CN101437969B

CN101437969B - Copper alloy having high strength, high electroconductivity and superior bend formability

Info

Publication number: CN101437969B
Application number: CN2007800165290A
Authority: CN
Inventors: 有贺康博; 畚野章; 工藤健; 梶原桂
Original assignee: Kobe Steel Ltd
Current assignee: Kobe Steel Ltd
Priority date: 2006-05-26
Filing date: 2007-05-23
Publication date: 2011-03-02
Anticipated expiration: 2027-05-23
Also published as: JP2007314847A; JP4006460B1; CN101437969A

Abstract

The present invention relates to a copper alloy having high strength, high electrical conductivity, and excellent bendability, the copper alloy containing, in terms of mass %, 0.4 to 4.0% ofNi; 0.05 to 1.0% of Si; and, as an element M, one member selected from 0.005 to 0.5% ofP, 0.005 to 1.0% of Cr, and 0.005 to 1.0% of Ti, with the remainder being copper and inevitable impurities, in which an atom number ratio M/Si of elements M and Si contained in a precipitate having a size of 50 to 200 nm in a microstructure of the copper alloy is from 0.01 to 10 on average, the atom number ratio being measured by a field emission transmission electron microscope with a magnification of 30,000 and an energy dispersive analyzer. According to the invention, it is possible to provide a copper alloy having high strength, high electrical conductivity, and excellent bendability.

Description

The copper alloy of high strength, high conductivity and has excellent bending properties

Technical field

The present invention relates to the good copper nisiloy of a kind of high strength, high conductivity and bendability is alloy, for example, relate to a kind of good copper alloy, it is as being used for household electrical appliances, semiconductor device with mechanism components such as electrical and electronic parts materials such as semiconductor devices such as lead frame, printed circuit board (PCB), shutter parts, bus, terminal connections post or the industry copper alloy lath with equipment etc.

Background technology

Along with to electronics miniaturization and light-weighted requirement, electrical and electronic parts is carrying out miniaturization and lightweight.And, for the miniaturization of this electrical and electronic parts and the miniaturization and the lightweight of lightweight and terminal component, for the Cu alloy material that is used for these parts, its thickness of slab and width also diminish, in IC, also using thickness of slab is the thin copper alloy of 0.1～0.15mm.

Consequently, the Cu alloy material that is used for these electrical and electronic parts requires higher intensity.For example, automobile requires high strength copper alloy plate more than the 800MPa with terminal stud etc.

In addition, the tendency of the described thin plateization of electrical and electronic parts and change in a narrow margin makes the electroconductibility sectional area partly of Cu alloy material reduce.In order to compensate the decline of the electroconductibility that reduces to cause because of this sectional area, require Cu alloy material self to have the above favorable conductive rate of electric conductivity 40%IACS.

In addition, the copper alloy that is used for these terminal studs, terminal, switch, rly., lead frame etc. requires above-mentioned high strength and high conductivity mostly, and this is from needless to say, but also requires the strict bendabilities such as 90 ° of bendings behind the fluting.

At present, as high-intensity Cu alloy material, known have 42 alloys (Fe-42% quality Ni alloy).This 42 alloy has the tensile strength of about 580MPa size, and nonuniformity is also little, and bendability is also good.But this 42 alloy can not satisfy the requirement of the above high strength of 800MPa.In addition, because this 42 alloy contains a large amount of Ni, so also there is the price problem of higher.

Therefore, the above-mentioned good and cheap Corson alloy (Cu-Ni-Si is an alloy) of various characteristics is used to electrical and electronic parts usefulness.This Corson alloy is nickel silicide compound (Ni ₂Si) with respect to the alloy of the solid solution of copper limit with the temperature considerable change, for by Q-tempering hardened precipitation hardening type alloy, thermotolerance and hot strength are all good, up to the present, also be widely used in conduction with various springs or high tensile power with electric wire etc.

But concerning this Corson alloy, when improving the intensity of Cu alloy material, electroconductibility and bendability also reduce.That is, for high-intensity Corson alloy, forming good electrical conductivity and bendability is very difficult problem, so seek further to improve intensity, electroconductibility and bendability.

