CN106460095A - Copper alloy sheet material, production method therefor, and electrical/electronic component comprising said copper alloy sheet material - Google Patents
Copper alloy sheet material, production method therefor, and electrical/electronic component comprising said copper alloy sheet material Download PDFInfo
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- CN106460095A CN106460095A CN201580028078.7A CN201580028078A CN106460095A CN 106460095 A CN106460095 A CN 106460095A CN 201580028078 A CN201580028078 A CN 201580028078A CN 106460095 A CN106460095 A CN 106460095A
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/10—Alloys based on copper with silicon as the next major constituent
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- 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
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- 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
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Abstract
Provided is a copper alloy material having excellent conductivity and stress-relaxation resistance, as well as bending workability, said copper alloy material being suitable for connectors used in on-vehicle parts and surrounding infrastructure mainly for EVs and HEVs, as well as photovoltaic systems, and also suitable for lead frames, relays, switches, sockets, and the like. Also provided is a production method therefor. The present invention is a copper alloy sheet material that includes 0.10-0.50 mass% of Cr, and 0.01-0.50 mass% of Mg, and contains one selected from the group consisting of a first additive element group containing a total of 0.00-0.20 mass% of at least one of Zr and Ti, and a second additive element group containing a total of 0.00-0.50 mass% of at least one of Zn, Fe, Sn, Ag, Si, and Ni, with the remainder comprising Cu and unavoidable impurities, wherein in a cross section perpendicular to the sheet width direction (TD), the surface area ratio of crystal particles having a particle size of 30 [mu]m or less is 30-70%. The present invention is also a production method therefor, and an electrical/electronic component comprising said copper alloy sheet material.
Description
Technical field
The present invention relates to a kind of Cu alloy material and manufacture method thereof, this Cu alloy material is suitable for electric automobile (EV:
Electric Vehicle), mixed power electric car (HEV:Hybrid Electric Vehicle) centered on vehicle-mounted portion
The connector of part and periphery base configuration, photovoltaic power generation system etc. and lead frame, relay, switch, socket etc..
Background technology
The on-vehicle parts centered on EV, HEV and periphery base configuration, photovoltaic power generation system etc. connector, with
And in the purposes such as lead frame, relay, switch, socket, generally use Cu alloy material.Technology with EV, HEV in recent years
Exploitation competition and the requirement improving with its performance together, the Towards Higher Voltage of circuit power, the miniaturization band of electronic equipment size
The high current densityization of circuit come develops, corresponding, resistance heating when needing to improve further energising and and its
Circuit connection reliability together.When solving this problem, for Cu alloy material, it is desirable to for suppressing resistance heating
High conductivity, at the excellent anti-stress relaxation properties of adstante febre holding circuit connection reliability.Additionally, in miniaturization etc.
In, from the viewpoint of the free degree improving part design, need processability as bendability good.
As the alloy system with moderate intensity and high conductivity, can enumerate copper-chromium (Cu-Cr) is that copper closes
Gold, copper-zirconium (Cu-Zr) series copper alloy, copper-thin titanium (the thin Ti of Cu-) series copper alloy etc..In such copper alloy, typically
For, compared with the worked structure obtained by utilizing processing, the bendability of recrystallized structure obtained after heat treatment is good
Good.In patent document 1, by adjusting alloying component and the manufacturing condition of Cu-Cr series copper alloy, after thus controlling recrystallization
Crystallization particle diameter and coefficient of alteration, improve bendability and anti-stress relaxation properties.In patent document 2, by adjusting
Cu-Cr series copper alloy, Cu-Zr series copper alloy, the alloying component of Cu-thin Ti series copper alloy and manufacturing condition, so that conduct
The Cube orientation prosperity of recrystallization orientation, improves bendability and anti-stress relaxation properties.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2013-129889 publication
Patent document 2:No. 5170916 publications of Japanese Patent No.
Content of the invention
Invent problem to be solved
The on-vehicle parts centered on EV, HEV and periphery base configuration, photovoltaic power generation system etc. connector, with
And in lead frame, relay, switch, socket etc., for the connection reliability of holding circuit, need resistance when because of energising to send out
Heat waits and maintains contact pressure during additional heat.According to such requirement, for Cu alloy material, it is desirable to high electric conductivity and resistance to
Stress relaxation properties.Additionally, from the viewpoint of the free degree of part design, also require that bendability is good.
In patent document 1, describe the technology of following alloy material:By adjusting alloying component and manufacturing condition, control
Recrystallization particle diameter processed and coefficient of alteration thereof, thus have anti-stress relaxation properties and good bendability concurrently.This material allows
Stress mitigation rate (SRR:Stress Relaxation Ratio) up to 25%.But, as described above, as entering one from now on
The material using under conditions of the high current density of circuit of step, it is desirable to improve anti-stress relaxation properties further.
