CN101014725A - Copper alloy for electric and electronic instruments - Google Patents
Copper alloy for electric and electronic instruments Download PDFInfo
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- CN101014725A CN101014725A CN 200580023486 CN200580023486A CN101014725A CN 101014725 A CN101014725 A CN 101014725A CN 200580023486 CN200580023486 CN 200580023486 CN 200580023486 A CN200580023486 A CN 200580023486A CN 101014725 A CN101014725 A CN 101014725A
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Abstract
Disclosed is a copper alloy for electrical and electronic devices consisting of 1-3 mass% of Ni, 0.2-1.2 mass% of Ti, 0.02-0.2 mass% of either one or both of Mg and Zr, 0.1-1 mass% of Zn and the balance of Cu and unavoidable impurities. The copper alloy for electrical and electronic devices contains at least one of an intermetallic compound of Ni, Ti and Mg, an intermetallic compound of Ni, Ti and Zr and an intermetallic compound of Ni, Ti, Mg and Zr, and has a stress relaxation of not more than 20% when maintained at 150 DEG C for 1000 hours. Also disclosed is a method for producing such a copper alloy for electrical and electronic devices.
Description
Technical field
The present invention relates to the copper alloy that is used for electric and electronic apparatus and element that its characteristic has improved.
Background technology
In the past, as the common material that is used for electric and electronic apparatus and element, except that the stainless steel-like steel, copper (Cu) class materials such as the phosphor bronze of electroconductibility and excellent thermal conductivity, red metal, brass also were widely used.
In recent years, the requirement to miniaturization, lightweight and the consequent high-density installationization of electric and electronic apparatus and element improves.If the propelling miniaturization, then the contact area of contact part will reduce, and the thickness of the plate of use is also wanted attenuation, in order to keep and equal in the past reliability, needs the higher material of intensity.Junctor is usually by the mechanism of chimeric mutually (joint) switches on or the exchange of information signal by the contact pressure (connecing pressure) of " deflection " of material, i.e. distortion generation regulation.Therefore, the minimizing owing to this contact pressure in use causes chimeric (joint) power to reduce, thereby can not switch on or the exchange message signal, and this is fatal defective.Reduction that will this chimeric (joint) power is called stress relaxation (anti-creep) characteristic, to the material requirements stress relaxation characteristics that is used for these electronic units can deterioration, be the copper alloy of proof stress relaxation property excellence.
In addition, according to the kind of junctor, the CPU (central processing unit) that is connected PC etc. sometimes is like this on the machine with heating.At this moment, connector material promotes stress relaxation owing to being heated, and chimeric (joint) power reduces rapidly, therefore is necessary to have the function of quick heat radiating.Exothermic character results from the electroconductibility of material, requires the higher material of electric conductivity.In addition, the requirement of the material that electroconductibility is high also is urgently to wish from using high-frequency message exchange from now on.
In addition, the miniaturization of electric apparatus and element is also to the material requirements excellent in vending workability.In a direction of miniaturization, the slimming of apparatus and element is just arranged.Advance the low level (highly low) of junctor owing to slimming.Therefore, in junctor, require the more good material of processibility.
Since these reasons, expectation strength height, the excellent electroconductibility of maintenance, and the material of proof stress relaxation property and excellent in bending workability.Particularly, require the material with following performance: intensity is more than the 600MPa, and the preferred 50%IACS of electric conductivity is above, stress relaxation rate is, the relaxation rate behind 150 ℃ * 1000h is below 20%, and the index R/t of bendability is preferred below 1.In addition, go back more than the demand intensity 650MPa material that electric conductivity 55%IACS is above.
As the method that increases Strength of Metallic Materials, carry out following method usually: to the material solution strengthening method of other elements that imported processing strained work strengthening method or solid solution, make second to separate out the precipitation strength method of strengthening mutually.
The Cu-Be alloy (C17200) that utilized the precipitation strength method, Cu-Ni-Si alloy (C70250), Cu-Fe alloy (C19400), Cu-Cr alloy (C18040) etc. are arranged.But though C17200 can be by using the mechanism for intensifying of separating out Be in the Cu parent phase, making intensity is more than the 1000MPa, and stress relaxation rate is below 20%, and bendability is also good, and electric conductivity is about 25%IACS.In addition, beryllium (Be) also has worry for using on its environmental problem, and this also is true.
Though C70250 can reach more than the 600MPa intensity by separate out the intermetallic compound that comprises Ni-Si in the Cu parent phase, stress relaxation rate is below 20%, and bendability is also good, and electric conductivity can not reach more than the 50%IACS.
C19400 uses the mechanism for intensifying of separating out iron (Fe) in the Cu parent phase, and intensity reaches more than the 600MPa, and electric conductivity also is about 65%IACS, the characteristic but stress relaxation rate and bendability can not meet the demands.
The electric conductivity of C18040 is about 80%IACS, and intensity is about 600MPa, but same with C19400, stress relaxation rate and the bendability characteristic that can not meet the demands.
Therefore,, can not be met the material that requires characteristic even adopt any precipitation strength method, therefore, strong request exploitation novel material.
At this situation, a following example is arranged, at the copper alloy that is used for electronic equipments and element, the Ni-Ti intermetallic compound is separated out, thereby improve intensity and electroconductibility.
The another one example is by add aluminium (Al), silicon (Si), manganese (Mn), magnesium (Mg) in the Cu-Ni-Ti alloy, can improve the binding property of lead frame and resin.
But,, therefore, can not satisfy in recent years performance along with electronic equipments and element and improve characteristic requirement copper alloy even these copper alloys can not meet the desired intensity, electric conductivity, bendability and proof stress relaxation property simultaneously.
The another one example is, separates out by make the Ni-Ti intermetallic compound in copper, improves each characteristic.
Consider in conjunction with the accompanying drawings, from following record above-mentioned and other feature and advantage can be clear and definite more of the present invention.
Description of drawings
Fig. 1 is the mode declaration pattern specification figure of the test method of stress relaxation characteristics.
Fig. 2 is the mode declaration pattern specification figure of the test method of solder attachment.
Summary of the invention
According to the present invention, provide following method.
(1), a kind of copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality %, 0.2 the Ti of～1.2 quality %, 0.02 the Mg of～0.2 quality % and any one or two kinds among the Zr, and the Zn of 0.1～1 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Mg, comprise Ni, the intermetallic compound of Ti and Zr, perhaps comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Mg and Zr, and the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%;
(2), (1) described copper alloy that is used for electric and electronic apparatus and element, wherein, comprise the intermetallic compound of Ni, Ti and Mg, the median size that comprises the intermetallic compound of Ni, Ti and Zr or comprise the intermetallic compound of Ni, Ti, Mg and Zr is 5～100nm, distribution density is 1 * 10
10～10
13Individual/mm
2, and the crystallization particle diameter of parent phase is below the 10 μ m;
(3), a kind of copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality %, 0.2 the Ti of～1.2 quality %, 0.02 the Sn of～0.2 quality % and any one or two kinds among the Si, and the Zn of 0.1～1 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Sn, comprise Ni, the intermetallic compound of Ti and Si, perhaps comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Sn and Si, and the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%;
(4), (1) described copper alloy that is used for electric and electronic apparatus and element, wherein, comprise the intermetallic compound of Ni, Ti and Sn, the median size that comprises the intermetallic compound of Ni, Ti and Si or comprise the intermetallic compound of Ni, Ti, Sn and Si is 5～100nm, distribution density is 1 * 10
10～10
13Individual/mm
2, and the crystallization particle diameter of parent phase is below the 10 μ m;
(5), a kind of manufacture method that is used for the copper alloy of electric and electronic apparatus and element, this method is to make the method for the copper alloy that is used for electric and electronic apparatus and element any in the item of (1)～(4), it is characterized in that, comprise following each operation: carry out more than 850 ℃ below 35 seconds solution treatment, be cooled to 300 ℃ with the speed of cooling more than 50 ℃/second from the temperature of this solution treatment, then, with surpass 0% and the rolling processing rate below 50% carry out cold rolling, under 450～600 ℃, carry out 5 hours with interior ageing treatment;
(6), a kind of manufacture method that is used for the copper alloy of electric and electronic apparatus and element, this method is to make the method for the copper alloy that is used for electric and electronic apparatus and element any in the item of (1)～(4), it is characterized in that, comprise following each operation: carry out more than 850 ℃ below 35 seconds solution treatment, be cooled to 300 ℃ with the speed of cooling more than 50 ℃/second from the temperature of this solution treatment, then under 450～600 ℃, carry out 5 hours with interior ageing treatment;
(7), a kind of copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality % and the Ti of 0.2～1.4 quality %, and the ratio of the quality percentage of above-mentioned Ni and Ti (Ni/Ti) is 2.2～4.7, and contain the Mg that adds up to 0.02～0.3 quality % and Zr one or both of, 0.1 the Zn of～5 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Mg, comprise Ni, the intermetallic compound of Ti and Zr, or comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Mg and Zr, and the distribution density of above-mentioned intermetallic compound is 1 * 10
9～1 * 10
13Individual/mm
2, tensile strength is more than the 650MPa and electric conductivity is more than the 55%IACS, the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%;
(8), a kind of copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality % and the Ti of 0.2～1.4 quality %, and the ratio of the quality percentage of above-mentioned Ni and Ti (Ni/Ti) is 2.2～4.7, and contain the Mg that adds up to 0.02～0.3 quality % and Zr one or both of, 0.1 the Zn of～5 quality %, Sn is above 0% and below 0.5 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Mg, comprise Ni, the intermetallic compound of Ti and Zr, or comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Mg and Zr, and the distribution density of above-mentioned intermetallic compound is 1 * 10
9～1 * 10
13Individual/mm
2, tensile strength is more than the 650MPa and electric conductivity is more than the 55%IACS, the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%;
(9), a kind of copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality % and the Ti of 0.2～1.4 quality %, and the ratio of the quality percentage of above-mentioned Ni and Ti (Ni/Ti) is 2.2～4.7, and contain the Mg of 0.02～0.3 quality % and the Zn of 0.1～5 quality %, Zr, Hf, In, among the Ag any one or add up to more than two kinds surpasses 0% and below 1.0 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Mg, comprise Ni, the intermetallic compound of Ti and Zr, or comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Mg and Zr, and the distribution density of above-mentioned intermetallic compound is 1 * 10
9～1 * 10
13Individual/mm
2, tensile strength is more than the 650MPa and electric conductivity is more than the 55%IACS, the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%;
(10), a kind of copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality % and the Ti of 0.2～1.4 quality %, and the ratio of the quality percentage of above-mentioned Ni and Ti (Ni/Ti) is 2.2～4.7, and contain the Mg of 0.02～0.3 quality % and the Zn of 0.1～5 quality %, Sn is above 0% and below 0.5 quality %, Zr, Hf, In, among the Ag any one or add up to more than two kinds surpasses 0% and below 1.0 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Mg, comprise Ni, the intermetallic compound of Ti and Zr, perhaps comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Mg and Zr, and the distribution density of above-mentioned intermetallic compound is 1 * 10
9～1 * 10
13Individual/mm
2, tensile strength is more than the 650MPa and electric conductivity is more than the 55%IACS, the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%; And
(11), a kind of manufacture method that is used for the copper alloy of electric and electronic apparatus and element, this method is to make the method for the copper alloy that is used for electric and electronic apparatus and element any in the item of (7)～(10), it is characterized in that, comprise following operation: carrying out more than 1 time or 2 times separating out thermal treatment with the timeliness of interior time in 5 hours under 450～650 ℃ the temperature, in the state before this timeliness is separated out thermal treatment, has the following electroconductibility of 35%IACS.
Below, the manufacture method of the copper alloy that is used for electric and electronic apparatus and element of the copper alloy that is used for electric and electronic apparatus and element of above-mentioned (1)～(4) record and above-mentioned (5)～(a 6) record merged be called the 1st embodiment.
The manufacture method of copper alloy that is used for electric and electronic apparatus and element of the copper alloy that is used for electric and electronic apparatus and element of above-mentioned (7)～(10) record and above-mentioned (11) record merged be called the 2nd embodiment.
Here, unless otherwise specified, so-called the present invention is the whole meaning that comprises the above-mentioned the 1st and the 2nd embodiment.
Embodiment
Explain the present invention below.
The inventor etc. make second to separate out the precipitation strength method research strengthened mutually and adopt in the reinforcement of the intermetallic compound that contains nickel (Ni) and titanium (Ti) and find in employing, by adding magnesium (Mg), zirconium (Zr), tin (Sn), silicon (Si) etc. intermetallic compound is changed, can make the basic material that requires characteristic that satisfies for intensity, electric conductivity, bendability, proof stress relaxation property and solder attachment.
In addition, in the present invention, particularly the 1st embodiment of the present invention, comprise in electric and electronic apparatus and the element being used for vehicle-mounted instrument.
Below, set forth the 1st embodiment of the present invention.
In the present invention, particularly the 1st embodiment of the present invention, by the intermetallic compound (following note is made " Ni-Ti-Mg-Zr ") that is formed on the intermetallic compound that comprises Ni, Ti and Mg (following note is made " Ni-Ti-Mg ") of separating out in the Cu parent phase, the intermetallic compound (following note is made " Ni-Ti-Zr ") that comprises Ni, Ti and Zr or comprises Ni, Ti, Mg and Zr, can improve each characteristic of alloy significantly.These are different fully with the situation that forms the Ni-Ti precipitate in alloy in the past, and these intermetallic compounds show high intensity, electric conductivity and proof stress relaxation property.
