workability due to inclusions occurred in the elastic region 6 times and 7 times. The bending workability was not sufficient.
In contrast, the present invention example confirmed excellent results in castability, strength (0.2% yield strength), electrical conductivity, stress relaxation resistance (residual stress ratio), and bending workability. Further, as a result of 10 times of the tensile test, it was confirmed that no fracture of the tensile test specimen in the elastic region occurred, and the processability was particularly excellent.
Based on the above, it was confirmed that the examples of the present invention can provide a copper alloy for electronic and electrical devices and a copper alloy strip for electronic and electrical devices, which are excellent in conductivity, cold workability, bending workability, and castability.
Industrial applicability
Provided are a copper alloy for electronic and electrical equipment, a copper alloy strip for electronic and electrical equipment, a module for electronic and electrical equipment, a terminal, a bus bar, and a movable piece for a relay, which have excellent conductivity, cold workability, bending workability, and castability even when used for a component that is reduced in thickness with reduction in size.
Claims (14)
1. A copper alloy for electronic and electrical equipment, characterized in that,
contains 0.15 mass% or more and less than 0.35 mass% of Mg and 0.0005 mass% or more and less than 0.01 mass% of P, the remainder being Cu and unavoidable impurities,
the conductivity of the conductive film is over 75 percent IACS,
and the content [ Mg ] of Mg and the content [ P ] of P satisfy the following relation:
〔Mg〕+20×〔P〕＜0.5，
a content of H is 10 mass ppm or less, a content of O is 100 mass ppm or less, a content of S is 50 mass ppm or less, a content of C is 10 mass ppm or less,
wherein the unit of the content of Mg and the content of P is mass%.
2. The copper alloy for electronic and electrical equipment according to claim 1,
the content [ Mg ] of Mg and the content [ P ] of P satisfy the following relation:
〔Mg〕/〔P〕≤400，
wherein the unit of the content of Mg and the content of P is mass%.
3. The copper alloy for electronic and electrical equipment according to claim 1 or 2,
the 0.2% yield strength in a tensile test in a direction orthogonal to the rolling direction is 300MPa or more.
4. The copper alloy for electronic and electrical equipment according to any one of claims 1 to 3,
the residual stress rate is more than 50% under the conditions of 150 ℃ and 1000 hours.
5. A copper alloy strip for electronic and electrical equipment, which comprises the copper alloy for electronic and electrical equipment according to any one of claims 1 to 4.
6. The copper alloy strip for electronic and electrical equipment according to claim 5,
the surface is provided with a Sn plating layer or an Ag plating layer.
7. A package for electrical and electronic equipment, comprising the copper alloy strip for electrical and electronic equipment according to claim 5 or 6.
8. The assembly for an electronic and electric device according to claim 7,
the surface is provided with a Sn plating layer or an Ag plating layer.
9. A terminal comprising the copper alloy strip for electrical and electronic equipment according to claim 5 or 6.
10. A terminal as recited in claim 9,
the surface is provided with a Sn plating layer or an Ag plating layer.
11. A bus bar comprising the copper alloy strip for electronic/electrical equipment according to claim 5 or 6.
12. The bus bar according to claim 11,
the surface is provided with a Sn plating layer or an Ag plating layer.
13. A movable piece for a relay, characterized by comprising the copper alloy strip for an electric and electronic device according to claim 5 or 6.