Additionally, the Cu-Cr series copper alloy of patent document 2 record, Cu-Zr series copper alloy, Cu-thin Ti series copper alloy pass through
Make to improve bendability as the Cube orientation prosperity of recrystallization orientation, held concurrently by adjusting alloying component and manufacturing condition
Tool anti-stress relaxation properties.SRR is sometimes up to 30%, if as described above, the high electric current in view of further from now on circuit is close
Degreeization, then there is the leeway improved further in anti-stress relaxation properties.
In view of the foregoing, the problem of the present invention is to provide a kind of Cu alloy material and manufacture method, this copper alloy
Material is suitable for the on-vehicle parts centered on technological progress significant EV, HEV and periphery base configuration, sunshine in recent years and sends out
The connector using in electricity system etc. and lead frame, relay, switch, socket etc., its electric conductivity is high, proof stress relaxes spy
Property is excellent, and has bendability concurrently.
For solving the means of problem
From the above point of view, for the on-vehicle parts coping with centered on EV, HEV and periphery base configuration, too
The copper alloy material that the requirement performance of the connector of photovoltaic power generation system etc. and lead frame, relay, switch, socket etc. improves
Material, the present inventor is repeated research.Itself it was found that by the Cr containing 0.10 mass %~0.50 mass %, 0.10
The Mg of quality %~0.50 mass % and at least one in adding up to Zr, Ti of 0.01 mass %~0.20 mass %, conjunction
Being calculated as at least one in Zn, Fe, Sn, Ag, Si, Ni of 0.01 mass %~0.50 mass %, remaining part is by Cu and inevitable
The manufacturing condition aspect of Cu alloy material that constitutes of impurity make an effort, form worked structure and that recrystallized structure mixes be specific
The metal structure of half softening tissue such that it is able to have excellent anti-stress relaxation properties and bendability concurrently.Thereby, it is possible to
To the Cu alloy material having high electric conductivity, anti-stress relaxation properties and good bendability concurrently.The present invention is based on this
Opinion and complete.
That is, according to the present invention, following means are provided.
(1) a kind of copper alloy plate, this copper alloy plate contains the Cr of 0.10 mass %~0.50 mass %, 0.01 matter
The Mg of amount %~0.50 mass %, and containing in the group being made up of the 1st addition element group and the 2nd addition element group
Kind, remaining part is made up of Cu and inevitable impurity, and the 1st addition element group contains and adds up to 0.00 mass %~0.20 matter
Amount % Zr, Ti at least one, the 2nd addition element group contain add up to 0.00 mass %~0.50 mass % Zn,
At least one in Fe, Sn, Ag, Si, Ni (wherein, selected from by least one in above-mentioned Zr, Ti and Zn, Fe, Sn, Ag, Si,
One in the group of at least one composition in Ni can be containing more than any one, it is also possible to does not contains any one, and is any
Adding ingredient), described copper alloy plate is characterised by,
On the cross section vertical with plate width direction TD, particle diameter be less than 30 μm crystal grain have 30%~70% area
Rate.
(2) copper alloy plate as described in (1), wherein, containing selected from by the 1st addition element group and the 2nd addition element group
At least one in the group of composition, the 1st addition element group contains in Zr, the Ti adding up to 0.01 mass %~0.20 mass %
At least one, the 2nd addition element group contains Zn, Fe, Sn, Ag, Si, the Ni adding up to 0.01 mass %~0.50 mass %
In at least one.
(3) copper alloy plate as described in (1) or (2), wherein, makes the initial stage bearing strength test to material surface be 0.2%
The 80% of proof stress, places 1000 hours in 150 DEG C, and stress mitigation rate now is less than 20%,
During 90 ° of W bendings, R/t is 1.0, does not cracks.
(4) copper alloy plate as according to any one of (1)~(3), wherein, electrical conductivity is more than 60%IACS.
(5) manufacture method of a kind of copper alloy plate, which is the system of copper alloy plate according to any one of (1)~(4)
Make method, it is characterised in that this manufacture method has successively:
A () casts with the melting of the corresponding alloy raw material of copper alloy plate
B () carries out homogeneous heating at 850 DEG C~1050 DEG C
C (), 750 DEG C of hot-working carried out above, after hot-working terminates, is cooled to 700 DEG C with 1.3 DEG C/sec~1.6 DEG C/sec
D () carries out cold working with the working modulus of less than 90%
(e) after 350 DEG C~650 DEG C heat treatment carrying out 10 minutes~24 hours, below cooling velocity 2 DEG C/min
It is cooled to 300 DEG C
F () finishes with the working modulus of less than 50%
(g) 250 DEG C~650 DEG C carry out 5 seconds~10 hours go strain annealing.
(6) a kind of electrical and electronic parts, it is made up of the copper alloy plate according to any one of (1)~(4).
The above-mentioned and other feature and advantage of the present invention can definitely by following record.