As mentioned above, when Ni-Ti was dispersed in the Cu parent phase imperceptibly, intensity improved in mechanism owing to precipitation strength, and electric conductivity rises simultaneously.At this moment, Ni-Ti-Mg, Ni-Ti-Zr or Ni-Ti-Mg-Zr compare with the situation of separating out Ni-Ti respectively or compoundly fine being dispersed in the Cu parent phase thus, show very large amount of reinforcement.By this effect, can obtain having the material of good intensity and electric conductivity.In addition, even disperse the Ni-Ti compound simultaneously, this effect also can occur, and the high more amount of reinforcement of the branch bulk density of Ni-Ti-Mg, Ni-Ti-Zr or Ni-Ti-Mg-Zr is big more.At this moment, the branch bulk density of Ni-Ti-Mg, Ni-Ti-Zr or Ni-Ti-Mg-Zr is compared with Ni-Ti, more than the preferred equivalent.
In addition, when the intermetallic compound (following note is made " Ni-Ti-Sn-Si ") of separating out the intermetallic compound (following note is made " Ni-Ti-Si ") that contains the intermetallic compound that comprises Ni, Ti and Sn (following note is made " Ni-Ti-Sn "), comprise Ni, Ti and Si, comprising Ni, Ti, Sn and Si, found above-mentioned same effect.
Then, the counter stress relaxation property describes.Be dispersed in imperceptibly in the Cu parent phase with Ni-Ti and compare, Ni-Ti-Mg, Ni-Ti-Zr or Ni-Ti-Mg-Zr respectively or compoundly fine when being dispersed in the Cu parent phase, the proof stress relaxation property significantly improves.In contrast, under the situation that the Ni-Ti precipitate is only arranged, stress relaxation rate can not reach below 20%.
Think that this is because compare the crystalline texture difference of Ni-Ti-Mg, Ni-Ti-Zr or Ni-Ti-Mg-Zr with the Ni-Ti compound.Be distributed in the Cu parent phase by the intermetallic compound that this crystalline texture is different is fine, can significantly improve the proof stress relaxation property.
So-called stress relaxation is the dislocation moving in the metal, the phenomenon of strain relief, and the force rate Ni-Ti compound of the pinned dislocation of Ni-Ti-Mg, Ni-Ti-Zr or Ni-Ti-Mg-Zr is big, shows to be difficult for lax phenomenon.
Even the intermetallic compound of this phenomenon Ni-Ti-Sn, Ni-Ti-Si or Ni-Ti-Sn-Si is identified too, by forming these precipitates, can make proof stress relaxation property excellence, and the material with desired characteristics.
This desired characteristics obtains by the component content of following provisions.
It is because when Ni was very few, the amount of reinforcement that produces was little owing to separating out, and can not obtain full intensity, in addition, can not improve the proof stress relaxation property that the content of Ni is defined as 1～3 quality %.In addition, when Ni is too much,, thereby cause the reduction of electric conductivity because superfluous Ni can be solid-solubilized in the parent phase after ageing treatment.In addition, solid solution temperature becomes near the temperature of fusing point, can not be industrial with stable technology manufacturing.Have again, need high temperature, solution treatment for a long time, can produce grain coarsening, the problem that the bendability difference is such.Preferred 1.4～2.6 quality % of the content of Ni, more preferred 1.8～2.3 quality %.
The reason that the content of Ti is limited to 0.2～1.2 quality % is that when Ti was very few, the amount of reinforcement that produces was little owing to separating out, and can not obtain full intensity, in addition, can not improve the proof stress relaxation property.In addition, when Ti is too much,, thereby cause the reduction of electric conductivity because superfluous Ti can be solid-solubilized in the parent phase after ageing treatment.In addition, need high temperature, solution treatment for a long time, can produce grain coarsening, the problem that the bendability difference is such.Preferred 0.5～1.1 quality % of the content of Ti, more preferred 0.7～1.0 quality %.
Mg forms intermetallic compound (below be also referred to as " precipitate ") with Ni, Ti and Zr etc., makes raisings such as intensity, electric conductivity, bendability, proof stress relaxation property.The reason that the content of Mg is defined as 0.02～0.2 quality % is, when Mg was very few, the precipitate etc. that comprises Ni, Ti and Mg was few, so the stress relaxation rate variance.In addition, when Mg is too much, need high temperature, solution treatment for a long time, grain coarsening, bendability is poor.In addition, even carry out ageing treatment, superfluous Mg also can become solid solution condition, the electric conductivity variation.In addition, stress relaxation rate variance.The influence that this composition difference that is considered to the element of precipitate causes.Preferred 0.05～0.15 quality % of the content of Mg, more preferred 0.08～0.12 quality %.
The reason that the content of Zr is defined as 0.02～0.2 quality % is identical with Mg.Preferred 0.05～0.15 quality % of the content of Zr, more preferred 0.08～0.12 quality %.
Sn forms precipitate with Ni, Ti, Si, makes raisings such as intensity, electric conductivity, bendability, proof stress relaxation property.The reason that the content of Sn is defined as 0.02～0.2 quality % is, when Sn was very few, the precipitate etc. that comprises Ni, Ti and Sn was few, so the stress relaxation rate variance.In addition, when Sn was too much, superfluous Sn also can become solid solution condition, and electric conductivity, bendability are poor.In addition, stress relaxation rate variance.The influence that this composition difference that is considered to the element of precipitate causes.Preferred 0.05～0.15 quality % of the content of Sn, more preferred 0.08～0.12 quality %.
The reason that the content of Si is defined as 0.02～0.2 quality % is, when Si was very few, the precipitate etc. that comprises Ni, Ti, Si was few, so intensity and proof stress relaxation property are poor.In addition, since remaining Ni solid solution, poorly conductive.In addition, when Si was too much, when forming the precipitate of expectation, superfluous Si can be solid-solubilized in the copper parent phase and electric conductivity is descended.Preferred 0.05～0.15 quality % of the content of Si, more preferred 0.08～0.12 quality %.
The size of above-mentioned intermetallic compound is, the median size in as the suitable particle diameter of equal-volume ball is generally 1～100nm, preferred 5～100nm, and in addition, distribution density is 1 * 10
10～10
13Individual/mm
2The time, intensity and excellent in bending workability, therefore preferred.
When the median size of intermetallic compound was too small, the effect deficiency by the intensity of separating out generation improves when excessive, produced the problem that is unfavorable for by the intensity raising of separating out generation.The more preferred 10～60nm of median size, especially preferred 20～50nm.The median size of intermetallic compound is by controlling the Heating temperature and the heat-up time of timeliness operation.Temperature is high more, and the time is long more, and median size is big more.On the contrary, temperature is low more, and the time is short more, and median size is more little.
In addition, when the distribution density of intermetallic compound is too small, improve the effect deficiency, when excessive, form thick precipitate at crystal boundary easily, and the problem that bendability worsens takes place owing to separate out the intensity of generation.Distribution density more preferred 3 * 10
10～5 * 10
12Individual/mm
2, especially preferred 1 * 10
11～3 * 10
12Individual/mm
2In addition, the distribution density of intermetallic compound by the appropriate combination timeliness separate out thermal treatment, timeliness is separated out cold working, solution treatment, the hot rolled condition of carrying out before the thermal treatment and is controlled.In addition, the distribution density of precipitate is measured the number of precipitate by transmission electron microscope observation, and it is (individual/mm to calculate the number of per unit area
2).
On the other hand, below the preferred 10 μ m of the crystallization particle diameter of parent phase.When the crystallization particle diameter of parent phase was excessive, bendability reduced.Below the preferred 5 μ m.The lower value of the crystallization particle diameter of parent phase has no particular limits, but is generally 3 μ m.Here, the crystallization particle diameter is meant major diameter.The crystallization particle diameter of parent phase is by controlling the Heating temperature and the heat-up time of solid solution operation.Temperature is high more, and the time is long more, and the crystallization particle diameter is big more.On the contrary, temperature is low more, and the time is short more, and the crystallization particle diameter is more little.
Zn has the solder attachment of raising, prevents to electroplate the effect of peeling off.Preferable use of the present invention is an electronic machine, and its most of parts engage with scolding tin.Therefore, the raising of solder attachment and the raising of part reliability are closely related, and are the indispensable characteristic that requires in the electronic machine purposes.Existing recently discuss (for example ， Shen Copper Ji Intraoperative Yan Jiu Hui Chi vol.026 (1987) p51-p56) of the effect of Zn.Wherein, when adding Zn, it is good that heat-resisting separability becomes.This be because, by adding Zn, can suppress the generation of space (ボ イ De), in addition, can suppress Si to the concentrating of the interface of fertile material and diffusion layer, therefore can improve heat-resisting separability.This example is the Cu-Ni-Si alloy of precipitation type alloy equally, even the 1st embodiment of the present invention also can be confirmed same effect.
The content of Zn be limited to 0.1～1 quality % be because, when Zn is very few, show not go out the effect of heat-resisting peel property, when Zn is too much, have the problem cause the electric conductivity reduction.Preferred 0.2～0.8 quality % of the content of Zn, more preferred 0.35～0.65 quality %.
With the stress relaxation rate of the copper alloy that is used for electric and electronic apparatus and element when keeping 1000 hours down for 150 ℃ of the present invention, particularly the 1st embodiment of the present invention is below 20%.Preferred below 18%, more preferred lower value has no particular limits below 16%, is 10%.
The copper alloy of the present invention, special the 1st embodiment of the present invention is made by hot rolling, cold rolling, solution treatment, ageing treatment, the pinch pass of further carrying out as required, the such operation of stress relieving.In this manufacturing process, the condition by the speed of cooling in control solution treatment (temperature) and the cooling thereafter can be controlled at scope of the present invention with above-mentioned intermetallic compound.Heat is pricked temperature and for example is made as 850 ℃～1000 ℃, and that then carries out cold rollingly for example can carry out with the working modulus more than 90%.
In addition, in an embodiment of the manufacture method of the present invention, particularly the 1st embodiment of the present invention, carrying out 35 seconds more than 850 ℃ with interior solution treatment, be cooled to 300 ℃ with the speed of cooling more than 50 ℃/second from the temperature of this solution treatment, then, to surpass 0% and carry out cold rollingly in the rolling processing rate below 50%, under 450 ℃～600 ℃, carry out 5 hours with interior ageing treatment.In addition, in another embodiment of the manufacture method of the present invention, particularly the 1st embodiment of the present invention, carrying out 35 seconds more than 850 ℃ with interior solution treatment, be cooled to 300 ℃ with the speed of cooling more than 50 ℃/second from the temperature of this solution treatment, then, under 450 ℃～600 ℃, carry out 5 hours with interior ageing treatment.The working modulus of pinch pass thereafter is preferred below 30%.
In the present invention, special the 1st embodiment of the present invention, solution treatment is preferably being carried out in 35 seconds more than 850 ℃.Solid solubility temperature is crossed when hanging down, and does not carry out recrystallize, and causes the remarkable decline (deterioration) of bendability.In addition,, there are crystallization precipitate or thick precipitate, can not obtain the highest precipitation strength amount with the timeliness of back even the situation that recrystallize carries out also can become not solutionizing state.Have again, also worry the remaining reduction that causes bendability owing to them.Cooling after the solution treatment preferably is cooled to 300 ℃ with the speed of cooling more than 50 ℃/second.This is because speed of cooling hour can cause that the element of solid solution is temporarily separated out.Because the precipitate of this moment is thick, therefore be unfavorable for strengthening.
The upper limit of solid solubility temperature preferably is controlled at below 1000 ℃ from the one-tenth of fuel etc. originally.When solution time is long, because the alligatoring of crystal grain makes bendability worsen.In more preferred 25 seconds.
The cold rolling of solution treatment back preferably do not carried out, or its cold working rate is below 50% when carrying out.When cold working rate was too high, bendability worsened.Be more preferably below 30%.
Ageing treatment is preferably being carried out in 5 hours under 450～600 ℃.Aging temperature is crossed when hanging down, and separates out deficiency, undercapacity.When aging temperature is too high, the precipitate alligatoring, unfavorable to intensity.Preferred 480～560 ℃.
In the present invention, particularly the 1st embodiment of the present invention, so-called final plastic working direction when the final plastic working of implementing is rolling processing, is meant rolling direction, is the drawing direction during drawing (wire drawing).In addition, so-called plastic working is rolling processing or drawing processing, does not comprise that with rectifications (aligning) such as tension force levellers be the processing of purpose.
Below, set forth the 2nd embodiment of the present invention.
In the present invention, particularly the 2nd embodiment of the present invention, by the intermetallic compound (following note is made " Ni-Ti-Mg-Zr ") that is formed on the intermetallic compound that comprises Ni, Ti and Mg (following note is made " Ni-Ti-Mg ") of separating out in the Cu parent phase, the intermetallic compound (following note is made " Ni-Ti-Zr ") that comprises Ni, Ti and Zr or comprises Ni, Ti, Mg and Zr, can improve each characteristic of alloy significantly.These are different fully with the situation that formation Ni-Ti in alloy in the past separates out, and these intermetallic compounds show high intensity, electroconductibility and proof stress relaxation property.
As mentioned above, when Ni-Ti was dispersed in the Cu parent phase imperceptibly, intensity improved in mechanism owing to precipitation strength, and electric conductivity rises simultaneously.At this moment, Ni-Ti-Mg, Ni-Ti-Zr or Ni-Ti-Mg-Zr compare with the situation of separating out Ni-Ti respectively or compoundly fine being dispersed in the Cu parent phase thus, demonstrate very large amount of reinforcement.By this effect, can obtain having the material of good intensity and electric conductivity.In addition, even disperse the Ni-Ti compound simultaneously, this effect also can occur, and the branch bulk density of Ni-Ti-Mg, Ni-Ti-Zr or Ni-Ti-Mg-Zr is high more, and amount of reinforcement is big more.At this moment, the branch bulk density of Ni-Ti-Mg, Ni-Ti-Zr or Ni-Ti-Mg-Zr is compared with Ni-Ti, more than the preferred equivalent.3 yuan of these Ni-Ti system or multi-element compounds also help the raising of proof stress relaxation property.