14. The movable piece for a relay according to claim 13,
the surface is provided with a Sn plating layer or an Ag plating layer.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-069079 | 2016-03-30 | ||
| JP2016069079 | 2016-03-30 | ||
| JP2017-063258 | 2017-03-28 | ||
| JP2017063258A JP6226097B2 (en) | 2016-03-30 | 2017-03-28 | Copper alloy for electronic and electrical equipment, copper alloy sheet material for electronic and electrical equipment, electronic and electrical equipment parts, terminals, bus bars, and movable pieces for relays |
| PCT/JP2017/012993 WO2017170733A1 (en) | 2016-03-30 | 2017-03-29 | Copper alloy for electronic and electrical equipment, copper alloy plate strip for electronic and electrical equipment, component for electronic and electrical equipment, terminal, busbar, and movable piece for relays |
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| Publication Number | Publication Date |
|---|---|
| CN108431256A true CN108431256A (en) | 2018-08-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780005496.3A Pending CN108431256A (en) | 2016-03-30 | 2017-03-29 | Electronic electric equipment copper alloy, electronic electric equipment copper alloy plate web, electronic electric equipment component, terminal, busbar and relay movable plate |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP3438299B1 (en) |
| JP (1) | JP6226097B2 (en) |
| KR (1) | KR102327539B1 (en) |
| CN (1) | CN108431256A (en) |
| MX (1) | MX2018011711A (en) |
| TW (1) | TWI709651B (en) |
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|---|---|---|---|---|
| CN110172609A (en) * | 2019-05-16 | 2019-08-27 | 红河学院 | A kind of high-strength high-conductivity copper magnesium system alloy and preparation method thereof |
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| EP3348659B1 (en) | 2015-09-09 | 2020-12-23 | Mitsubishi Materials Corporation | Copper alloy for electronic/electrical device, copper alloy plastically-worked material for electronic/electrical device, component for electronic/electrical device, terminal, and busbar |
| US11319615B2 (en) | 2016-03-30 | 2022-05-03 | Mitsubishi Materials Corporation | Copper alloy for electronic and electrical equipment, copper alloy plate strip for electronic and electrical equipment, component for electronic and electrical equipment, terminal, busbar, and movable piece for relay |
| WO2017170699A1 (en) | 2016-03-30 | 2017-10-05 | 三菱マテリアル株式会社 | Copper alloy for electronic and electrical equipment, copper alloy plate strip for electronic and electrical equipment, component for electronic and electrical equipment, terminal, busbar, and movable piece for relays |
| WO2019189558A1 (en) | 2018-03-30 | 2019-10-03 | 三菱マテリアル株式会社 | Copper alloy for electronic/electric device, copper alloy sheet/strip material for electronic/electric device, component for electronic/electric device, terminal, and busbar |
| JP6780187B2 (en) | 2018-03-30 | 2020-11-04 | 三菱マテリアル株式会社 | Copper alloys for electronic / electrical equipment, copper alloy strips for electronic / electrical equipment, parts for electronic / electrical equipment, terminals, and busbars |
| JP7180101B2 (en) * | 2018-03-30 | 2022-11-30 | 三菱マテリアル株式会社 | Copper alloys for electronic and electrical equipment, copper alloy sheet materials for electronic and electrical equipment, parts for electronic and electrical equipment, terminals and bus bars |
| JP7180102B2 (en) * | 2018-03-30 | 2022-11-30 | 三菱マテリアル株式会社 | Copper alloys for electronic and electrical equipment, copper alloy sheet materials for electronic and electrical equipment, parts for electronic and electrical equipment, terminals and bus bars |
| JP6863409B2 (en) * | 2018-12-26 | 2021-04-21 | 三菱マテリアル株式会社 | Copper alloy plate, copper alloy plate with plating film and manufacturing method of these |
| WO2020137726A1 (en) | 2018-12-26 | 2020-07-02 | 三菱伸銅株式会社 | Copper alloy plate, plating film-attached copper alloy plate, and methods respectively for manufacturing these products |
| CN114761590B9 (en) * | 2019-11-29 | 2023-12-08 | 三菱综合材料株式会社 | Copper alloy, copper alloy plastic working material, electronic/electrical device module, terminal, bus bar, and heat dissipating substrate |
| EP4067517A4 (en) * | 2019-11-29 | 2023-11-22 | Mitsubishi Materials Corporation | Copper alloy, copper alloy plastic-processed material, component for electronic and electric devices, terminal, bus bar, and heat dissipation substrate |
| JP7443737B2 (en) | 2019-12-10 | 2024-03-06 | 三菱マテリアル株式会社 | Copper alloy plate, copper alloy plate with plating film, and manufacturing method thereof |
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| JP6226097B2 (en) | 2017-11-08 |
| EP3438299B1 (en) | 2023-05-03 |
| KR20180125446A (en) | 2018-11-23 |
| TWI709651B (en) | 2020-11-11 |
| EP3438299A4 (en) | 2019-12-18 |
| EP3438299A1 (en) | 2019-02-06 |
| TW201807204A (en) | 2018-03-01 |
| MX2018011711A (en) | 2018-12-19 |
| JP2017186662A (en) | 2017-10-12 |
| KR102327539B1 (en) | 2021-11-16 |
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