Invention effect
The Cu alloy material of the present invention has high electric conductivity, excellent anti-stress relaxation properties and good bending machining concurrently
Property, be suitable for the on-vehicle parts centered on EV, HEV and periphery base configuration, photovoltaic power generation system etc. connector and
Lead frame, relay, switch, socket are used, it is possible to increase these on-vehicle parts and periphery base configuration, photovoltaic power generation system
Deng circuit connection reliability.Additionally, the manufacture method of the Cu alloy material of the present invention can manufacture possesses above-mentioned excellent physical property
Cu alloy material.
Detailed description of the invention
The preferred embodiment of the Cu alloy material of the present invention is illustrated.Herein, " Cu alloy material " refers to (processing
Before there is regulation alloy composition) copper alloy raw material are processed into the copper alloy material of regulation shape (such as plate, bar, paper tinsel etc.)
Material.Hereinafter, as embodiment, sheet material, web are illustrated, but its shape is not limited to this.
The Cu alloy material of the present invention is characterised by, which is a kind of copper alloy plate, and this copper alloy plate contains 0.10
The Cr of quality %~0.50 mass %, the Mg of 0.01 mass %~0.50 mass %, and containing selected from by the 1st addition element group and
One in the group of the 2nd addition element group composition, remaining part is made up of Cu and inevitable impurity, and the 1st addition element group contains
Having at least one in Zr, Ti of adding up to 0.00 mass %~0.20 mass %, the 2nd addition element group contains and adds up to
At least one in Zn, Fe, Sn, Ag, Si, Ni of 0.00 mass %~0.50 mass %, the feature of described copper alloy plate exists
In, on the cross section vertical with plate width direction TD, particle diameter is the area occupation ratio that the crystal grain of less than 30 μm has 30%~70%.Pass through
Meet the scope of this regulation, can obtain having concurrently high electric conductivity, anti-stress relaxation properties, the material of good bendability
Material, wherein, electrical conductivity (EC:Electrical Conductivity) it is more than 60%IACS, and, make on material surface
Initial stage bearing strength test is the 80% of 0.2% proof stress, places 1000 hours, stress mitigation rate now in 150 DEG C
(SRR) being less than 20%, further, in 90 ° of W bendings, R/t is less than 1.0.Structure to the Cu alloy material of the present invention below
Tissue, alloying component is become to be described in detail.Lower limit for stress mitigation rate is not particularly limited, and for example, more than 0%.
Further, in 90 ° of W bendings, the lower limit for the R/t not cracked is not particularly limited, and for example, more than 0.Additionally,
Higher limit for electrical conductivity is not particularly limited, for example, below 101%IACS.
<The material structure of the Cu alloy material of the present invention>
Half softening tissue that the Cu alloy material of the present invention has worked structure and recrystallized structure mixes, to plate width side
When observing to the vertical cross section (cross section being made up of rolling direction RD and thickness of slab direction ND) of TD, on this cross section, particle diameter
It is the area occupation ratio that the crystallization of less than 30 μm has 30%~70%.Lower limit for described particle diameter is not particularly limited, for example
It is more than 1 μm.Plate width direction TD also referred to as rolls vertical direction.Plate width direction TD not merely refers to the short side direction of sheet material,
Rolling direction RD when manufacturing relative to sheet material is vertical and also hangs down relative to the rolling surface normal direction (thickness of slab direction ND) of sheet material
Straight direction is plate width direction TD.
As described later, the worked structure of the Cu alloy material of the present invention carries out heat by the material forming above-mentioned alloy and adds
Implement cold working after work and obtain.Generally, the crystallization particle diameter of the material after hot-working is up to about 100 μm, the crystal boundary in material
Density is little.Therefore, carrying out in worked structure obtained from cold working to it, the grain boundary density in material also reduces, proof stress
Relaxation properties becomes good.On the other hand, the recrystallized structure in the present invention is to make it by carrying out heat treatment to worked structure
Obtained from recrystallization, crystallization particle diameter is less than 30 μm, compared with the material after the hot-working based on worked structure, and crystal grain
Footpath is little, and therefore the grain boundary density in material is big, compared with worked structure, and anti-stress relaxation properties difference.
On the other hand, the present invention has according to the crystallization that particle diameter on the cross section vertical with plate width direction TD is less than 30 μm
The mode of the area occupation ratio of 30%~70% is controlled such that it is able to prevents the decline of anti-stress relaxation properties, and is able to maintain that
Good bendability.It should be noted that preferably, area occupation ratio is to observe 40000 μm2The region of left and right is measured
's.If observing this region, even if then to copper alloy plate, whole region is not measured, it is also possible to obtain the area occupation ratio of target.
Even if additionally, copper alloy plate is processed for miscellaneous part a part of in the case of, by closing from this parts pair and copper
The cross section that the plate width direction TD of gold sheet material is vertical carries out specific, observes 40000 μm2The region of left and right, it is also possible to measure target
Area occupation ratio.