At present, motion a kind of method that improves this Corson alloy intensity, electroconductibility and bendability.For example, according to patent documentation 1, Ni, Si have not only been stipulated, also define Sn, Nn, Fe, P, Mg, Pb amount etc., and not only keeping electroconductibility, also keep the separability of anti-scolding tin, heat-resistant creep characteristic, anti-migration spy, the hot workability of bend, simultaneously, improve intensity and punching processing.

According to patent documentation 2, not only stipulate Ni, Si, but also regulation Mg amount and be present in the precipitate in the alloy and the particle diameter that is situated between in thing is the number of the per unit area more than the 10 μ m improves electric conductivity, intensity and hot strength.

According to patent documentation 3, not only contain Ni, Si, also contain Mg, limit the content of S simultaneously, improve proper intensity, electric conductivity, bendability, stress buffer characteristic, coating stopping property.

According to patent documentation 4, restriction Fe amount is below 0.1%, and intensity, electric conductivity and bendability are improved.

According to patent documentation 5, Jie is below the 10 μ m in the size of thing, and Jie who limits 5～10 μ m sizes makes intensity, electric conductivity, bendability, erosion resistance, plating raising in the thing number.

According to patent documentation 6, control Ni ₂The dispersion state of Si precipitate improves intensity, electric conductivity, bendability.

According to patent documentation 7, the crystalline extension shape by regulation copper coin surface structure has improved wear resistant.

Patent documentation 1:(Japan) spy opens flat 9-No. 209061 communiques

Patent documentation 2:(Japan) spy opens flat 8-No. 225869 communiques

Patent documentation 3:(Japan) spy opens communique 2002-No. 180161

Patent documentation 4:(Japan) spy opens communique 2001-No. 207229

Patent documentation 5:(Japan) spy opens communique 2001-No. 49369

Patent documentation 6:(Japan) spy opens communique 2005-No. 89843

Patent documentation 5:(Japan) spy opens flat 5-No. 279825 communiques

But, in the patent documentation 1, only each component content of Corson alloy is stipulated, only be controlled to and be grouped into, can not get full intensity, and also can not get full intensity in the reality.

In the patent documentation 2, paying close attention to the copper nisiloy is alloy organizing, though stipulated that existing precipitate and Jie in size, the number of thing, do not further investigate tissue, does not also stipulate the solutionizing operation, so can not get full intensity.

In the patent documentation 3, electric conductivity is low, does not reach requirement and (is 29～33%LACS) among the embodiment, in addition, makes S be reduced to the amount of regulation, may cause the increase of manufacturing cost, and impracticable.

Shown in patent documentation 4, only Fe is limited in below 0.1%, can not get sufficient electric conductivity, intensity and bendability.

In the patent documentation 5, pay close attention to the tissue of Corson alloy,, tissue is not furtherd investigate though stipulated size, the number of the existing thing that is situated between, also insufficient to the control of solutionizing operation in addition, so can not get full intensity.

In the patent documentation 6, pay close attention to the tissue of Corson alloy, make projection electron microscope tissues observed by 1,000,000 times, nickel silicide precipitate (Ni ₂Si) median size is 3～10nm, establishes to be spaced apart below the 25nm dispersion state of control precipitate simultaneously.But, be that the content of Ni, Si is too much basically, therefore, electric conductivity is insufficient.

In the patent documentation 7, though stipulated the extension shape of the crystal grain of copper coin surface structure, only the shape by crystal grain can not get full intensity, and also insufficient to the control of solutionizing operation, so electric conductivity is insufficient.

Summary of the invention

The present invention develops for solving such problem, and it provides a kind of copper nisiloy series copper alloy, and this alloy is high strength, high conductivity, and has both the alloy of good bendability.

That is, the present invention relates to following (1)～(9).

(1) contains Ni:0.4～4.0%, Si:0.05～1.0% in quality %, in addition,, contain and be selected from as element M

P：0.005～0.5％、

Cr：0.005～1.0％、

A kind of element in Ti:0.005～1.0%,

Surplus is made up of copper and unavoidable impurities, wherein,

Element M that contains in electric field emission type transmission electron microscope this copper alloy tissue, by 30000 times of multiplying powers and the energy dispersion type analytical equipment precipitate that determine, 50～200nm size and the atomicity of Si are than M/Si average out to 0.01～10.