In addition, by an amount of solid solution Mg, Sn, can not reduce electroconductibility and intensity and proof stress relaxation property are improved.
These desired characteristics can obtain by the component content of following provisions.
It is because when Ni was very few, the amount of reinforcement that produces was little owing to separating out, and can not obtain full intensity, in addition, can not improve the proof stress relaxation property that the content of Ni is defined as 1～3 quality %.In addition, when Ni is too much,, thereby cause the reduction of electric conductivity because superfluous Ni can be solid-solubilized in the parent phase after ageing treatment.In addition, solid solution temperature is near the temperature fusing point, can not be industrial with stable technology manufacturing.Have again, need high temperature, solution treatment for a long time, can produce grain coarsening, the problem that the bendability difference is such.Preferred 1.2～2.4 quality % of the content of Ni, more preferred 1.4～2.2 quality %.
The reason that the content of Ti is limited to 0.2～1.4 quality % is that when Ti was very few, the amount of reinforcement that produces was little owing to separating out, and can not obtain full intensity, in addition, can not improve the proof stress relaxation property.In addition, when Ti is too much,, thereby cause the reduction of electric conductivity because superfluous Ti can be solid-solubilized in the parent phase after ageing treatment.In addition, need high temperature, solution treatment for a long time, can produce grain coarsening, the problem that the bendability difference is such.Preferred 0.3～1.0 quality % of the content of Ti, more preferred 0.35～0.9 quality %.
The reason that the ratio of the quality percentage of Ni and Ti (Ni/Ti) is defined as 2.2～4.7 scope is, because the compound that multi-element compounds such as Ni-Ti system or Ni-Ti-Mg system are formed as the chemical theory amount among the Cu is separated out, therefore, need to cooperate in the proper ratio.Be not under the situation of this ratio, solute element is unfavorable for the generation of compound, solid solution takes place electroconductibility is reduced, and is therefore not preferred.Ni/Ti preferred 2.6～3.8, more preferred 2.8～3.6.
Mg forms intermetallic compound (below be also referred to as " precipitate ") with Ni, Ti and Zr etc., makes raisings such as intensity, electric conductivity, bendability, proof stress relaxation property.The content of Mg and Zr one or both of adds up to the reason that is defined as 0.02～0.3 quality % to be, when very few, since comprise Ni, Ti and Mg precipitate, comprise the precipitate of Ni, Ti and Zr and/or comprise the precipitate of Ni, Ti, Mg and Zr few, so intensity variation.In addition, in the time of too much, need high temperature, solution treatment for a long time, grain coarsening, bendability is poor.In addition, even carry out ageing treatment, superfluous Mg and/or Zr also can become solid solution condition, the conduction rate variance.Preferred 0.05～0.18 quality % of the total of the content of Mg and Zr one or both of, more preferred 0.08～0.15 quality %.
The distribution density of above-mentioned intermetallic compound is 1 * 10
9～10
13Individual/mm
2The time, intensity and excellent in bending workability, therefore preferred.
When the distribution density of intermetallic compound was too small, the effect deficiency that the intensity that produces by separating out improves when excessive, formed thick precipitate easily on the crystal boundary, and the such problem of bendability deterioration takes place.Distribution density is more preferably 3 * 10
10～5 * 10
12Individual/mm
2, preferred especially 1 * 10
11～3 * 10
12Individual/mm
2In addition, the distribution density of intermetallic compound by the appropriate combination timeliness separate out thermal treatment, timeliness is separated out cold working, solution treatment, the hot rolled condition of carrying out before the thermal treatment and is controlled.
In addition, the distribution density of precipitate is measured the number of precipitate by transmission electron microscope observation, and it is (individual/mm to calculate the number of per unit area
2).
Zn has the solder attachment of raising, prevents to electroplate the effect of peeling off.Preferable use of the present invention is an electronic machine, and its most of parts engage with scolding tin.Therefore, the raising of solder attachment and the raising of part reliability are closely related, and are the indispensable characteristic that requires in the electronic machine purposes.Existing recently discuss (for example ， Shen Copper Ji Intraoperative Yan Jiu Hui Chi vol.026 (1987) p51-p56) of the effect of Zn.Wherein, when adding Zn, it is good that heat-resisting separability becomes.This be because, by adding Zn, can suppress the generation in space, in addition, can suppress Si to the concentrating of the interface of fertile material and diffusion layer, so can improve heat-resisting separability.This example is the Cu-Ni-Si alloy of precipitation type alloy equally, even the 2nd embodiment of the present invention also can be confirmed same effect.
The content of Zn be limited to 0.1～5 quality % be because, when Zn is very few, show not go out the effect of heat-resisting peel property, when Zn is too much, have the problem cause the electric conductivity reduction.Preferred 0.2～3.0 quality % of the content of Zn, more preferred 0.3～1 quality %.
Sn makes raisings such as proof stress relaxation property with the Mg solid solution.In addition, in the cooling of hot rolling of carrying out more than 900 ℃ or solution treatment, have the thick effect of separating out that suppresses Ni-Ti, and promote the precipitation-hardening amount that intensity is improved.Because this alloy system is realized the ideal solid solution condition of nearly all atom solid solution under the high-temperature more than 900 ℃, therefore, can prevent thick the separating out under the fast high temperature of atomic diffusion, this is important for obtaining good precipitation strength, but can realize this effect better by adding Sn, and improve because timeliness is separated out the intensity and the proof stress relaxation property of generation.In addition, can prevent thick separating out, improve bendability to crystal boundary etc.The content of Sn increases more, and above-mentioned effect is high more, but Sn is when too much, and superfluous Sn becomes solid solution condition, the conduction rate variance.The content of Sn is above 0% and below 0.5 quality %, preferred 0.05～0.25 quality %.
Zr, Hf, In and Ag form precipitate etc. with Ni, Ti, make raisings such as intensity, electric conductivity, proof stress relaxation property.Content increases more, and above-mentioned effect is high more, when still surpassing 1.0 quality %, just needs high temperature, solution treatment for a long time, grain coarsening, and bendability is poor.In addition, even carry out ageing treatment, superfluous atom also can become solid solution condition, the conduction rate variance.The total content of Zr, Hf, In and Ag is above 0% and below 1.0 quality %, preferred 0.05～0.5 quality %, more preferred 0.07～0.3 quality %.
The tensile strength of the copper alloy that is used for electric and electronic apparatus and element of the present invention, particularly the 2nd embodiment of the present invention is more than the 650MPa.More than the preferred 750Ma, higher limit has no particular limits, and is 850MPa.
The electric conductivity of the copper alloy that is used for electric and electronic apparatus and element of the present invention, particularly the 2nd embodiment of the present invention is more than the 55%IACS.More than the preferred 60%IACS, higher limit has no particular limits, and is 70%IACS.
With the stress relaxation rate of the copper alloy that is used for electric and electronic apparatus and element when keeping 1000 hours down for 150 ℃ of the present invention, particularly the 2nd embodiment of the present invention is below 20%.Preferred below 18%, more preferred lower value has no particular limits below 16%, is 10%.
The copper alloy of the present invention, special the 2nd embodiment of the present invention is made by the processing of for example casting, homogenize, hot rolling, cold rolling, solution treatment, ageing treatment, the pinch pass of further carrying out as required, these operations of stress relieving.
During casting, for preventing to cause and the segregation of solute element preferably improve speed of cooling, in addition finally solidifying portion etc., when too fast, can form the cavity in the ingot bar, quality be reduced, perhaps, improve the internal stress of ingot bar, become the reason of subsurface defect, therefore, preferably carry out with 1～100 ℃/second speed of cooling.More preferably carry out with 10～80 ℃/second.
In homogenizing anneal, separate out and make it solid solution for what prevent thick Ni-Ti based compound, preferably under the temperature more than the solid solubility temperature corresponding, carry out with the solute atoms amount of alloy.In addition, under the temperature more than the necessary temp, understand the oxidation that encourages Ti, Mg, elements such as Zr, Hf, the qualities such as plating tack of product are reduced, therefore not preferred.So the temperature that keeps ingot bar before hot rolling, is more preferably under 960～1000 ℃ and carries out preferably at 900～1000 ℃ usually at 800～1050 ℃.In order to make its abundant solid solution and anti-oxidation, the hold-time is preferred more than 1 hour in 10 hours.Reach under the slow situation of the heat-up rate that keeps temperature, can produce thick precipitate, therefore, preferably heat up with the temperature more than 3 ℃/minute.
In addition, begin in the cooling that finishes at hot rolled, in order to suppress separating out of solute atoms, the cooling of the spray by adopting the cold water below 20 ℃ waits and improves speed of cooling usually.Preferred 5～300 ℃/second, be more preferably 50～300 ℃/second.
In this operation, during operation by cold rolling minimizing thickness of slab, separate out thermal treatment by under 450～650 ℃ temperature, carrying out 1 time or 2 times 5 hours with the timeliness of interior time, can obtain excellent intensity, electroconductibility, proof stress relaxation property and bendability.
Timeliness is separated out thermal treatment temp and is crossed when hanging down, and separates out deficiency, intensity and electroconductibility deficiency, and when too high, thickization of precipitate, unfavorable to intensity.Preferred 480 ℃～620 ℃.
Timeliness is separated out in preferred 4 hours of the heat treatment period, and lower value is 0.1 hour.
In addition, separate out heat treated operation, can further improve intensity and electroconductibility by carry out more than 2 times this timeliness in cold rolling front and back.This be because, by the fine compound of separating out by the 1st time timeliness, can further improve the density of the cold rolling next time middle dislocation that imports, the dislocation of this moment becomes the 2nd later timeliness and separates out and separate out the karyogenesis site when precipitate is separated out in the thermal treatment, and further improve the density of precipitate, realize higher intensity.Therefore, the 1st time aging condition preferably adopts the highest condition of precipitate density.
In addition, given play to its effect in the thermal treatment in order to separate out in this timeliness, by doing one's utmost to increase the solid solution capacity of solute atoms under the state before separating out, its effect enlarges markedly.That is, before timeliness is separated out thermal treatment, form good solid solution condition, separate out thermal treatment by timeliness and realize high-density/fine precipitation state, occur the characteristic of high strength, high conduction, high proof stress relaxation property thus.Solid solubility uses electroconductibility as index usually, but the electroconductibility before timeliness is separated out thermal treatment is when to be 35%IACS following, and intensity, proof stress relaxation property improve.Surpass under the situation of electroconductibility of 35%IACS, the solute atoms quantitative change of separating out thermal treatment middle-high density/separate out imperceptibly in timeliness is few, and intensity and proof stress relaxation property are poor.Below the more preferred 30%IACS.
In the present invention, particularly in the 2nd embodiment of the present invention, so-called final plastic working direction when the final plastic working of implementing is rolling processing, is meant rolling direction, during drawing (wire drawing) direction, is meant the drawing direction.In addition, so-called plastic working is rolling processing or drawing processing, does not comprise that the rectification (aligning) with tension force leveller etc. is the processing of purpose.
The copper alloy that is used for electric and electronic apparatus and element of the present invention is not limited thereto, and for example goes for junctor, terminal, rly., switch, lead frame etc.
According to the present invention, can provide the novel copper alloy that is used for electric and electronic apparatus and element of intensity, electric conductivity, bendability, proof stress relaxation property and solder attachment excellence.
The copper alloy of the present invention, particularly the 1st embodiment can have following performance: intensity is more than the 600MPa, stress relaxation rate is below 20% for the relaxation rate behind 150 ℃ * 1000h, electric conductivity is more than the 50%IACS, the R/t of bendability index is below 1, and these metallic substance are the alloy materials that are fit to electric and electronic apparatus and element and vehicle mounted terminal/junctor or rly./switch etc.
In addition, the copper alloy of the present invention, particularly the 2nd embodiment can have following performance: intensity is more than the 650MPa, stress relaxation rate is, relaxation rate behind 150 ℃ * 1000h is below 20%, electric conductivity is more than the 55%IACS, and these metallic substance are the alloy materials that are fit to electric and electronic apparatus and element and vehicle mounted terminal/junctor or rly./switch etc.
Below, based on embodiment the present invention is described in more detail, but the present invention is not limited thereto.
Embodiment
Embodiment 1
Ni, the Ti, Mg, Zr, Zn, Sn and the Si that contain amount shown in table 1～4 with the high-frequency melting furnace melting, and surplus is the alloy of the composition of Cu, this alloy of casting under 10～30 ℃/second speed of cooling, obtaining thickness is that 30mm, width are that 100mm, length are the ingot bar of 150mm.This ingot bar after keeping 1 hour under 1000 ℃, is processed into the heat bundle plate that thickness is about 10mm with hot rolls.With the two sides of this hot-finished material about 1.0mm that prunes, remove oxide film, then, cold rolling one-tenth thickness is after the 0.29mm, carries out 950 ℃ * 15 seconds solution treatment in non-active gas, is cooled to 300 ℃ with the speed of cooling after the solid solution about 3 seconds (about 300 ℃/second).Be cold rolled to 0.23mm again, carry out 550 ℃ * 2 hours ageing treatment, roll after 0.2mm thickness, carry out 350 ℃ * 2 hours low-temperature annealings, obtain example 1～18 of the present invention and 40～57 and the sheet material of comparative example 21～34,60～67 and 70～73, as for the examination material.
Size of [1] tensile strength of the various sheet materials that obtain like this by the investigation of following method, [2] electric conductivity, [3] stress relaxation characteristics (SR), [4] bendability (R/t), [5] crystallization particle diameter (GS), [6] precipitate (PPT) and density, [7] solder attachment.The measuring method of each assessment item is as follows.