On the cross section vertical with plate width direction TD of the copper alloy plate of the present invention, crystallization particle diameter is the district of less than 30 μm
In the case that territory is less than 30%, worked structure is excessive, and bendability is insufficient.Additionally, the district that crystallization particle diameter is less than 30 μm
In the case that territory is more than 70%, recrystallized structure is excessive, and anti-stress relaxation properties declines.Specified in the present invention, above-mentioned half softens
Tissue be formed by meet obtained from manufacturing condition described later.Additionally, the crystallization particle diameter in the present invention refers to crystal grain
Major diameter and the major diameter in minor axis.
(alloying component)
<Cr>
Cr by copper alloy parent phase separate out, it is possible to increase intensity and anti-stress relaxation properties and do not damage electric conductivity.
In the present invention, Cr contains 0.10 mass %~0.50 mass %, and preferably 0.15 mass %~0.40 mass % is excellent further
Elect 0.20 mass %~0.35 mass % as.When Cr amount is very few, the amount of the Cr in copper parent phase or the compound containing Cr reduces, because of
This cannot obtain desired intensity, anti-stress relaxation properties.Additionally, in heat treatment step, recrystallization is excessively carried out, it is difficult to
Obtain half above-mentioned softening tissue.On the other hand, when Cr amount is too much, following problems is produced:The decline of electric conductivity, due to copper parent phase
In the intensity that causes of the generation of coarsening compound decline, the harmful effect to bendability.
<Mg>
Mg plays a role as solid solution element in copper parent phase such that it is able to improve intensity and anti-stress relaxation properties.?
In the present invention, Mg contains 0.01 mass %~0.50 mass %, preferably 0.05 mass %~0.40 mass %, further preferably
It is 0.10 mass %~0.30 mass %.When content is very few, it is impossible to fully obtain the improvement effect of above-mentioned each characteristic.Additionally,
In heat treatment step, recrystallization is excessively carried out, it is impossible to obtain above-mentioned half softening tissue.On the other hand, when content is too much, generation is led
Electrical decline, the dysgenic problem to processability (such as hot-workability).Mg passes through in copper parent phase as solid solution unit
Element plays a role, thus improves anti-stress relaxation properties, does not therefore add forming compound with Mg as P and making preferably simultaneously
Its element separating out.
<Ti、Zr>
In the present invention, Ti, Zr of the 1st addition element that can add as any adding ingredient analyse in copper parent phase
Go out such that it is able to improve intensity and anti-stress relaxation properties.In which of the present invention, can contain and add up to 0.01 matter
Amount %~0.20 mass %, preferably 0.05 mass %~0.15 mass %, more preferably 0.10 mass %~0.15 matter
In Ti, Zr of amount % at least a kind.When content is very few, its additive effect is insufficient;When too much, produce the decline of electric conductivity, right
The dysgenic problem of processability (such as hot-workability).
<Zn、Fe、Sn、Ag、Si、Ni>
As the preferred embodiment of the present invention, by adding Zn, Fe, Sn, Ag, Si, Ni of the 2nd addition element as arbitrarily adding
Addition divides, it is possible to increase the material behaviors such as intensity, anti-stress relaxation properties, briquettability, plating.In the case of Gai, can contain
Add up to 0.01 mass %~0.50 mass %, be preferably 0.05 mass %~0.40 mass %, more preferably 0.10 matter
At least one in Zn, Fe, Sn, Ag, Si, Ni of amount %~0.30 mass %.When content is very few, the interpolation of the 2nd addition element
Effect is insufficient;When content is too much, sometimes produce electric conductivity decline, to the harmful effect of processability (such as hot-workability),
The problem that raw material cost increases.
(manufacture method)
Then, the preferred case of manufacture method of the Cu alloy material of the present invention is illustrated.
When the common manufacturing process of Cu alloy material of the present invention is shown, melt casting, b. homogeneous by carrying out a. successively
Change heat treatment, c. hot-working, d. cold working, e. heat treatment, f. finishes, g. goes strain annealing to manufacture.Excellent further
Choosing after hot working and carries out face cutting before cold working.
This manufacture method has with in the past with the process number of degree, sets each process conditions by suitable simultaneously, can
Realize the raising of the material behavior of target.Such as following detailed description, the cooling speed in the manufacture method of the present invention, after hot-working
Degree and cold worked working modulus critically important, as operation afterwards finishing, go strain annealing can implement repeatedly.