(2) as the copper alloy (below, be also referred to as first mode of the present invention) of (1) record, it is characterized in that,

Described element M is P,

0.2～7.0/μ of number density average out to m described copper alloy tissue, by described electric field emission type transmission electron microscope and energy dispersion type analytical equipment precipitate that determine, 50～200nm size ²The average atom concentration of the P that contains in the precipitate of this scope size is 0.1～50at%, simultaneously, at the number of establishing by loaded the crystal grain that the backscattering electron diffraction determines as the crystal orientation method of analysis of system at the electric field emission type transmission electron microscope is n, if when the crystal grain that determines separately directly is x, directly be below the 10 μ m with the average crystal grain that (∑ x)/n represents.

(3) as the copper alloy of (2) record, it is in quality %, also contains to add up among 0.01～3.0% Cr, Ti, Fe, Mg, Co, the Zr one or more.

(4) as the copper alloy of (1) record, it is characterized in that,

Described element M is Cr,

0.2～20/μ of number density average out to m described copper alloy tissue, by described electric field emission type transmission electron microscope and energy dispersion type analytical equipment precipitate that determine, 50～200nm size ²The average atom concentration of the Cr that contains in the precipitate of this scope size is 0.1～80at%, simultaneously, at the number of establishing by loaded the crystal grain that the backscattering electron diffraction determines as the crystal orientation method of analysis of system in the electric field emission type scanning electronic microscope is n, when if the crystal grain that determines separately directly is x, with the average crystal grain that (∑ x)/n represents directly is 30 μ m following (below, be also referred to as second mode of the present invention).

(5) as the copper alloy of (4) record, it is in quality %, also contains to add up among 0.01～3.0% Ti, Fe, Mg, Co, the Zr one or more.

(6) as the copper alloy of (1) record, it is characterized in that,

Described element M is Ti,

0.2～20/μ of number density average out to m described copper alloy tissue, by described electric field emission type transmission electron microscope and energy dispersion type analytical equipment precipitate that determine, 50～200nm size ²The average atom concentration of the Cr that contains in the precipitate of this scope size is 0.1～50at%, simultaneously, at the number of establishing by loaded the crystal grain that the backscattering electron diffraction determines as the crystal orientation method of analysis of system in the electric field emission type scanning electronic microscope is n, when if the crystal grain that determines separately directly is x, with the average crystal grain that (∑ x)/n represents directly is 20 μ m following (below, be also referred to as second mode of the present invention).

(7) as the copper alloy of copper alloy of (6) record, it is in quality %, also contains to add up to 0.01～3.0% Fe, Mg, among Co, the Zr one or more.

(8) as each described copper alloy of (1)～(7), it also contains Zn:0.005～3.0% in quality %.

(9) as each described copper alloy of (1)～(8), it also contains Sn:0.01～5.0% in quality %.

In first mode of the present invention, the average crystal grain footpath miniaturization that makes copper nisiloy series copper alloy tissue improves the bendability of copper alloy below 10 μ m.And, it is characterized by, the effect of embolization that the crystal grain-growth that contains P precipitate (below, be also referred to as phosphide, phosphorus compound) by Ni-Si-P, Fe-P, Fe-Ni-P, Ni-Si-Fe-P etc. suppresses is realized this crystal grain miniaturization in the tissue.

Present inventors have found the crystal grain-growth of the described P of containing precipitate effect of embolization that suppresses and the common Ni that does not contain P ₂Si is that the effect of embolization of precipitate is compared obviously greatly.And, found that also the size of this effect of embolization is contained about the content of the P of P precipitate (atomic percent) simultaneously.

In other words, make average crystal grain footpath miniaturization 10 in the in fact present copper nisiloy series copper alloy tissue

Be difficult below the μ m, it is owing to only do not contain the common Ni of P that this reason is speculated as ₂Si is that its effect of embolization of precipitate has big boundary.