[1] tensile strength (TS)
Measure 3 JIS-13B test films that downcut from the calendering parallel direction according to JIS-Z2241, represent with its mean value (MPa).
[2] electric conductivity (EC)
Making is used four-terminal method from the test film of 10 * 150mm of calendering parallel direction cutting-out, measures 2 in the thermostatic bath that is controlled to be 20 ℃ (± 1 ℃), represents with its mean value (%IACS).In addition, terminal pitch is from being 100mm.
[3] stress relaxation characteristics (SR)
According to NEC material industry meeting standard basis EMAS-3003, under the condition of 150 ℃ * 1000h, measure.Fig. 1 is the explanatory view of the test method of stress relaxation characteristics.Fig. 1 (a) for pattern mensuration initial stage dependent variable δ is shown
0Explanatory view.1 expression test film, 4 expression test portion platforms.The employing cantilever method applies as 80% of 0.2% endurance of pre-stress.Then, expose up to 1000hr down at 150 ℃.Test film is positioned at position shown in Fig. 1 (b).Among Fig. 1 (b), the position that the strained test film does not take place in 3 expressions.Permanent strain amount δ
tBe H
t-H
1Value.
Therefore, stress relaxation rate (%) is used δ
t/ δ
0* 100 expressions.This test is that investigation is keeping the STRESS VARIATION under certain strained situation for a long time when being used in terminal material etc., and relaxation rate is more little, and alloy is good more.
[4] bendability (R/t)
Sheet material is cut to wide 10mm, and long 25mm (the parallel note with rolling direction of length direction is made GW, for the vertical direction note is made BW) carries out crooked W (90 °) with radius of curvature R=0 to it, with 50 times opticmicroscope visual observation bends crack-free is arranged.Metewand is to obtain and can access non-cracked limit bending radius, and represent with R/t (R is a bending radius, and t is a thickness of slab).
[5] crystallization particle diameter (GS)
Observe the preceding crystal structure of final processing by scanning electron microscope (200～1000 times), measure according to the process of chopping of JIS-H0501.
[6] precipitate (PPT)
To become diameter 3mm for the examination material die, after the two jet grinding methods of use are carried out thin-film grinding, take 5000～500000 times photo, measure the particle diameter and the density of precipitate on this photo with the transmission electron microscope of acceleration voltage 300kV.When the particle diameter of mensuration precipitate and density, by measuring its number, to get rid of the partial deviations of number with n=10 (n is the visual field number of observation).It is (individual/mm that its number is scaled per unit area
2).
[7] solder attachment
According to Fig. 2 pattern the explanatory view test scolding tin tack that illustrates.To be cut to 20 * 20mm for the examination material, the electrolytic degreasing of implementing material surface is as pre-treatment, and making thickness is the material 13 of 6mm.Water full (Sheng Ru) Sn-Pb SnPb63 material on the surface of material 13, make solder sections 12, be fixed on the iron wire 11 (being about 100mm) of the φ 2mm that has coated Cu on the Fe line thereon, and make material 13 and above-mentioned line 11 meet at right angles (Fig. 2 (a)).
The test film of above-mentioned line 11 has been adhered in heating in atmosphere, measures the iron wire 11 of heating front and back and the scolding tin strength of joint of material 13.Heating condition is in thermostatic bath and is set at 150 ℃ * 500h, after taking out from thermostatic bath, adopts air-cooled its fully cooling at leisure that makes, and shown in (b), carries out the tension test along the direction of arrow then, measures and bears a heavy burden.The condition of tension test is that load cell (a mouthful De セ Le) speed setting is 10mm/min, and at room temperature measures.In tension test, obtain from tensile strength for the test materials 13 of the interface peel of examination line 11 of material and solder sections 12.In addition, not from interface peel but the experiment material that iron wire 11 pulls up from solder sections 12 is judged to be the poor adhesion of iron wire 11 and scolding tin, not as evaluation object.
Similarly, also measure the tensile strength before the thermal treatment, and measure the intensity of the test materials 13 before the thermal treatment and the intensity of the test materials after the thermal treatment 13, this intensity reduction amount is 50% when following, be evaluated as zero, 50% to be evaluated as when above *.Bond strength is not passed in time and to reduce (intensity survival rate height) person's solderability good, the reliability height.
In addition, in the evaluation of precipitate, carry out transmission electron microscope observation, carry out the analysis of 5～10 precipitates, confirm the analysis peak of Ni, Ti, Mg, Zr and Sn, Si by transmission electron microscope accessory EDX analytical equipment (energy dispersion type device).In addition, take diffraction image, different diffraction image when confirm forming with formation Ni-Ti precipitate with transmission electron microscope.That is, so-called diffraction image difference, expression has formed the precipitate beyond the Ni-Ti.In the shooting of diffraction image, select to have the crystal grain of about 10～100 precipitates, implement characterization and evaluation.
The evaluation result of above-mentioned [1]～[7] is concluded and is shown in table 1～4.
Table 1
| Example of the present invention | Ni (quality %) | Ti (quality %) | Mg (quality %) | Zr (quality %) | Zn (quality %) | TS (MPa) | EC (％IACS) | SR (％) | R/t (GW) | R/t (BW) | GS (μm) | PPT (nm) | PPT (×10 10/mm 2) | Solder attachment |
| 1 | 1.55 | 0.57 | 0.08 | ---- | 0.51 | 601 | 55.3 | 19 | 0.5 | 0.5 | 4.4 | 20 | 21 | ○ |
| 2 | 2.11 | 0.78 | 0.12 | ---- | 0.55 | 685 | 52.7 | 18 | 0.5 | 0.5 | 4.8 | 22 | 15 | ○ |
| 3 | 2.54 | 0.94 | 0.14 | ---- | 0.42 | 702 | 50.8 | 16 | 0.5 | 0.5 | 4.7 | 20 | 6 | ○ |
| 4 | 2.90 | 1.07 | 0.18 | ---- | 0.44 | 732 | 48.2 | 14 | 1.0 | 1.0 | 4.9 | 21 | 16 | ○ |
| 5 | 1.56 | 0.58 | ---- | 0.07 | 0.51 | 605 | 55.7 | 17 | 0.5 | 0.5 | 4.8 | 20 | 163 | ○ |
| 6 | 2.08 | 0.77 | ---- | 0.11 | 0.25 | 675 | 52.0 | 15 | 0.5 | 0.5 | 4.8 | 23 | 65 | ○ |
| 7 | 2.51 | 0.93 | ---- | 0.13 | 0.55 | 694 | 50.2 | 14 | 0.5 | 0.5 | 4.9 | 41 | 156 | ○ |
| 8 | 2.95 | 1.09 | ---- | 0.19 | 0.60 | 745 | 49.0 | 12 | 1.0 | 1.0 | 4.1 | 20 | 5 | ○ |
| 9 | 2.01 | 0.74 | 0.05 | ---- | 0.44 | 681 | 53.8 | 19 | 0.5 | 0.5 | 4.2 | 23 | 5 | ○ |
| 10 | 2.10 | 0.78 | 0.11 | ---- | 0.50 | 710 | 51.7 | 16 | 0.5 | 0.5 | 4.3 | 33 | 15 | ○ |
| 11 | 2.14 | 0.79 | ---- | 0.05 | 0.52 | 723 | 50.8 | 18 | 0.5 | 0.5 | 4.3 | 22 | 54 | ○ |
| 12 | 2.15 | 0.80 | ---- | 0.05 | 0.46 | 727 | 50.6 | 15 | 0.5 | 0.5 | 4.4 | 21 | 62 | ○ |
| 13 | 2.02 | 0.75 | 0.07 | 0.08 | 0.52 | 684 | 53.5 | 18 | 0.5 | 0.5 | 4.4 | 23 | 46 | ○ |
| 14 | 2.05 | 0.76 | 0.10 | 0.10 | 0.51 | 694 | 52.9 | 14 | 0.5 | 0.5 | 4.8 | 12 | 5 | ○ |
| 15 | 2.01 | 0.74 | 0.06 | 0.08 | 0.50 | 681 | 53.8 | 19 | 0.5 | 0.5 | 4 | 13 | 165 | ○ |
| 16 | 2.17 | 0.80 | 0.09 | 0.06 | 0.70 | 733 | 50.1 | 15 | 0.5 | 0.5 | 4.2 | 33 | 6 | ○ |
| 17 | 2.10 | 0.58 | 0.10 | ---- | 0.23 | 710 | 51.7 | 17 | 0.5 | 0.5 | 4.9 | 8 | 12 | ○ |
| 18 | 2.11 | 0.55 | ---- | 0.11 | 0.66 | 714 | 51.5 | 16 | 0.5 | 0.5 | 4.3 | 32 | 165 | ○ |
Table 2
| Comparative example | Ni (quality %) | Ti (quality %) | Mg (quality %) | Zr (quality %) | Zn (quality %) | TS (MPa) | EC (％IACS) | SR (％) | R/t (GW) | R/t (BW) | GS (μm) | PPT (nm) | PPT (×10 10/mm 2) | Solder attachment |
| 21 | 0.88 | 0.33 | ---- | ---- | 0.45 | 506 | 59.3 | 41 | 0.5 | 0.5 | 4.2 | 23 | 123 | ○ |
| 22 | 3.30 | 1.22 | ---- | ---- | 0.34 | 701 | 38.2 | 33 | 2.0 | 2.0 | 12.4 | 24 | 15 | ○ |
| 23 | 3.51 | 0.38 | ---- | ---- | 0.44 | 488 | 32 | 48 | 1.5 | 1.5 | 13.3 | 22 | 53 | ○ |
| 24 | 2.91 | 2.50 | ---- | ---- | 0.54 | 685 | 32.7 | 33 | 2.0 | 2.0 | 13.2 | 12 | 6 | ○ |
| 25 | 2.20 | 0.81 | 0.01 | ---- | 0.55 | 702 | 50.8 | 35 | 0.5 | 0.5 | 4.8 | 43 | 53 | ○ |
| 26 | 2.10 | 0.78 | 0.55 | ---- | 0.55 | 732 | 42.3 | 25 | 2.0 | 2.0 | 4.5 | 34 | 125 | ○ |
| 27 | 2.08 | 0.77 | ---- | 0.01 | 0.34 | 622 | 56.0 | 40 | 1.0 | 1.0 | 12.5 | 23 | 265 | ○ |
| 28 | 2.12 | 0.79 | ---- | 0.60 | 0.55 | 633 | 43.6 | 22 | 2.0 | 2.0 | 10.9 | 44 | 46 | ○ |
| 29 | 2.11 | 0.78 | 0.005 | 0.007 | 0.23 | 612 | 55.4 | 44 | 1.0 | 1.0 | 11.5 | 45 | 15 | ○ |
| 30 | 2.08 | 0.77 | 0.56 | 0.66 | 0.30 | 622 | 41.6 | 28 | 2.0 | 2.0 | 12.2 | 23 | 156 | ○ |
| 31 | 2.53 | 0.94 | 0.20 | ---- | ---- | 721 | 38.1 | 18 | 1.0 | 1.0 | 4.4 | 32 | 22 | × |
| 32 | 2.10 | 0.78 | ---- | 0.13 | ---- | 723 | 37.3 | 19 | 1.0 | 1.0 | 4.9 | 44 | 34 | × |
| 33 | 2.20 | 0.81 | 0.23 | ---- | 1.50 | 712 | 39.3 | 19 | 0.5 | 0.5 | 5.5 | 34 | 54 | ○ |
| 34 | 2.90 | 1.07 | ---- | 0.30 | 2.02 | 733 | 38.3 | 19 | 0.5 | 0.5 | 3.9 | 54 | 43 | ○ |
Table 3
| Example of the present invention | Ni (quality %) | Ti (quality %) | Sn (quality %) | Si (quality %) | Zn (quality %) | TS (MPa) | EC (％IACS) | SR (％) | R/t (GW) | R/t (BW) | GS (μm) | PPT (nm) | PPT (×10 10/mm 2) | Solder attachment |
| 40 | 1.64 | 0.65 | 0.08 | ---- | 0.43 | 604 | 54.7 | 20 | 0.5 | 0.5 | 4.4 | 21 | 12 | ○ |
| 41 | 2.16 | 0.79 | 0.13 | ---- | 0.52 | 688 | 51.8 | 17 | 0.5 | 0.5 | 4.5 | 23 | 105 | ○ |
| 42 | 2.63 | 1.03 | 0.15 | ---- | 0.36 | 705 | 50.8 | 14 | 0.5 | 0.5 | 4.5 | 27 | 98 | ○ |
| 43 | 2.90 | 1.15 | 0.19 | ---- | 0.42 | 735 | 47.6 | 12 | 1.0 | 1.0 | 4.6 | 22 | 15 | ○ |
| 44 | 1.60 | 0.67 | ---- | 0.08 | 0.47 | 608 | 54.9 | 17 | 0.5 | 0.5 | 4.6 | 27 | 66 | ○ |
| 45 | 2.08 | 0.86 | ---- | 0.12 | 0.19 | 679 | 51.7 | 15 | 0.5 | 0.5 | 4.2 | 31 | 24 | ○ |
| 46 | 2.57 | 0.96 | ---- | 0.14 | 0.50 | 697 | 49.5 | 11 | 0.5 | 0.5 | 4.3 | 43 | 15 | ○ |
| 47 | 2.97 | 1.13 | ---- | 0.19 | 0.58 | 748 | 48.7 | 11 | 1.0 | 1.0 | 4.7 | 22 | 15 | ○ |
| 48 | 2.08 | 0.75 | 0.06 | ---- | 0.43 | 684 | 53.4 | 17 | 0.5 | 0.5 | 4.8 | 45 | 23 | ○ |
| 49 | 2.14 | 0.82 | 0.15 | ---- | 0.47 | 714 | 50.9 | 15 | 0.5 | 0.5 | 4.2 | 33 | 24 | ○ |
| 50 | 2.22 | 0.82 | ---- | 0.06 | 0.43 | 727 | 50.4 | 17 | 0.5 | 0.5 | 4.5 | 23 | 42 | ○ |
| 51 | 2.25 | 0.84 | ---- | 0.11 | 0.43 | 730 | 49.7 | 13 | 0.5 | 0.5 | 4.0 | 21 | 45 | ○ |
| 52 | 2.03 | 0.76 | 0.08 | 0.09 | 0.52 | 688 | 53.0 | 16 | 0.5 | 0.5 | 4.2 | 25 | 16 | ○ |