<Melt casting>
Prepare the Mg containing the Cr of 0.10 mass %~0.50 mass % and 0.01 mass %~0.50 mass %, remaining part by
The copper alloy raw material that Cu and inevitable impurity are constituted.Or, prepare containing 0.10 mass %~0.50 mass % Cr,
The Mg of 0.01 mass %~0.50 mass %, and containing selected from by containing add up to 0.01 mass %~0.20 mass % Zr,
The 1st at least one addition element group in Ti and containing add up to the Zn of 0.01 mass %~0.50 mass %, Fe, Sn, Ag,
At least one in the group of the 2nd at least one addition element group composition in Si, Ni, remaining part is by Cu and inevitable impurity
The copper alloy raw material constituting.Utilize calciner implement to melt casting to this copper alloy raw material and cool down, had
The ingot casting of predetermined component.Melting casting can utilize usual way to carry out.
<Homogenize heat treatment>
The heat treatment that homogenizes is the composition homogeneous in order to make compound contained in ingot casting solid solution in copper parent phase, make ingot casting
Change and implement.Thereby, it is possible to fully obtain the effect of the composition adding, furthermore it is possible to the deviation of the characteristic reducing in material.
In the present invention, it is preferred to 850 DEG C~1050 DEG C temperature, more preferably at 900 DEG C~1050 DEG C, further preferably at 950 DEG C
~1050 DEG C of heat treatments that homogenize carrying out 0.5 hour~12 hours.
<Hot-working>
Hot-working (hot rolling etc.) is carried out to the ingot casting after the heat treatment that just carries out homogenizing, makes thickness of slab thinning.Hot-working exists
The temperature of more than 750 DEG C terminates, and afterwards with 1.3 DEG C/s~1.6 DEG C/s cooling (such as water-cooled) to 700 DEG C, carries out water-cooled afterwards.
Being terminated at high temperature by making hot-working, the crystallization particle diameter after processing becomes big, further by slowing to the cooling velocity of 700 DEG C,
Crystal grain-growth, the crystallization particle diameter of therefore obtained after hot rolling material grows to the scope of regulation.Thus, not only as rear one
The anti-stress relaxation properties of worked structure obtained in the cold working of operation improves, and becomes in heat treatment step and tie
The crystal grain boundary of brilliant starting point reduces, and is therefore readily obtained half softening tissue as target.Excessively slow to the cooling velocities of 700 DEG C
When, utilizing homogenizes is heat-treated the addition element being solid-solution in copper parent phase form precipitation with coarsening compound when cooling, nothing
Method fully obtains addition element effect.Additionally, grow up when cooling coarse grains, the crystal grain of material obtained after hot rolling
Footpath is more than the scope of regulation, in the heat treatment step as later procedure, it is difficult to obtain half softening tissue as target.This
Outward, to the cooling velocity of 700 DEG C too fast when, during cooling, crystal grain is not fully grown up, the crystallization particle diameter of material obtained after hot rolling
Less than prescribed limit, in the heat treatment step as later procedure, it is difficult to obtain half softening tissue as target.
<Face is cut>
Face cutting is utilized to remove the oxidation overlay film being formed at material surface after hot-working.Face cutting process can be any
Carry out.Face cutting can utilize known method to carry out.
<Cold working>
Material after working modulus opposite with less than 90% is cut carries out cold working (for example cold rolling).Working modulus is preferably
30%~85%, working modulus more preferably 50%~85%.In the case that cold worked working modulus is excessive, as rear one
In the heat treatment step of operation, easily carry out recrystallization, it is impossible to obtain half softening tissue as target.Additionally, it is cold worked
It when working modulus is too small, is possible to be difficult to recrystallization occur, therefore preferably with 30% in the heat treatment step as later procedure
Above working modulus carries out cold working.
<Heat treatment>
For the material after cold working, carry out the heat treatment of 10 minutes~24 hours at 450 DEG C~650 DEG C.Utilize at heat
Reason, there is recrystallization, can obtain medium-softization tissue, in addition, separate out fine in copper parent phase in a part for worked structure
Precipitate, intensity, electric conductivity, anti-stress relaxation properties improve.In the case that low temperature carries out short time process, in heat treatment
When be difficult to occur recrystallization, do not simply fail to obtain half softening tissue as target, and amount of precipitation be few, and separate out compound
Particle diameter excessively fine, therefore cannot expectation strength, electric conductivity, the raising of anti-stress relaxation properties.Additionally, it is long at high temperature
In the case of time-triggered protocol, when heat treatment, recrystallization is excessively carried out, and does not simply fail to obtain half softening tissue as target, and
And the compound coarsening separating out, electric conductivity improves, but cannot expectation strength, the raising of anti-stress relaxation properties.Additionally, when
Effect heat treatment after to 300 DEG C cooling velocity be preferably≤2 DEG C/min.By make to the cooling velocity of 300 DEG C be this model
Enclose, intensity, electric conductivity, anti-stress relaxation properties can be improved further.
<Finishing>
Material after heat treatment is carried out finishing (finish rolling by the working modulus with less than 50%, more preferably 10~40%
Deng).Utilizing finishing, intensity improves, but electric conductivity, anti-stress relaxation properties, bendability decline.Finishing rate is excessive
In the case of, electric conductivity, anti-stress relaxation properties, bendability are remarkably decreased, afterwards go in strain annealing operation, it is difficult to
Have the recovery of these characteristics and the maintenance of intensity concurrently.