At this, as alloying constituent, even contain P, the precipitate that is present in the copper alloy tissue is not all to be to contain the P precipitate yet.That is, in the copper alloy tissue of reality, except that containing the P precipitate, also be mixed with other the Ni that does not contain P ₂Precipitates such as Si system.In other words, be mixed with effect of embolization that crystal grain-growth suppresses big contain effect of embolization that P precipitate and crystal grain-growth suppress other Ni little, that do not contain P ₂Precipitates such as Si system.

Therefore, the effect of embolization of actual crystal grain-growth inhibition exists with ... the amount that contains the P precipitate of copper alloy tissue.In other words, for the average crystal grain footpath miniaturization that makes the copper alloy tissue below 10 μ m, a certain amount of above P precipitate that contains is present in the copper alloy tissue.

About this point, the present invention does not directly limit the amount that contains the P precipitate that is present in the copper alloy tissue, but (atomic percent of the P in whole precipitates of 50～200nm) is controlled the amount that contains the P precipitate by being present in described specific dimensions in the copper alloy tissue.This be because, only select and contain the P precipitate and analyze, measure containing the P precipitate and do not contain among other the precipitate of P from be blended in the copper alloy tissue, efficient is low and measure incorrect.

Therefore, the present invention is an object with whole precipitates (no matter whether containing whole precipitates of P) of these specific dimensions, measures the atomic percent of P, according to the average atom concentration of the P in this precipitate, and the amount that contains the P precipitate in the control copper alloy tissue.In addition, as this prerequisite, the present invention guarantees the number density of whole precipitates (compound) of (qualification) described specific dimensions.

Thus, the present invention brings into play the big effect of embolization that crystal grain-growth suppresses, and the average crystal grain footpath miniaturization that makes copper nisiloy series copper alloy tissue is below 10 μ m, thus the bendability of raising copper alloy.

To the assurance of the number density of these specific dimensions precipitates (compound) with to the control of the average atom concentration of P in the precipitate, as prerequisite, the speed of cooling after heat-up rate in the time of can handling by content in the scope of the invention such as control P and control solutionizing and solutionizing are handled realizes.And, if the average atom concentration of the P that contains in this precipitate is not controlled (control contains P precipitate amount), just be difficult to the average crystal grain of copper nisiloy series copper alloy tissue directly miniaturization below 10 μ m.

In addition, the present invention is in order to keep high electric conductivity, and the content of Ni, Si that is controlled to be the basic alloy composition is lower.And, make the described P of containing precipitate or contain Ni ₂The precipitate of other of Si is fine separates out, and improves intensity.Even, also become high strength so the content of control Ni, Si is lower.

Second mode of the present invention is characterised in that, even what contain in the copper nisiloy series copper alloy tissue contains its solution treatment temp high temperatureization of Cr precipitate, can not carry out solid solution yet, but exist (remaining) in tissue, and utilize the special character of the effect of embolization of performance crystal grain-growth inhibition as precipitate.

That is, containing under the situation of Cr, in copper nisiloy series copper alloy tissue, forming Ni-Si-Cr, Si-Cr etc. and contain Cr precipitate (may also be referred to as Crization thing, Cr compound).Have its solution treatment temp and for example reach high temperature about 900 ℃ even these contain the Cr precipitate, also do not carry out solid solution, but exist (remaining) in tissue as precipitate, and the special character of the effect of embolization that suppresses of performance crystal grain-growth.And, this crystal grain-growth that contains the Cr precipitate suppress effect of embolization with do not contain Cr so that contain the Cr precipitate, be common (present) Ni ₂Si is that the effect of embolization of precipitate is compared, and is obviously big.

Certainly, because the high temperatureization of solution treatment temp contains the also solid solution to a certain extent of Cr precipitate, self can not avoid the growth of crystal grain.But, if compare, then suppressing the degree strictness of its crystal grain-growth with the crystal grain that does not contain Cr and even contain common (at present) of Cr precipitate, average crystal grain directly is the following degree of described 30 μ m.Therefore, can realize the high temperatureization very of solution treatment temp, can increase considerably the solid solution capacity of Ni, Si, in the age hardening of back is handled, can increase considerably the fine precipitate amount of Ni-Si.Consequently, thickization in average crystal grain footpath can not make reductions such as bendability, can realize the more high strength of copper alloy.