| 53 | 2.13 | 0.81 | 0.12 | 0.11 | 0.44 | 698 | 52.7 | 12 | 0.5 | 0.5 | 4.6 | 13 | 31 | ○ |
| 54 | 2.02 | 0.78 | 0.07 | 0.08 | 0.42 | 684 | 53.2 | 20 | 0.5 | 0.5 | 4.4 | 15 | 156 | ○ |
| 55 | 2.26 | 0.89 | 0.09 | 0.15 | 0.63 | 736 | 49.4 | 14 | 0.5 | 0.5 | 4.3 | 35 | 264 | ○ |
| 56 | 2.16 | 0.65 | 0.10 | ---- | 0.18 | 714 | 51.0 | 15 | 0.5 | 0.5 | 4.7 | 9 | 51 | ○ |
| 57 | 2.17 | 0.58 | ---- | 0.12 | 0.63 | 717 | 51.0 | 14 | 0.5 | 0.5 | 4.7 | 36 | 55 | ○ |
Table 4
| Comparative example | Ni (quality %) | Ti (quality %) | Sn (quality %) | Si (quality %) | Zn (quality %) | TS (MPa) | EC (％IACS) | SR (％) | R/t (GW) | R/t (BW) | GS (μm) | PPT (nm) | PPT (×10 10/mm 2) | Solder attachment |
| 60 | 0.95 | 0.42 | ---- | ---- | 0.37 | 509 | 58.4 | 39 | 0.5 | 0.5 | 4.9 | 27 | 135 | ○ |
| 61 | 3.33 | 1.25 | ---- | ---- | 0.25 | 704 | 44.3 | 31 | 2.0 | 2.0 | 11.5 | 25 | 15 | ○ |
| 62 | 3.59 | 0.44 | ---- | ---- | 0.39 | 492 | 41.0 | 47 | 1.5 | 1.5 | 12.5 | 23 | 56 | ○ |
| 63 | 2.91 | 2.50 | ---- | ---- | 0.47 | 688 | 38.3 | 32 | 2.0 | 2.0 | 12.2 | 13 | 5 | ○ |
| 64 | 2.27 | 0.84 | 0.01 | ---- | 0.50 | 705 | 50.2 | 33 | 0.5 | 0.5 | 4.4 | 45 | 42 | ○ |
| 65 | 2.18 | 0.83 | 0.56 | ---- | 0.53 | 735 | 41.4 | 24 | 2.0 | 2.0 | 4.2 | 34 | 12 | ○ |
| 66 | 2.15 | 0.82 | ---- | 0.01 | 0.26 | 626 | 55.0 | 39 | 1.0 | 1.5 | 10.5 | 27 | 26 | ○ |
| 67 | 2.15 | 0.80 | ---- | 0.62 | 0.47 | 636 | 43.2 | 22 | 2.0 | 2.0 | 10.2 | 44 | 66 | ○ |
| 70 | 2.31 | 0.89 | 0.03 | ---- | ---- | 711 | 50.7 | 33 | 0.5 | 0.5 | 4.1 | 34 | 33 | × |
| 71 | 2.22 | 0.85 | 0.26 | ---- | ---- | 733 | 42.3 | 34 | 0.5 | 0.5 | 4.2 | 45 | 55 | × |
| 72 | 2.32 | 0.76 | 0.38 | ---- | 1.47 | 699 | 39.0 | 24 | 1.0 | 1.0 | 4.9 | 37 | 34 | ○ |
| 73 | 2.33 | 0.56 | ---- | 0.16 | 1.95 | 683 | 36.2 | 30 | 2.0 | 2.0 | 10.8 | 55 | 33 | ○ |
By table 1, table 3 can be clear and definite, it is excellent specific property below 20% that example 1～18,40～57 of the present invention all has stress relaxation characteristics.
In contrast, comparative example 21 can not obtain sufficient precipitation strength amount, so tensile strength is poor because the Ni amount is few.In addition, owing to do not add Mg and Zr, therefore, the stress relaxation rate variance.
Comparative example 22 needs high temperature, solution treatment for a long time because Ni and Ti, grain coarsening, and bendability is poor.In addition, after the ageing treatment, superfluous Ni, Ti also can be solid-solubilized in the parent phase, therefore conduct electricity rate variance.In addition, owing to do not add Mg and Zr, therefore, the stress relaxation rate variance.
Comparative example 23 needs high temperature, solution treatment for a long time because Ni, grain coarsening, and bendability is poor.In addition, because the Ni surplus helps the density of the Ni-Ti precipitate of intensity to reduce, tensile strength is poor.Even carry out ageing treatment, superfluous Ni also can be solid-solubilized in the parent phase, therefore conducts electricity rate variance.In addition, owing to do not add Mg and Zr, therefore, the stress relaxation rate variance.
Comparative example 24 needs high temperature, solution treatment for a long time because Ti, grain coarsening, and bendability is poor.In addition, even carry out ageing treatment, superfluous Ti also can be solid-solubilized in the parent phase, therefore conducts electricity rate variance.In addition, owing to do not add Mg and Zr, therefore, the stress relaxation rate variance.
Comparative example 25 is because Mg is few, and therefore, the precipitate that comprises Ni, Ti, Mg is few, the stress relaxation rate variance.
Comparative example 26 is because Mg is many, even carry out ageing treatment, superfluous Mg also can become solid solution condition, and electric conductivity, bendability are all poor.In addition, stress relaxation rate variance.
Comparative example 27 is because Zr is few, and therefore, the precipitate that comprises Ni, Ti, Zr is few, the stress relaxation rate variance.
Comparative example 28 needs high temperature, solution treatment for a long time because Zr, grain coarsening, and bendability is poor.In addition, even carry out ageing treatment, superfluous Zr also can be solid-solubilized in the parent phase, therefore conducts electricity rate variance.Have, stress relaxation rate is also poor again.
Comparative example 29 is because Mg, Zr lack, and therefore, the precipitate that comprises Ni, Ti, Mg, Zr is few, the stress relaxation rate variance.
Therefore comparative example 30, needs high temperature, solution treatment for a long time because Mg, Zr are many, grain coarsening, and bendability is poor.In addition, even carry out ageing treatment, superfluous Mg, Zr also can be solid-solubilized in the parent phase, therefore conduct electricity rate variance.Have, stress relaxation rate is also poor again.
Comparative example 31,32 is not owing to there is Zn, so the solder attachment deterioration.
Comparative example 33,34 is because Zn is many, so electric conductivity reduces.
In addition, comparative example 21～34th, the comparative example of the invention of above-mentioned (1) and (2) record.
Therefore comparative example 60, can not obtain sufficient precipitation strength amount, so tensile strength is poor because Ni is few.In addition, the density of Ni-Ti precipitate is insufficient and do not add Sn, Si, therefore, and the stress relaxation rate variance.
Therefore comparative example 61, needs high temperature, solution treatment for a long time because Ni and Ti are many, grain coarsening, and bendability is poor.In addition, even carry out ageing treatment, superfluous Ni, Ti also can be solid-solubilized in the parent phase, therefore conduct electricity rate variance.In addition, owing to do not add Sn, Si, therefore, the stress relaxation rate variance.
Comparative example 62 needs high temperature, solution treatment for a long time because Ni, grain coarsening, and bendability is poor.In addition, because the Ni surplus helps the density of the Ni-Ti precipitate of intensity to reduce, tensile strength is poor.In addition, even carry out ageing treatment, superfluous Ni also can be solid-solubilized in the parent phase, therefore conducts electricity rate variance.In addition, owing to do not add Sn, Si, therefore, the stress relaxation rate variance.
Comparative example 63 needs high temperature, solution treatment for a long time because Ti, grain coarsening, and bendability is poor.In addition, even carry out ageing treatment, superfluous Ti also can be solid-solubilized in the parent phase, therefore conducts electricity rate variance.In addition, owing to do not add Sn, Si, therefore, the stress relaxation rate variance.
Comparative example 64 is because Sn is few, and therefore, the precipitate that comprises Ni, Ti, Sn is few, the stress relaxation rate variance.
Comparative example 65 is because Sn is many, even carry out ageing treatment, superfluous Sn also can become solid solution condition, and electric conductivity, bendability are all poor.In addition, stress relaxation rate variance.
Comparative example 66 is because Si is few, and therefore, the precipitate that comprises Ni, Ti, Si is few, the stress relaxation rate variance.
Comparative example 67 needs high temperature, solution treatment for a long time because Si, grain coarsening, and bendability is poor.In addition, even carry out ageing treatment, superfluous Si also can be solid-solubilized in the parent phase, therefore conducts electricity rate variance.Have, stress relaxation rate is also poor again.
Comparative example 70,71 is not owing to there is Zn, so the solder attachment deterioration.
Comparative example 72,73 is because Zn is many, so electric conductivity reduces.
In addition, above-mentioned comparative example 60～67,70～73rd, the comparative example of the invention of above-mentioned (3) and (4) record.
Use the example of the present invention 15 same alloys of forming with the foregoing description 1, solution treatment condition, the cold working condition of carrying out afterwards, the aging condition that carries out are subsequently carried out various changes.Other are created conditions similarly to Example 1.In addition, carry out the mensuration of assessment item [1]～[7] similarly to Example 1.Table 5 illustrates solid solution condition and evaluation result.
Table 5
| Solutionizing | Cold working rate (%) | Timeliness | TS (MPa) | EC (％IACS) | SR (％) | R/t (GW) | R/t (BW) | GS (μm) | PPT (nm) | PPT (×10 10/mm 2) | Solder attachment | ||||
| Temperature (℃) | Time (sec) | Speed of cooling (℃/s) | Temperature (℃) | Time (hr) | |||||||||||
| Example of the present invention | |||||||||||||||
| 81 | 1000 | 15 | 330 | 20 | 550 | 2 | 690 | 52.9 | 18 | 0.75 | 0.75 | 6 | 17 | 187 | ○ |
| 82 | 950 | 30 | 110 | 30 | 475 | 1 | 688 | 52.0 | 19 | 0.5 | 0.75 | 5 | 18 | 118 | ○ |
| 83 | 950 | 15 | 70 | 10 | 550 | 2 | 677 | 54.1 | 18 | 0.5 | 0.5 | 5 | 13 | 231 | ○ |
| 84 | 900 | 15 | 100 | 35 | 500 | 3 | 654 | 56.3 | 20 | 0.5 | 0.5 | 3 | 12 | 210 | ○ |
| 85 | 950 | 5 | 200 | 25 | 525 | 1.5 | 690 | 52.9 | 19 | 0.5 | 0.5 | 4 | 11 | 103 | ○ |
| 86 | 850 | 15 | 150 | 10 | 550 | 3 | 689 | 53.0 | 18 | 0.5 | 0.5 | 5 | 12 | 129 | ○ |
| 87 | 950 | 15 | 300 | 20 | 525 | 3.5 | 681 | 53.8 | 19 | 0.5 | 0.5 | 4 | 13 | 165 | ○ |
| 88 | 950 | 15 | 200 | 0 | 475 | 4 | 602 | 50.3 | 17 | 0 | 0 | 6 | 12 | 229 | ○ |
| Comparative example | |||||||||||||||
| 91 | 950 | 15 | 35 | 20 | 525 | 3 | 622 | 57.2 | 24 | 0.5 | 0.5 | 5 | 13 | 65 | ○ |
| 92 | 900 | 15 | 25 | 20 | 525 | 3 | 612 | 58.0 | 27 | 0.5 | 0.75 | 5 | 12 | 77 | ○ |
| 93 | 800 | 15 | 110 | 20 | 525 | 3 | 639 | 56.9 | 26 | 0.75 | 0.75 | 3 | 10 | 52 | ○ |
| 94 | 800 | 30 | 105 | 20 | 525 | 3 | 629 | 56.0 | 28 | 0.75 | 0.75 | 5 | 11 | 49 | ○ |
| 95 | 950 | 60 | 130 | 20 | 525 | 3 | 690 | 52.9 | 18 | 1.5 | 1.5 | 11 | 12 | 223 | ○ |
| 96 | -do not have- | -do not have- | -do not have- | ＞90 | 525 | 3 | 634 | 58.3 | 33 | ＞2 | ＞2 | --- | 8 | 169 | ○ |
| 97 | 950 | 15 | 200 | 60 | 525 | 3 | 612 | 59.0 | 33 | ＞2 | ＞2 | 4 | 12 | 128 | ○ |
| 98 | 950 | 15 | 200 | 20 | 625 | 3 | 561 | 59.4 | 34 | 0.75 | 0.75 | 6 | 667 | 4 | ○ |
| 99 | 950 | 15 | 200 | 20 | 400 | 3 | 533 | 47.0 | 42 | 0.75 | 0.75 | 8 | 2 | 321 | ○ |
| 100 | 950 | 15 | 200 | 20 | 525 | 7 | 553 | 59.7 | 32 | 0.75 | 0.75 | 3 | 333 | 3 | ○ |
Can be clear and definite from table 5, example 81～88 of the present invention has excellent characteristic.