<Go strain annealing>
By carrying out strain annealing to the material after finishing, intensity declines, but electric conductivity, anti-stress relaxation properties,
Bendability is improved.In the present invention, it is preferred to the temperature of 250 DEG C~650 DEG C carry out 5 seconds~10 hours go strain
Annealing.Low temperature carry out the short time process in the case of, sometimes in finishing reduce electric conductivity, anti-stress relaxation properties,
Bendability cannot recover.Additionally, when high temperature carries out long time treatment excessively, intensity is remarkably decreased sometimes.
The Cu alloy material of the present invention has high electric conductivity, anti-stress relaxation properties, good bendability concurrently, is suitable for
In the connector of the on-vehicle parts centered on EV, HEV and periphery base configuration, photovoltaic power generation system etc. and lead frame,
Relay, switch, socket etc..
Embodiment
Hereinafter, based on embodiment, the present invention is described in more detail, but the invention is not restricted to this.
The copper alloy raw material of raw material are melted casting, makes ingot casting, after the heat treatment that homogenizes, carry out heat at once and add
Work, terminates hot-working more than 750 DEG C, after control cooling velocity is cooled to 700 DEG C, carries out water-cooled.After water-cooled, face is utilized to cut
Remove the oxidation overlay film of material, carry out cold working afterwards, carry out the heat treatment of 10 minutes~24 hours at 450 DEG C~650 DEG C, with
The cooling velocity of 2 DEG C/min cools down.After cooling, proceed the finish rolling of the working modulus of less than 50%, 250 DEG C~650
DEG C temperature carry out 5 seconds~10 hours go strain annealing, thus obtain Cu alloy material.Fallen into by the condition making each operation
In the range of regulation, obtain the sample with the example of the Cu alloy material tissue as target.Additionally, as comparative example,
The different material of making ingot casting composition, manufacture method.Final thickness of slab is all set to 1.0mm by the material making.
It should be noted that after each heat treatment, rolling, oxidation, the state of rugosity according to material surface carry out acid
Wash, surface grinding.
To such material to be tested manufacturing, implement following evaluation test.
(structure observation)
The cross section that metallurgical microscopes pair is vertical with the plate width direction TD of material is utilized to carry out observing (by rolling direction RD and plate
The cross section that thick direction ND is constituted), calculate the area occupation ratio that crystallization particle diameter is 30 μm of area below.Observation is carried out as follows:
For the material after heat treatment step, the cross section vertical with plate width direction TD is implemented wet lapping and polishing is ground, utilize
With chromic acid:Water=1:After the liquid of the ratio mixing of 1 (Capacity Ratio) carries out the corrosion of several seconds to abradant surface, utilize metallurgical microscopes
Multiplying power with 50 times~500 times is observed.Additionally, for the area occupation ratio that crystallization particle diameter is 30 μm of area below, ask as follows
Go out.Firstly, for the region observing 200 μ m 200 μm on photo, with the intervals of 10 μm be little trellis divide observation photo,
In the case that crystallization particle diameter is the region of more than half that 30 μm of particles below meet each little lattice, regard this little lattice as crystallization
Particle diameter is 30 μm of area below.Afterwards, to regarding that the sum of little lattice that crystallization particle diameter is 30 μm of area below is counted as
Number.With regard as crystallization particle diameter be the sum of little lattice of 30 μm of area below divided by the sum of the little lattice observed, be multiplied by
100, using obtained value as the area occupation ratio that crystallization particle diameter is 30 μm of area below.
(tensile strength (TS:Tensile Strength))
According to JIS Z2241,3 test films cutting out from rolling parallel direction are measured, its mean value is shown.Will
It is qualified that TS is that more than 400MPa is set to, and is set to defective by TS less than 400MPa.
(EC)
In the thermostat remaining 20 DEG C (± 0.5 DEG C), utilize four-terminal method contrast resistance to measure, calculate electricity
Conductance.It should be noted that terminal pitch is from for 100mm.
(SRR)
According to Japan Shen Tong association JCBA T309:2004 " relax examination based on the stress of the bending of copper and copper alloy lamellar
Proved recipe method ", utilizes cantilever method (using cantilever beam A seating fixture), is 0.2% making the initial stage bearing strength test to material surface
The 80% of proof stress, is measured under conditions of keeping 1000 hours for 150 DEG C.The rectangular of wide 10mm made by test film
Shape, the length direction making test film is consistent with rolling parallel direction.The computational methods of stress mitigation rate are based on Japanese Patent No.