This size that contains the effect of embolization of Cr precipitate also is subjected to contain greatly about the content (atomic percent) of the Cr in the Cr precipitate.In other words, it is difficult in fact making average crystal grain footpath miniaturization in present copper nisiloy series copper alloy tissue.It is owing to do not contain the common Ni of Cr that its reason is speculated as ₂Si is the cause that precipitate has the big boundary of effect of embolization.

At this, even contain Cr as alloy, the precipitate that is present in the copper alloy tissue is not all to be to contain the Cr precipitate yet.That is, in the copper alloy tissue of reality, except that containing the Cr precipitate, also be mixed with other the Ni that does not contain Cr ₂Precipitates such as Si system.In other words, be mixed with effect of embolization that crystal grain-growth suppresses big contain effect of embolization that Cr precipitate and crystal grain-growth suppress other Ni little, that do not contain Cr ₂Precipitates such as system are separated out by Si system.

Therefore, the effect of embolization of actual crystal grain-growth inhibition exists with ... the amount that contains the Cr precipitate of copper alloy tissue.In other words, for the average crystal grain footpath miniaturization that makes the copper alloy tissue below 10 μ m, a certain amount of above Cr precipitate that contains is present in the copper alloy tissue.

About this point, the present invention does not directly limit the amount that contains the Cr precipitate that is present in the copper alloy tissue, but by be present in the copper alloy tissue described specific dimensions (atomic percent of the Cr in whole precipitates of 50～200nm) is controlled the amount that contains the Cr precipitate.This be because, only select and contain the Cr precipitate and analyze, measure containing the Cr precipitate and do not contain among other precipitates of Cr from be blended in the copper alloy tissue, efficient is low and measure incorrect.

Therefore, the present invention is an object with whole precipitates (no matter whether containing whole precipitates of Cr) of these specific dimensions, measure the atomic percent of Cr,, the amount that contains the Cr precipitate in the copper alloy tissue is controlled according to the average atom concentration of the Cr in this precipitate.In addition, as this prerequisite, the present invention guarantees the number density of whole precipitates (compound) of (qualification) described specific dimensions.

Thus, among the present invention, the big effect of embolization that the performance crystal grain-growth suppresses, the average crystal grain footpath miniaturization that makes copper nisiloy series copper alloy tissue improves the bendability of copper alloy below 30 μ m.

To the assurance of the number density of the precipitate (compound) of these specific dimensions with to the control of the average atom concentration of the Cr in the precipitate, as prerequisite, the speed of cooling after heat-up rate during by content in the scope of the invention such as control Cr and the processing of control solution and solution are handled realizes.And, if the average atom concentration of the Cr that contains in this precipitate is not controlled (containing the control of Cr precipitate amount), just be difficult to make the average crystal grain footpath miniaturization of copper nisiloy series copper alloy tissue below 30 μ m, particularly below the 10 μ m.

In addition, the present invention is in order to keep high electric conductivity, and the content of Ni, Si that is controlled to be the basic alloy composition is lower.And, make the described Cr of containing precipitate or contain Ni ₂The precipitate of other of Si is fine separates out, and improves intensity.Even, also become high strength so the content of control Ni, Si is lower.

Third Way of the present invention is characterised in that, contain in the copper nisiloy series copper alloy tissue even to contain its solution treatment temp of Ti precipitate be high temperatureization, can not carry out solid solution yet, but exist (remaining) in tissue, and utilize the special character of the effect of embolization of its performance crystal grain-growth inhibition as precipitate.

That is, containing under the situation of Ti, in copper nisiloy series copper alloy tissue, forming Ni-Si-Ti etc. and contain Ti precipitate (may also be referred to as Tiization thing, Ti compound).Have its solution treatment temp and for example reach high temperature about 900 ℃ even these contain the Ti precipitate, also can not carry out solid solution, but exist (remaining) in tissue as precipitate, and the special character of the effect of embolization that suppresses of performance crystal grain-growth.And, the effect of embolization that this crystal grain-growth that contains the Ti precipitate suppresses with do not contain Ti so that contain the Ti precipitate, be common (present) Ni ₂Si is that the effect of embolization of precipitate is compared, and is obviously big.