In contrast, comparative example 91,92 is because speed of cooling is slow, so precipitate becomes thick, so the stress relaxation rate variance.
Comparative example 93 is because the solutionizing temperature is low, therefore helps the solid solution of the element of separating out to tail off, and the density of separating out during ageing treatment diminishes, the stress relaxation rate variance.
Comparative example 94 is because the solutionizing temperature is low, therefore helps the solid solution of the element of separating out to tail off, and the density of separating out during ageing treatment diminishes, the stress relaxation rate variance.
Comparative example 95 is because solution time is long, so crystal grain becomes thick, and bendability is poor.
Therefore comparative example 96 does not carry out recrystallize owing to do not carry out solution treatment, and the cold working rate after the hot rolling is more than 90%, so, be organized as fibrously, can not measure the crystallization particle diameter.In addition, help the precipitate of separating out few, therefore, bendability, stress relaxation rate variance.
Comparative example 97 is owing to the cold working rate height after the solution treatment, and therefore, bendability is poor.
Comparative example 98 is because the aging temp height, so precipitate becomes thick, so intensity difference.
Comparative example 99 is owing to the aging temp height, so the size of precipitate is small, so intensity difference.
Comparative example 100 is because aging time is long, so precipitate becomes thick, so intensity difference.
In addition, comparative example 91～100th, the comparative example of the invention of above-mentioned (5) and (6) record.
Embodiment 3
What is called in the product of the present invention has the characteristic of high conductivity and intensity and proof stress relaxation property excellence, is by being that compound occurs at the thermal treatment middle-high density of timeliness precipitation annealing/separate out imperceptibly in the Cu parent phase between the multi-element metal of body material with Ni-Ti system, Ni-Ti-Mg system, Ni-Ti-Zr system, other Ni-Ti.Therefore, must do one's utmost to increase the solid solution capacity of solute atoms under the state before timeliness is separated out operation, be below the 35%IACS as the electroconductibility of solid solubility index of this moment, below the more preferred 30%IACS.Therefore, separate out in the operation of handling the front, 1. casting speed, the heat treated heat-up rate and keep temperature and hold-time, the hot rolling of 3. carrying out subsequently and the speed of cooling in the hot rolling to carry out in accordance with the following methods of homogenizing that 2. carries out subsequently in timeliness.
Ni, Ti, Mg, Zn, Sn, Zr, Hf, In and the Ag and the surplus that contain amount shown in table 6～10 by the high-frequency melting furnace melting are the alloy of the composition of Cu, and it is that 30mm, width are that 100mm, length are the ingot bar of 150mm that casting obtains thickness.Under 1～100 ℃/second speed of cooling, carry out.
Behind the homogenizing anneal of this ingot bar through 800～1050 ℃ * 1h, be processed into the hot-rolled sheet of the about 10mm of thickness by hot rolling.Heat up with the speed more than 3 ℃/minute.
In addition, hot rolling is carried out under 10～300 ℃/second speed of cooling.
With the two sides of this hot-finished material about 1.0mm that prunes, remove oxide film, then obtain the sheet material that thickness is 0.1～2mm by cold working.This sheet material is processed/thermal treatment according to operation shown below 1～4,5-1～5-4,6-1～6-4 and 7-1～7-4, obtains each test materials.
[operation 1]
After cold rolling, in non-active gas, under 850～1000 ℃ temperature, carry out 15～600 seconds solution treatment, then carry out cold working, under 450～650 ℃ temperature, carry out 1 time 5 hours with interior timeliness precipitation annealing, to surpass 0 and this annealed material is carried out final cold working in the working modulus below 30%, and carry out 150～500 ℃ stress relieving, make test materials.
[operation 2]
After cold rolling, in non-active gas, under 850～1000 ℃ temperature, carry out 15～600 seconds solution treatment, then, carry out under cold working more than 1 time and 450～650 ℃ the temperature more than 2 times 5 hours alternately with interior timeliness precipitation annealing, to surpass 0 and the final annealing material is carried out final cold working in the working modulus below 30%, and carry out 150～500 ℃ stress relieving, make test materials.
[operation 3]
After cold rolling, carry out 1 time 5 hours with interior timeliness precipitation annealing under 450～650 ℃ temperature, the working modulus with 0～30% is carried out final cold working to this annealed material, and carries out 150～500 ℃ stress relieving, makes test materials.
[operation 4]
Carry out cold working more than 2 times and under 450～650 ℃ temperature 5 hours more than 2 times alternately with interior timeliness precipitation annealing, to surpass 0 and the final annealing material is carried out final cold working in the working modulus below 30%, and carry out 150～500 ℃ stress relieving, make test materials.
[operation 5-1～5-4]
The timeliness precipitation annealing of operation 1,2,3,4 more than one or two in, carry out in the temperature that surpasses 650 ℃.With these operations respectively as operation 5-1～5-4.
[operation 6-1～6-4]
In the timeliness precipitation annealing of operation 1,2,3,4 more than one or two in, carry out in the temperature of 450 ℃ of less thaies.With these operations respectively as operation 6-1～6-4.
[operation 7-1～7-4]
In operation 1,2,3,4, carry out the timeliness precipitation annealing above under the state of 35%IACS to carry out timeliness precipitation annealing electric conductivity before.With these operations respectively as operation 7-1～7-4.
For the various sheet materials that obtain like this, investigation [1] tensile strength (TS), [2] electric conductivity (EC), [3] stress relaxation characteristics (SR), [4] bendability, the density of [5] precipitate (PPT), [6] solder attachment.[1] evaluation of the density of tensile strength, [2] electric conductivity, [3] stress relaxation characteristics, [5] precipitate, [6] solder attachment similarly to Example 1.The measuring method of other assessment items is as follows.
[4] bendability (R/t)
Sheet material is cut to wide 0.5mm, and long 25mm carries out crooked W (90 °) with the bending radius (R) identical with thickness of slab (t) to it, with 50 times opticmicroscope visual observation bends crack-free is arranged.Metewand is not represent with zero when curved surface breaks that when breaking usefulness * expression is arranged.
In addition, the evaluation of precipitate is also identical with embodiment 1.
The evaluation result of above-mentioned [1]～[6] is concluded and is shown in table 6～10.
Table 6
| Numbering | Ni quality % | Ti quality % | Zn quality % | Mg quality % | The Ni/Ti ratio | The operation numbering | TS MPa | EC ％IACS | SR ％ | Bendability | Solder attachment | PPT ×10 12/mm 2 |
| Embodiment 201 | 2.01 | 0.63 | 0.51 | 0.11 | 3.19 | 1 | 655 | 55.8 | 16 | ○ | ○ | 1 |
| Embodiment 202 | 2.10 | 0.64 | 0.52 | 0.09 | 3.28 | 2 | 702 | 56.0 | 16 | ○ | ○ | 1 |
| Embodiment 203 | 1.81 | 0.56 | 0.49 | 0.11 | 3.23 | 3 | 670 | 61.2 | 19.5 | ○ | ○ | 1 |
| Embodiment 204 | 1.92 | 0.60 | 0.50 | 0.11 | 3.20 | 4 | 688 | 61.8 | 19 | ○ | ○ | 1 |
| Embodiment 205 | 2.30 | 0.72 | 0.51 | 0.11 | 3.19 | 3 | 718 | 58.7 | 19 | ○ | ○ | 2 |
| Embodiment 206 | 2.50 | 0.78 | 0.51 | 0.11 | 3.21 | 4 | 765 | 56.8 | 18 | ○ | ○ | 3 |
| Embodiment 207 | 1.50 | 0.47 | 0.52 | 0.09 | 3.19 | 2 | 668 | 57.2 | 16 | ○ | ○ | 1 |
| Embodiment 208 | 1.30 | 0.40 | 0.52 | 0.09 | 3.25 | 2 | 659 | 58.1 | 16 | ○ | ○ | 1 |
| Embodiment 209 | 1.80 | 0.50 | 0.50 | 0.06 | 3.60 | 2 | 675 | 57.0 | 17 | ○ | ○ | 1 |
| Embodiment 210 | 2.01 | 0.72 | 0.51 | 0.09 | 2.79 | 3 | 670 | 61.3 | 19 | ○ | ○ | 1 |
| Embodiment 211 | 2.03 | 0.61 | 1.00 | 0.11 | 3.33 | 4 | 667 | 63.1 | 19.5 | ○ | ○ | 1 |
| Embodiment 212 | 1.81 | 0.56 | 3.00 | 0.12 | 3.23 | 2 | 685 | 55.8 | 17 | ○ | ○ | 1 |
| Embodiment 213 | 2.03 | 0.60 | 0.49 | 0.15 | 3.38 | 4 | 685 | 61.5 | 19 | ○ | ○ | 1 |
| Embodiment 214 | 1.81 | 0.60 | 0.50 | 0.20 | 3.02 | 3 | 670 | 61.2 | 18 | ○ | ○ | 1 |
| Embodiment 215 | 2.03 | 0.65 | 0.51 | 0.11 | 3.12 | 2 | 675 | 56.8 | 15 | ○ | ○ | 3 |
| Embodiment 216 | 1.81 | 0.55 | 0.51 | 0.12 | 3.29 | 3 | 666 | 61.1 | 19.5 | ○ | ○ | 0.3 |
Table 6 (continuing)
| Numbering | Ni quality % | Ti quality % | Zn quality % | Mg quality % | The Ni/Ti ratio | The operation numbering | TS MPa | EC ％IACS | SR ％ | Bendability | Solder attachment | PPT ×10 12/mm 2 |
| Comparative example 217 | 3.31 | 1.03 | 0.50 | 0.08 | 3.21 | 2 | 715 | 49.1 | 21 | × | ○ | 4 |
| Comparative example 218 | 0.71 | 0.22 | 0.51 | 0.09 | 3.23 | 2 | 620 | 58.1 | 24 | ○ | ○ | 0.1 |
| Comparative example 219 | 2.01 | 0.37 | 0.48 | 0.09 | 5.43 | 3 | 655 | 51.3 | 27 | ○ | ○ | 1 |
| Comparative example 220 | 2.03 | 1.35 | 0.50 | 0.12 | 1.50 | 3 | 660 | 48.2 | 22 | ○ | ○ | 1 |
| Comparative example 221 | 1.81 | 0.52 | 0.00 | 0.12 | 3.48 | 2 | 665 | 58.6 | 20 | ○ | × | 1 |
| Comparative example 222 | 1.90 | 0.60 | 0.52 | 0.00 | 3.17 | 3 | 550 | 61.3 | 44 | ○ | ○ | 1 |
| Comparative example 223 | 1.91 | 0.62 | 0.55 | 0.01 | 3.08 | 2 | 565 | 56.3 | 38 | ○ | ○ | 1 |
| Comparative example 224 | 1.91 | 0.63 | 0.56 | 0.50 | 3.03 | 2 | 670 | 45.4 | 19 | × | ○ | 1 |
| Comparative example 225 | 1.95 | 0.66 | 0.51 | 0.10 | 2.95 | 3 | 621 | 43.1 | 27 | ○ | ○ | 0.0001 |
| Comparative example 226 | 2.01 | 0.60 | 0.52 | 0.13 | 3.35 | 4 | 670 | 56.8 | 22 | × | ○ | 100 |
| Comparative example 226-1 | 1.81 | 0.52 | 7.02 | 0.10 | 3.48 | 2 | 651 | 45.2 | 22 | ○ | ○ | 1 |
Table 7
| Numbering | Ni quality % | Ti quality % | Zn quality % | Mg quality % | Sn quality % | The Ni/Ti ratio | The operation numbering | TS MPa | EC ％IACS | SR ％ | Bendability | Solder attachment | PPT ×10 12/mm 2 |