No. 5307305 computational methods recorded.That is, heat treatment forward direction cantilever be maintained at testing stand test film give elastic limit should
During the pre-stress of the 80% of power, it is distance δ that the position of test film front end is in away from reference position0Height.By it at 150 DEG C
Thermostat in keep 1000 hours (give pre-stress in the state of above-mentioned test film is heat-treated), remove load
After to be in away from said reference position be distance H the position of test film front endtHeight.Additionally, to examination during not load stress
Testing piece in the case of carry out above-mentioned heat treatment, it is distance H that the position of test film front end is in away from said reference position1Height.
According to their relation, stress mitigation rate (%) is calculated as (Ht-H1)/(δ0-H1)×100.
(bendability)
Bending machining test basis JIS Z 2248 is carried out.Material is cut into wide 10mm, long 50mm, implements bending axis and roll
Direction processed vertically such 90 ° of W bending (GW:Good Way) or bending axis such 90 ° Ws bending parallel with rolling direction
(BW:Bad Way) after, utilize light microscope to observe bend surface with 200 times, investigating has flawless.For bending machining
Property, thickness of slab is set to the inner side bending radius of t, 90 ° of W bending when being set to R, under conditions of R/t is 1.0, by GW and BW two side
Situation about all not cracking is judged as well (A), and either one situation about cracking of GW and BW is judged as poor (D).
【Table 1】
Alloy No. | Cr | Mg | Ti | Zr | Zn | Fe | Sn | Ag | Si | Ni | Cu |
1 | 0.15 | 0.40 | Remaining part | ||||||||
2 | 0.25 | 0.10 | Remaining part | ||||||||
3 | 0.45 | 0.03 | Remaining part | ||||||||
4 | 0.25 | 0.10 | 0.10 | Remaining part | |||||||
5 | 0.25 | 0.03 | 0.13 | Remaining part | |||||||
6 | 0.25 | 0.10 | 0.05 | 0.05 | Remaining part | ||||||
7 | 0.25 | 0.10 | 0.20 | Remaining part | |||||||
8 | 0.25 | 0.10 | 0.05 | Remaining part | |||||||
9 | 0.25 | 0.10 | 0.10 | Remaining part | |||||||
10 | 0.25 | 0.10 | 0.40 | Remaining part | |||||||
11 | 0.25 | 0.10 | 0.03 | Remaining part | |||||||
12 | 0.25 | 0.10 | 0.10 | Remaining part | |||||||
13 | 0.25 | 0.10 | 0.20 | 0.03 | Remaining part | ||||||
14 | 0.35 | 0.10 | 0.10 | 0.15 | Remaining part | ||||||
15 | 0.05 | 0.10 | Remaining part | ||||||||
16 | 0.25 | 0.00 | Remaining part | ||||||||
17 | 0.25 | 1.00 | Remaining part | ||||||||
18 | 0.25 | 0.10 | 0.50 | Remaining part | |||||||
19 | 0.25 | 0.10 | 0.50 | Remaining part | |||||||
20 | 0.25 | 0.10 | 4.00 | Remaining part | |||||||
21 | 0.25 | 0.10 | 2.00 | Remaining part | |||||||
22 | 0.25 | 0.10 | 0.80 | Remaining part | |||||||
23 | 0.25 | 0.10 | 0.60 | Remaining part | |||||||
24 | 0.25 | 0.10 | 0.70 | Remaining part |
Table 1 summarizes the alloy composition of the ingot casting of making.Alloy No.1~14 within the scope of the invention, alloy
No.15~24 are outside scope.
Table 2 illustrates manufacture method within the scope of the invention and composition example also within the scope of the invention and composition
Comparative example outside the scope of the present invention.In example, TS >=400MPa, EC >=60%IACS, SRR≤20%, it is bending
Processability is good and has high electric conductivity, anti-stress relaxation properties, the Cu alloy material of good bendability concurrently.With this phase
Right, be unsatisfactory at the addition of alloying component in the comparative example of scope that present invention provide that, result be intensity, electric conductivity, resistance to should
Power relaxation properties and arbitrary characteristic difference of bendability.
Table 3 illustrate alloy composition within the scope of the invention and manufacture method example also within the scope of the invention and
Comparative example outside the scope of the present invention for the manufacture method.In example, TS >=400MPa, EC >=60%IACS, SRR≤20%,
It is bendability good and have high electric conductivity, anti-stress relaxation properties, the copper alloy material of good bendability concurrently
Material.On the other hand, for comparative example outside the scope of the present invention for the manufacturing condition, anti-stress relaxation properties, bendability
Arbitrary characteristic difference, the material as high target call performance is insufficient.
Cu alloy material in the scope of the present invention can have high electric conductivity, excellent anti-stress relaxation properties, good concurrently
Good bendability, is thus suitable for the on-vehicle parts centered on EV, HEV and periphery base configuration, solar power generation system
The connector of system etc. and lead frame, relay, switch, socket etc..