Certainly, because the high temperatureization of solution treatment temp contains the Ti precipitate and also carries out solid solution to a certain extent, self can not avoid the growth of crystal grain.But, compare with the crystal grain that does not contain Ti and even contain common (at present) of Ti precipitate, then suppress the degree strictness of its crystal grain-growth, average crystal grain directly is the following degree of described 30 μ m.Therefore, can realize the high temperatureization very of solution treatment temp, can increase considerably the solid solution capacity of Ni, Si, in the age hardening of back is handled, can increase considerably the fine precipitate amount of Ni-Si.Consequently, thickization in average crystal grain footpath can not make reductions such as bendability, can realize the more high strength of copper alloy.

This size that contains the effect of embolization of Ti precipitate also receives greatly to contain about the content (atomic percent) of the Ti in the Ti precipitate.In other words, in fact in present copper nisiloy series copper alloy tissue, make the reason of average crystal grain footpath miniaturization difficulty, supposition is owing to do not contain the common Ni of Ti ₂Si is the cause that precipitate has the big boundary of effect of embolization.

At this, as alloy, even contain Ti, the precipitate that is present in the copper alloy tissue is not all to be to contain the Ti precipitate yet.That is, in the copper alloy tissue of reality, except that containing the Ti precipitate, also be mixed with other the Ni that does not contain Ti ₂Precipitates such as Si system.In other words, be mixed with effect of embolization that crystal grain-growth suppresses big contain effect of embolization that Ti precipitate and crystal grain-growth suppress other Ni little, that do not contain Ti ₂Precipitates such as Si system.

Therefore, the effect of embolization of actual crystal grain-growth inhibition exists with ... the amount that contains the Ti precipitate of copper alloy tissue.In other words, for the average crystal grain footpath miniaturization that makes the copper alloy tissue below 20 μ m, a certain amount of above Ti precipitate that contains is present in the copper alloy tissue.

About this point, the present invention does not directly limit the amount that contains the Ti precipitate that is present in the copper alloy tissue, but (atomic percent of the Ti in whole precipitates of 50～200nm) comes the amount that contains the Ti precipitate is controlled according to being present in described specific dimensions in the copper alloy tissue.This be because, only select and contain the Ti precipitate and analyze, measure containing the Ti precipitate and do not contain among other precipitates of Ti from be blended in the copper alloy tissue, efficient is low and measure incorrect.

Therefore, the present invention is an object with whole precipitates (no matter whether containing whole precipitates of Ti) of these specific dimensions, measure the atomic percent of Ti,, the amount that contains the Ti precipitate in the copper alloy tissue is controlled by the average atom concentration of the Ti in this precipitate.In addition, as this prerequisite, the present invention guarantees the number density of whole precipitates (compound) of (qualification) described specific dimensions.

Thus, among the present invention, the big effect of embolization that the performance crystal grain-growth suppresses, and the average crystal grain footpath miniaturization that makes copper nisiloy series copper alloy tissue improves the bendability of copper alloy below 20 μ m.

To the assurance of the number density of the precipitate (compound) of these specific dimensions with to the control of the average atom concentration of the Ti in the precipitate, as prerequisite, the speed of cooling after heat-up rate during by content in the scope of the invention such as control Ti and the processing of control solution and solution are handled realizes.And, if the average atom concentration of the Ti that contains is not controlled (containing the control of Ti precipitate amount) in this precipitate, just be difficult to make the average crystal grain footpath miniaturization of copper nisiloy series copper alloy tissue below 20 μ m, below the 10 μ m especially.

In addition, among the present invention, in order to keep high electric conductivity, the content of Ni, Si that is controlled to be the basic alloy composition is lower.And, make the described Ti of containing precipitate or contain Ni ₂The precipitate of other of Si is fine separates out, and improves intensity.Even, also become high strength so the content of control Ni, Si is lower.