| Embodiment 227 | 2.01 | 0.63 | 0.51 | 0.11 | 0.15 | 3.19 | 1 | 685 | 55.6 | 16 | ○ | ○ | 1 |
| Embodiment 228 | 2.10 | 0.64 | 0.52 | 0.09 | 0.2 | 3.28 | 2 | 693 | 56.4 | 16 | ○ | ○ | 1 |
| Embodiment 229 | 1.81 | 0.56 | 0.49 | 0.11 | 0.3 | 3.23 | 3 | 688 | 60.1 | 18 | ○ | ○ | 1 |
| Embodiment 230 | 1.92 | 0.60 | 0.50 | 0.11 | 0.12 | 3.20 | 4 | 690 | 59.6 | 19 | ○ | ○ | 1 |
| Embodiment 231 | 2.01 | 0.63 | 0.51 | 0.11 | 0.08 | 3.19 | 2 | 666 | 55.7 | 16 | ○ | ○ | 1 |
| Embodiment 232 | 2.10 | 0.64 | 0.52 | 0.09 | 0.09 | 3.28 | 2 | 710 | 55.9 | 16 | ○ | ○ | 1 |
| Embodiment 233 | 1.81 | 0.56 | 0.49 | 0.11 | 0.07 | 3.23 | 3 | 680 | 60.2 | 19 | ○ | ○ | 1 |
| Embodiment 234 | 1.92 | 0.60 | 0.50 | 0.11 | 0.08 | 3.20 | 4 | 695 | 61.1 | 19 | ○ | ○ | 1 |
| Embodiment 235 | 2.30 | 0.72 | 0.51 | 0.11 | 0.08 | 3.19 | 3 | 725 | 58.0 | 19 | ○ | ○ | 2 |
| Embodiment 236 | 2.50 | 0.78 | 0.51 | 0.11 | 0.09 | 3.21 | 4 | 770 | 56.1 | 18 | ○ | ○ | 3 |
| Embodiment 237 | 1.50 | 0.47 | 0.52 | 0.09 | 0.07 | 3.19 | 2 | 675 | 56.5 | 16 | ○ | ○ | 1 |
| Embodiment 238 | 1.30 | 0.40 | 0.52 | 0.09 | 0.08 | 3.25 | 2 | 670 | 58.0 | 16 | ○ | ○ | 1 |
| Embodiment 239 | 1.80 | 0.50 | 0.50 | 0.06 | 0.08 | 3.60 | 2 | 686 | 56.3 | 17 | ○ | ○ | 1 |
| Embodiment 240 | 2.01 | 0.72 | 0.51 | 0.09 | 0.09 | 2.79 | 3 | 682 | 60.5 | 19 | ○ | ○ | 1 |
| Embodiment 241 | 2.03 | 0.61 | 1.00 | 0.11 | 0.07 | 3.33 | 4 | 680 | 62.5 | 19.5 | ○ | ○ | 1 |
| Embodiment 242 | 1.81 | 0.56 | 3.00 | 0.12 | 0.08 | 3.23 | 2 | 693 | 55.6 | 17 | ○ | ○ | 1 |
| Embodiment 243 | 2.03 | 0.60 | 0.49 | 0.15 | 0.08 | 3.38 | 4 | 695 | 60.7 | 19 | ○ | ○ | 1 |
| Embodiment 244 | 1.81 | 0.60 | 0.50 | 0.20 | 0.09 | 3.02 | 3 | 681 | 60.6 | 19 | ○ | ○ | 1 |
| Embodiment 245 | 2.03 | 0.65 | 0.51 | 0.11 | 0.07 | 3.12 | 2 | 686 | 56.5 | 15 | ○ | ○ | 3 |
| Embodiment 246 | 1.81 | 0.55 | 0.51 | 0.12 | 0.08 | 3.29 | 3 | 678 | 60.3 | 19.5 | ○ | ○ | 0.3 |
Table 7 (continuing)
| Numbering | Ni quality % | Ti quality % | Zn quality % | Mg quality % | Sn quality % | The Ni/Ti ratio | The operation numbering | TS MPa | EC ％IACS | SR ％ | Bendability | Solder attachment | PPT ×10 12/mm 2 |
| Comparative example 247 | 3.31 | 1.03 | 0.50 | 0.08 | 0.09 | 3.21 | 2 | 715 | 49.1 | 22 | × | ○ | 4 |
| Comparative example 248 | 0.71 | 0.22 | 0.51 | 0.09 | 0.07 | 3.23 | 2 | 620 | 58.9 | 25 | ○ | ○ | 0.1 |
| Comparative example 249 | 2.01 | 0.37 | 0.48 | 0.09 | 0.08 | 5.43 | 3 | 655 | 50.5 | 28 | ○ | ○ | 1 |
| Comparative example 250 | 2.03 | 1.35 | 0.50 | 0.12 | 0.08 | 1.50 | 3 | 660 | 48.1 | 22 | ○ | ○ | 1 |
| Comparative example 251 | 1.81 | 0.52 | 0.00 | 0.12 | 0.09 | 3.48 | 2 | 665 | 59.1 | 20 | ○ | × | 1 |
| Comparative example 252 | 1.90 | 0.60 | 0.52 | 0.00 | 0.07 | 3.17 | 3 | 550 | 52.2 | 45 | ○ | ○ | 1 |
| Comparative example 253 | 1.91 | 0.62 | 0.55 | 0.01 | 0.08 | 3.08 | 2 | 565 | 50.9 | 38 | ○ | ○ | 1 |
| Comparative example 254 | 1.91 | 0.63 | 0.56 | 0.50 | 0.09 | 3.03 | 2 | 670 | 45.1 | 20 | × | ○ | 1 |
| Comparative example 255 | 1.95 | 0.66 | 0.51 | 0.10 | 0.07 | 2.95 | 3 | 621 | 47.8 | 27 | ○ | ○ | 0.0001 |
| Comparative example 256 | 2.01 | 0.60 | 0.52 | 0.13 | 0.08 | 3.35 | 4 | 670 | 56.1 | 22 | × | ○ | 100 |
| Comparative example 257 | 1.81 | 0.52 | 0.52 | 0.12 | 2 | 3.48 | 2 | 680 | 48.1 | 20 | ○ | ○ | 1 |
| Comparative example 258 | 1.90 | 0.60 | 0.52 | 0.12 | 1.51 | 3.17 | 3 | 675 | 40.2 | 20 | ○ | ○ | 1 |
| Comparative example 258-1 | 1.81 | 0.52 | 7.02 | 0.10 | 0.09 | 3.48 | 2 | 651 | 43.2 | 22 | ○ | ○ | 1 |
Table 8
| Numbering | Ni quality % | Ti quality % | Zn quality % | Mg quality % | Other quality % | The Ni/Ti ratio | The operation numbering | TS MPa | EC ％IACS | SR ％ | Bendability | Solder attachment | PPT ×10 12/mm 2 |
| Embodiment 259 | 1.82 | 0.59 | 0.52 | 0.08 | 0.05Zr | 3.08 | 2 | 692 | 56.8 | 18 | ○ | ○ | 1 |
| Embodiment 260 | 1.85 | 0.51 | 0.55 | 0.09 | 0.04Hf | 3.63 | 3 | 685 | 60.5 | 195 | ○ | ○ | 1 |
| Embodiment 261 | 1.79 | 0.53 | 0.52 | 0.12 | 0.05In | 3.38 | 4 | 680 | 62.2 | 19 | ○ | ○ | 1 |
| Embodiment 262 | 1.79 | 0.53 | 0.52 | 0.12 | 0.1Ag | 3.38 | 4 | 702 | 60.2 | 19 | ○ | ○ | 1 |
| Comparative example 263 | 1.82 | 0.59 | 0.52 | 0.08 | 1.02Zr | 3.08 | 2 | 675 | 46.2 | 20 | × | ○ | 1 |
| Comparative example 264 | 1.85 | 0.51 | 0.55 | 0.09 | 1.10Hf | 3.63 | 3 | 670 | 44.3 | 22 | × | ○ | 1 |
| Comparative example 265 | 1.79 | 0.53 | 0.52 | 0.12 | 1.20In | 3.38 | 4 | 676 | 38.9 | 21 | × | ○ | 1 |
| Comparative example 266 | 1.79 | 0.53 | 0.52 | 0.12 | 1.3Ag | 3.38 | 4 | 685 | 48.0 | 20 | × | ○ | 1 |
Table 9
| Numbering | Ni quality % | Ti quality % | Zn quality % | Mg quality % | Sn quality % | Other quality % | The Ni/Ti ratio | The operation numbering | TS MPa | EC ％IACS | SR ％ | Bendability | Solder attachment | PPT ×10 12/mm 2 |
| Embodiment 267 | 1.82 | 0.59 | 0.52 | 0.08 | 0.09 | 0.05Zr | 3.08 | 2 | 702 | 56.1 | 18 | ○ | ○ | 1 |
| Embodiment 268 | 1.85 | 0.51 | 0.55 | 0.09 | 0.07 | 0.04Hf | 3.63 | 3 | 693 | 59.5 | 19.5 | ○ | ○ | 1 |
| Embodiment 269 | 1.79 | 0.53 | 0.52 | 0.12 | 0.09 | 0.05In | 3.38 | 4 | 690 | 61.1 | 19 | ○ | ○ | 1 |
| Embodiment 270 | 1.79 | 0.53 | 0.52 | 0.12 | 0.09 | 0.1Ag | 3.38 | 4 | 705 | 59.5 | 19 | ○ | ○ | 1 |
| Comparative example 271 | 1.82 | 0.59 | 0.52 | 0.08 | 0.09 | 1.02Zr | 3.08 | 2 | 680 | 45.5 | 20 | × | ○ | 1 |
| Comparative example 272 | 1.85 | 0.51 | 0.55 | 0.09 | 0.07 | 1.10Hf | 3.63 | 3 | 675 | 42.5 | 22 | × | ○ | 1 |
| Comparative example 273 | 1.79 | 0.53 | 0.52 | 0.12 | 0.09 | 1.20In | 3.38 | 4 | 684 | 39.0 | 21 | × | ○ | 1 |
| Comparative example 274 | 1.79 | 0.53 | 0.52 | 0.12 | 0.09 | 1.3Ag | 3.38 | 4 | 692 | 45.3 | 20 | × | ○ | 1 |
Table 10
| Numbering | Ni quality % | Ti quality % | Zn quality % | Mg quality % | Sn quality % | The Ni/Ti ratio | The operation numbering | TS MPa | EC ％IACS | SR ％ | Bendability | Solder attachment | PPT ×10 12/mm 2 |
| Comparative example 275 | 2.01 | 0.63 | 0.51 | 0.11 | - | 3.19 | 5-1 | 556 | 65.1 | 28 | ○ | ○ | 0.0004 |
| Comparative example 276 | 1.81 | 0.56 | 0.49 | 0.11 | - | 3.23 | 5-2 | 540 | 66.0 | 27 | ○ | ○ | 0.0003 |
| Comparative example 277 | 1.81 | 0.56 | 0.49 | 0.11 | 0.08 | 3.23 | 5-3 | 570 | 65.1 | 29 | ○ | ○ | 0.0003 |
| Comparative example 278 | 2.01 | 0.63 | 0.51 | 0.11 | - | 3.19 | 6-1 | 535 | 44.2 | 30 | ○ | ○ | 0.0002 |
| Comparative example 279 | 1.81 | 0.56 | 0.49 | 0.11 | - | 3.23 | 6-3 | 542 | 42.5 | 32 | ○ | ○ | 0.0001 |
| Comparative example 280 | 1.81 | 0.56 | 0.49 | 0.11 | 0.08 | 3.23 | 6-2 | 551 | 41.8 | 30 | ○ | ○ | 0.0001 |
| Comparative example 281 | 2.01 | 0.63 | 0.51 | 0.11 | - | 3.19 | 7-4 | 575 | 66.2 | 28 | ○ | ○ | 0.0001 |
| Comparative example 282 | 1.81 | 0.56 | 0.49 | 0.11 | - | 3.23 | 7-3 | 545 | 68.1 | 29 | ○ | ○ | 0.0001 |
| Comparative example 283 | 1.81 | 0.56 | 0.49 | 0.11 | 0.08 | 3.23 | 7-2 | 560 | 65.1 | 28 | ○ | ○ | 0.0001 |
| Embodiment 201 | 2.01 | 0.63 | 0.51 | 0.11 | - | 3.19 | 1 | 655 | 55.8 | 16 | ○ | ○ | 1 |
| Embodiment 228 | 2.10 | 0.64 | 0.52 | 0.09 | 0.2 | 3.28 | 2 | 693 | 56.4 | 16 | ○ | ○ | 1 |
| Embodiment 229 | 1.81 | 0.56 | 0.49 | 0.11 | 0.3 | 3.23 | 3 | 688 | 60.1 | 18 | ○ | ○ | 1 |
| Embodiment 204 | 1.92 | 0.60 | 0.50 | 0.11 | - | 3.20 | 4 | 688 | 61.8 | 19 | ○ | ○ | 1 |
Can be clear and definite by table 6, it is more than the 650MPa that example 201～216 of the present invention all has tensile strength, and electric conductivity is 55%IACS, and stress relaxation rate is the excellent specific property below 20%.
In contrast, comparative example 217 needs high temperature, solution treatment for a long time because Ni, grain coarsening, and bendability is poor.Therefore in addition, the Ni quantitative change of solid solution is many, conducts electricity rate variance.
Therefore comparative example 218, can not obtain sufficient precipitation strength amount, so tensile strength is poor because the Ni amount is few.
Comparative example 219,220 is because the Ni/Ti ratio is different with the scope of the present invention's regulation, and therefore, the amount of the element of solid solution increases, poorly conductive.
Comparative example 221 is not owing to cooperate Zn, therefore, and the solder attachment deterioration.
Comparative example 222,223 is not owing to cooperating Mg or its amount too small, and the precipitate that contains Ni, Ti, Mg is few, so undercapacity, and the Mg solid solution capacity is also few, so the stress relaxation rate variance.
Comparative example 224 is because Mg is an excess quantity, and therefore, even carry out ageing treatment, superfluous Mg also can become the state of solid solution, and electric conductivity, bendability are all poor.
Comparative example 225 is because the density of precipitate is low, so intensity and stress relaxation rate variance.
Comparative example 226 is because therefore the density height of precipitate forms thick precipitate easily on crystal boundary, and bendability is poor.
Comparative example 226-1 is because the Zn addition is many, and therefore, superfluous Zn becomes the state of solid solution, and electric conductivity reduces.
In addition, above-mentioned comparative example 217～226 and 226～1 is the comparative example of the invention of above-mentioned (7) record.
Can be clear and definite by table 7, it is more than the 650MPa that example 227～246 of the present invention all has tensile strength, and electric conductivity is 55%IACS, and stress relaxation rate is the excellent specific property below 20%.
In contrast, comparative example 247 needs high temperature, solution treatment for a long time because Ni, grain coarsening, and bendability is poor.Therefore in addition, the Ni quantitative change of solid solution is many, conducts electricity rate variance.
Therefore comparative example 248, can not obtain sufficient precipitation strength amount, so tensile strength is poor because the Ni amount is few.
Comparative example 249,250 is because the Ni/Ti ratio is different with the scope of the present invention's regulation, and therefore, the amount of the element of solid solution increases, poorly conductive.
Comparative example 251 is not owing to cooperate Zn, therefore, and the solder attachment deterioration.