Describe the present invention in conjunction with embodiments thereof, but applicants contemplate that, as long as no specifying, then originally
Invention is all not limited in any details of explanation, it should do not violating the spirit shown in appended claims and scope
In the case of carry out wide in range explanation.
This application claims based on Japanese Patent Application 2014-111771 submitting patent application in Japan on May 29th, 2014
Its content is introduced the application as a part for this specification contents by priority in reference form.
Claims (6)
1. a copper alloy plate, this copper alloy plate contain the Cr of 0.10 mass %~0.50 mass %, 0.01 mass %~
The Mg of 0.50 mass %, and containing the one in the group being made up of the 1st addition element group and the 2nd addition element group, remaining part
Be made up of Cu and inevitable impurity, the 1st addition element group contain add up to 0.00 mass %~0.20 mass % Zr,
At least one in Ti, the 2nd addition element group contain add up to the Zn of 0.00 mass %~0.50 mass %, Fe, Sn, Ag,
At least one in Si, Ni, wherein, selected from by least one and Zn, Fe, Sn, Ag, Si, the Ni in above-mentioned Zr, Ti at least
One in the group of a kind of composition can be containing more than any one, it is also possible to does not contains any one, and is any adding ingredient, institute
State copper alloy plate to be characterised by,
In the cross section vertical with plate width direction TD, particle diameter be less than 30 μm crystal grain have 30%~70% area occupation ratio.
2. copper alloy plate as claimed in claim 1, wherein, described copper alloy plate contains selected from by the 1st addition element group
With at least one in the group of the 2nd addition element group composition, the 1st addition element group contains and adds up to 0.01 mass %~0.20
At least one in Zr, Ti of quality %, the 2nd addition element group contains and adds up to 0.01 mass %~0.50 mass %
At least one in Zn, Fe, Sn, Ag, Si, Ni.
3. copper alloy plate as claimed in claim 1 or 2, wherein, making to the initial stage bearing strength test of material surface is 0.2% bullet
Property limit stress 80%, in 150 DEG C place 1000 hours, stress mitigation rate now is less than 20%,
During 90 ° of W bendings, R/t is 1.0, does not cracks.
4. the copper alloy plate as according to any one of claims 1 to 3, wherein, electrical conductivity is more than 60%IACS.
5. a manufacture method for copper alloy plate, which is the manufacture of copper alloy plate according to any one of Claims 1 to 4
Method, it is characterised in that this manufacture method has successively:
A () casts with the melting of the corresponding alloy raw material of copper alloy plate
B () carries out homogeneous heating at 850 DEG C~1050 DEG C
C (), 750 DEG C of hot-working carried out above, after hot-working terminates, is cooled to 700 DEG C with 1.3 DEG C/sec~1.6 DEG C/sec
D () carries out cold working with the working modulus of less than 90%
(e) after 350 DEG C~650 DEG C heat treatment carrying out 10 minutes~24 hours, with 2 DEG C/min of cool below of cooling velocity
To 300 DEG C
F () finishes with the working modulus of less than 50%
(g) 250 DEG C~650 DEG C carry out 5 seconds~10 hours go strain annealing.
6. an electrical and electronic parts, it is made up of the copper alloy plate according to any one of Claims 1 to 4.
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CN110753592A (en) * | 2017-06-30 | 2020-02-04 | 凤凰接触股份有限及两合公司 | Method for producing copper-containing components by selective laser sintering |
CN112281023A (en) * | 2020-11-23 | 2021-01-29 | 宁波博威合金材料股份有限公司 | Copper alloy material with excellent bending property and preparation method and application thereof |
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WO2024014172A1 (en) * | 2022-07-14 | 2024-01-18 | Jx金属株式会社 | Rolled copper foil, copper-clad laminate, method for producing copper-clad laminate, method for producing flexible printed wiring board, and method for producing electronic component |
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JPH0551671A (en) * | 1991-08-21 | 1993-03-02 | Nikko Kyodo Co Ltd | High-strength and high-conductivity copper alloy for electronic equipment excellent in bendability and stress relaxation property |
CN1856588A (en) * | 2003-09-19 | 2006-11-01 | 住友金属工业株式会社 | Copper alloy and method for production thereof |
JP2012012644A (en) * | 2010-06-30 | 2012-01-19 | Hitachi Cable Ltd | Method for manufacturing copper alloy, and copper alloy |
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CN110753592A (en) * | 2017-06-30 | 2020-02-04 | 凤凰接触股份有限及两合公司 | Method for producing copper-containing components by selective laser sintering |
CN112281023A (en) * | 2020-11-23 | 2021-01-29 | 宁波博威合金材料股份有限公司 | Copper alloy material with excellent bending property and preparation method and application thereof |
CN112281023B (en) * | 2020-11-23 | 2021-08-31 | 宁波博威合金材料股份有限公司 | Copper alloy material with excellent bending property and preparation method and application thereof |
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