Comparative example 252,253 is not owing to cooperating Mg or its amount too small, and the precipitate that contains Ni, Ti, Mg is few, so undercapacity, and the Mg solid solution capacity is also few, so the stress relaxation rate variance.
Comparative example 254 is because Mg is an excess quantity, and therefore, even carry out ageing treatment, superfluous Mg also can become the state of solid solution, and electric conductivity, bendability are all poor.
Comparative example 255 is because the density of precipitate is low, so intensity and stress relaxation rate variance.
Comparative example 256 is because therefore the density height of precipitate forms thick precipitate easily on crystal boundary, and bendability is poor.
Comparative example 257,258 is because the amount of Sn is many, therefore conducts electricity rate variance.
Comparative example 258-1 is because the Zn addition is many, and therefore, superfluous Zn becomes the state of solid solution, and electric conductivity reduces.
In addition, above-mentioned comparative example 247～258 and 258～1 is the comparative example of the invention of above-mentioned (8) record.
Can be clear and definite by table 8, it is more than the 650MPa that example 259～262 of the present invention all has tensile strength, and electric conductivity is 55%IACS, and stress relaxation rate is the excellent specific property below 20%.
In contrast, comparative example 263 is because Zr is an excess quantity, and therefore, superfluous Zr can become the state of solid solution, and electric conductivity, bendability are all poor.
Comparative example 264 is because Hf is an excess quantity, and therefore, superfluous Hf can become the state of solid solution, and electric conductivity, bendability are all poor.
Comparative example 265 is because In is an excess quantity, and therefore, superfluous In can become the state of solid solution, and electric conductivity, bendability are all poor.
Comparative example 266 is because Ag is an excess quantity, and therefore, superfluous Ag can become the state of solid solution, and electric conductivity, bendability are all poor.
In addition, above-mentioned comparative example 263～266 is the comparative example of the invention of above-mentioned (9) record.
Can be clear and definite by table 9, it is more than the 650MPa that example 267～270 of the present invention all has tensile strength, and electric conductivity is 55%IACS, and stress relaxation rate is the excellent specific property below 20%.
In contrast, comparative example 271 is because Zr is an excess quantity, and therefore, superfluous Zr can become the state of solid solution, and electric conductivity, bendability are all poor.
Comparative example 272 is because Hf is an excess quantity, and therefore, superfluous Hf can become the state of solid solution, and electric conductivity, bendability are all poor.
Comparative example 273 is because In is an excess quantity, and therefore, superfluous In can become the state of solid solution, and electric conductivity, bendability are all poor.
Comparative example 274 is because Ag is an excess quantity, and therefore, superfluous Ag can become the state of solid solution, and electric conductivity, bendability are all poor.
In addition, above-mentioned comparative example 263～266 is the comparative example of the invention of above-mentioned (10) record.
Can be clear and definite by table 10, it is more than the 650MPa that example 201,228,229 of the present invention and 204 all has tensile strength, and electric conductivity is 55%IACS, and stress relaxation rate is the excellent specific property below 20%.
In contrast, comparative example 275～277 is because aging temp is too high, so the density step-down of precipitate, intensity and stress relaxation rate variance.
Comparative example 278～280 is low excessively owing to aging temp, and therefore, the amount of separating out is insufficient, and density is low, so, intensity, electric conductivity and stress relaxation rate variance.
Comparative example 281～283 is separated out thermal treatment owing to carry out timeliness with the electroconductibility more than the 35%IACS under the state before timeliness is separated out thermal treatment, and therefore, timeliness is separated out the density step-down of the precipitate after the thermal treatment, intensity and stress relaxation rate variance.
In addition, above-mentioned comparative example 275～283 is the comparative example of the invention of above-mentioned (11) record.
Industrial applicibility
Copper alloy of the present invention goes for junctors such as the junctor, terminal material of electric and electronic apparatus and element or terminal material etc.
Though the present invention has been described according to its embodiment, but as long as we do not specify, will be understood that then our invention is not limited to any detail section of explanation, under the spirit and scope situation of the invention shown in violation of a right does not require, should be interpreted as wide scope.
The application advocates to be willing to that based on the spy that on June 2nd, 2004 filed an application in Japan the spy who files an application in Japan in 2004-165068 and on June 1st, 2005 is willing to the right of priority of 2005-161475, these are all here as reference, and choose the part of its content as the content of this specification sheets.
Claims (11)
1. copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality %, 0.2 the Ti of～1.2 quality %, 0.02 the Mg of～0.2 quality % and any one or two kinds among the Zr, and the Zn of 0.1～1 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Mg, comprise Ni, the intermetallic compound of Ti and Zr, or comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Mg and Zr, and the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%.
2. the described copper alloy that is used for electric and electronic apparatus and element of claim 1, wherein, comprise the intermetallic compound of Ni, Ti and Mg, the median size that comprises the intermetallic compound of Ni, Ti and Zr or comprise the intermetallic compound of Ni, Ti, Mg and Zr is 5～100nm, distribution density is 1 * 10
10～10
13Individual/mm
2, and the crystallization particle diameter of parent phase is below the 10 μ m.
3. copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality %, 0.2 the Ti of～1.2 quality %, 0.02 the Sn of～0.2 quality % and any one or two kinds among the Si, and the Zn of 0.1～1 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Sn, comprise Ni, the intermetallic compound of Ti and Si, or comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Sn and Si, and the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%.
4. the described copper alloy that is used for electric and electronic apparatus and element of claim 3, wherein, comprise the intermetallic compound of Ni, Ti and Sn, the median size that comprises the intermetallic compound of Ni, Ti and Si or comprise the intermetallic compound of Ni, Ti, Sn and Si is 5～100nm, distribution density is 1 * 10
10～10
13Individual/mm
2, and the crystallization particle diameter of parent phase is below the 10 μ m.
5. manufacture method that is used for the copper alloy of electric and electronic apparatus and element, this method is to make the method for the copper alloy that is used for electric and electronic apparatus and element any in the claim 1～4, comprise following each operation: in the solution treatment of carrying out more than 850 ℃ below 35 seconds, be cooled to 300 ℃ with the speed of cooling more than 50 ℃/second from the temperature of this solution treatment, then, to surpass 0% and carry out cold rollingly in the rolling processing rate below 50%, carry out 5 hours with interior ageing treatment at 450～600 ℃.
6. manufacture method that is used for the copper alloy of electric and electronic apparatus and element, this method is to make the method for the copper alloy that is used for electric and electronic apparatus and element any in the claim 1～4, comprise following each operation: in the solution treatment of carrying out more than 850 ℃ below 35 seconds, be cooled to 300 ℃ with the speed of cooling more than 50 ℃/second from the temperature of this solution treatment, then carry out 5 hours with interior ageing treatment at 450～600 ℃.
7. copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality % and the Ti of 0.2～1.4 quality %, and the ratio of the quality percentage of above-mentioned Ni and Ti (Ni/Ti) is 2.2～4.7, and contain the Mg that adds up to 0.02～0.3 quality % and Zr one or both of, 0.1 the Zn of～5 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Mg, comprise Ni, the intermetallic compound of Ti and Zr, or comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Mg and Zr, and the distribution density of above-mentioned intermetallic compound is 1 * 10
9～1 * 10
13Individual/mm
2, tensile strength is more than the 650MPa and electric conductivity is more than the 55%IACS, the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%.
8. copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality % and the Ti of 0.2～1.4 quality %, and the ratio of the quality percentage of above-mentioned Ni and Ti (Ni/Ti) is 2.2～4.7, and contain the Mg that adds up to 0.02～0.3 quality % and Zr one or both of, 0.1 the Zn of～5 quality %, Sn is above 0% and below 0.5 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Mg, comprise Ni, the intermetallic compound of Ti and Zr, or comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Mg and Zr, and the distribution density of above-mentioned intermetallic compound is 1 * 10
9～1 * 10
13Individual/mm
2, tensile strength is more than 650 MPa and electric conductivity is more than the 55%IACS, the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%.
9. copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality %, 0.2 the Ti of～1.4 quality %, and the ratio of the quality percentage of above-mentioned Ni and Ti (Ni/Ti) is 2.2～4.7, and contain the Mg of 0.02～0.3 quality % and the Zn of 0.1～5 quality %, Zr, Hf, In, among the Ag any one or add up to more than two kinds surpasses 0% and below 1.0 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Mg, comprise Ni, the intermetallic compound of Ti and Zr, or comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Mg and Zr, and the distribution density of above-mentioned intermetallic compound is 1 * 10
9～1 * 10
13Individual/mm
2, tensile strength is more than the 650MPa and electric conductivity is more than the 55%IACS, the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%.
10. copper alloy that is used for electric and electronic apparatus and element, it contains the Ni of 1～3 quality % and the Ti of 0.2～1.4 quality %, and the ratio of the quality percentage of above-mentioned Ni and Ti (Ni/Ti) is 2.2～4.7, and contain the Mg of 0.02～0.3 quality % and the Zn of 0.1～5 quality %, Sn is above 0% and below 0.5 quality %, Zr, Hf, In, among the Ag any one or add up to more than two kinds surpasses 0% and below 1.0 quality %, surplus is Cu and unavoidable impurities, it is characterized in that, contain and comprise Ni, the intermetallic compound of Ti and Mg, comprise Ni, the intermetallic compound of Ti and Zr, or comprise Ni, Ti, at least a intermetallic compound in the intermetallic compound of Mg and Zr, and the distribution density of above-mentioned intermetallic compound is 1 * 10
9～1 * 10
13Individual/mm
2, tensile strength is more than 650 MPa and electric conductivity is more than the 55%IACS, the stress relaxation rate when keeping 1000 hours down for 150 ℃ is below 20%.
11. manufacture method that is used for the copper alloy of electric and electronic apparatus and element, this method is to make the method for the copper alloy that is used for electric and electronic apparatus and element any in the claim 7～10, it is characterized in that, comprise following operation: carrying out more than 1 time or 2 times separating out thermal treatment with the timeliness of interior time in 5 hours under 450～650 ℃ the temperature, in the state before this timeliness is separated out thermal treatment, has the following electroconductibility of 35%IACS.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP165068/2004 | 2004-06-02 | ||
| JP2004165068A JP4646192B2 (en) | 2004-06-02 | 2004-06-02 | Copper alloy material for electrical and electronic equipment and method for producing the same |
| JP161475/2005 | 2005-06-01 |
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| CN101014725A true CN101014725A (en) | 2007-08-08 |
| CN100471970C CN100471970C (en) | 2009-03-25 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101978562B (en) * | 2008-03-19 | 2013-04-03 | 古河电气工业株式会社 | Metallic material for connector and process for producing the metallic material for connector |
| CN104583430A (en) * | 2012-07-26 | 2015-04-29 | 三菱电机株式会社 | Copper alloy and production method thereof |
| CN111771241A (en) * | 2018-02-17 | 2020-10-13 | 株式会社Uacj | Aluminum alloy substrate for magnetic disk, method for producing same, and magnetic disk using same |
| CN115917023A (en) * | 2020-06-30 | 2023-04-04 | 三菱综合材料株式会社 | Copper alloy, copper alloy plastic working material, electronic/electrical component, terminal, and heat dissipating substrate |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006093140A1 (en) * | 2005-02-28 | 2006-09-08 | The Furukawa Electric Co., Ltd. | Copper alloy |
| JP2006265731A (en) * | 2005-02-28 | 2006-10-05 | Furukawa Electric Co Ltd:The | Copper alloy |
| JP2007169765A (en) * | 2005-12-26 | 2007-07-05 | Furukawa Electric Co Ltd:The | Copper alloy and its production method |
| KR101049655B1 (en) | 2006-05-26 | 2011-07-14 | 가부시키가이샤 고베 세이코쇼 | Copper alloy with high strength, high conductivity and bendability |
| JP4934493B2 (en) * | 2007-05-09 | 2012-05-16 | 古河電気工業株式会社 | Heat treatment method for aging precipitation type alloy strip |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS63219540A (en) * | 1987-03-09 | 1988-09-13 | Dowa Mining Co Ltd | High-strength copper alloy for terminal and connector and its production |
| JPH07258804A (en) * | 1994-03-23 | 1995-10-09 | Nikko Kinzoku Kk | Production of copper alloy for electronic equipment |
-
2004
- 2004-06-02 JP JP2004165068A patent/JP4646192B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101978562B (en) * | 2008-03-19 | 2013-04-03 | 古河电气工业株式会社 | Metallic material for connector and process for producing the metallic material for connector |
| CN104583430A (en) * | 2012-07-26 | 2015-04-29 | 三菱电机株式会社 | Copper alloy and production method thereof |
| US10002684B2 (en) | 2012-07-26 | 2018-06-19 | Ngk Insulators, Ltd. | Copper alloy and method for manufacturing the same |
| CN111771241A (en) * | 2018-02-17 | 2020-10-13 | 株式会社Uacj | Aluminum alloy substrate for magnetic disk, method for producing same, and magnetic disk using same |
| CN111771241B (en) * | 2018-02-17 | 2021-12-24 | 株式会社Uacj | Aluminum alloy substrate for magnetic disk, method for producing same, and magnetic disk using same |
| CN115917023A (en) * | 2020-06-30 | 2023-04-04 | 三菱综合材料株式会社 | Copper alloy, copper alloy plastic working material, electronic/electrical component, terminal, and heat dissipating substrate |
| CN115917023B (en) * | 2020-06-30 | 2024-04-12 | 三菱综合材料株式会社 | Copper alloy, copper alloy plastic working material, module for electronic and electrical equipment, terminal, and heat-dissipating substrate |
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| Publication number | Publication date |
|---|---|
| JP2005344163A (en) | 2005-12-15 |
| CN100471970C (en) | 2009-03-25 |
| JP4646192B2 (en) | 2011-03-09 |
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