Thus, the present invention obtains an Albatra metal-, and this copper alloy possesses high strength, high conductivity and good bendability well-balancedly.

Description of drawings

Fig. 1 is that the drawing of expression copper alloy plate tissue of the present invention substitutes the TEM photo;

Fig. 2 is that the drawing of expression copper alloy plate tissue of the present invention substitutes the TEM photo;

Fig. 3 is that the drawing of expression copper alloy plate tissue of the present invention substitutes the TEM photo;

Fig. 4 is that the drawing of expression comparative example copper alloy plate tissue substitutes the TEM photo;

Embodiment

The invention provides an Albatra metal-, it is the copper alloy of high strength, high conductivity and has excellent bending properties, contains Ni:0.4～4.0%, Si:0.05～1.0% in quality %, in addition, as element M, contains and is selected from

P：0.005～0.5％、

Cr：0.005～1.0％、

A kind of element in Ti:0.005～1.0%,

Surplus is made up of copper and unavoidable impurities,

Element M that contains in field emission projection electron microscope this copper alloy tissue, by 30000 times of multiplying powers and the energy dispersion type analytical equipment precipitate that determine, 50～200nm size and the atomicity of Si are than M/Si average out to 0.01～10.

Below, in this manual, M represents to be selected from a kind of element among P, Cr and the Ti.

(M that contains in the precipitate and the atomicity of Si ratio)

The present invention is for the miniaturization in the crystal grain footpath that guarantees copper alloy, and preferably the atomicity of element M that contains in the above-mentioned electric field emission type transmission electron microscope of the alloy structure by 30000 times of multiplying powers and the energy dispersion type analytical equipment precipitate that determine, 50～200nm size and Si is than M/Si average out to 0.01～10.

When the atomicity of element M that contains in the precipitate and Si average less than 0.01 the time than M/Si, thickization of crystal grain, the possibility that bendability descends increases.On the other hand, when the atomicity of element M that contains in the precipitate and Si than M/Si average out to greater than 10 the time, solid solution Si amount too much, the possibility that electric conductivity descends increases.Therefore, element M that contains in the preferred precipitate and the atomicity of Si be than M/Si average out to 0.01～10, and more preferably 0.10～5.0.

Below, best mode of the present invention is elaborated.

At first, first mode one of optimal way of the present invention, of the present invention is described.

(one-tenth of copper alloy is grouped into)

As above-mentioned various uses, at first satisfy necessary intensity or electric conductivity to being used to, the copper nisiloy that also has first mode of the present invention of high bendability or proof stress damping characteristics is that the chemical ingredients of alloy is formed, and describes following.

In order to realize high strength, high conductivity, also has high bendability, first mode of the present invention is in quality %, for containing Ni:0.4～4.0%, Si:0.05～1.0% respectively, the copper alloy that P:0.005～0.5%, surplus are made up of copper and unavoidable impurities and the essentially consist formed.This consists of the crystal grain miniaturization that is used to make the copper alloy tissue, and control precipitate (Ni ₂Si) the average atom concentration of the P that contains in, be grouped into the important precondition that the aspect is considered from one-tenth.In addition, the % that puts down in writing in explanation of following each element is total mass %.

With respect to this essentially consist, can also contain and add up among 0.01～3.0% Cr, Ti, Fe, Mg, Co, the Zr one or more.In addition, also can contain Zn:0.005～3.0%.In addition, also can contain Sn:0.01～5.0%.

Ni：0.4～4.0％。

Ni has by crystallization to go out or separate out compound (Ni with Si ₂Si etc.), guarantee the effect of the intensity and the electric conductivity of copper alloy.In addition, also form compound with P.When the very few less than 0.4% of the content of Ni, because the growing amount of knot crystallization-precipitate is insufficient, thus not only can not get desirable intensity, but also make thickization of crystal grain of copper alloy tissue.In addition, the ratio that the crystalline substance that segregation easily takes place goes out thing uprises, and the deviation of end article characteristic increases.On the other hand, when the content of Ni surpasses 4.0% and too much the time, not only electric conductivity descends, and the precipitate number density is excessive, bendability descends.Therefore, establishing Ni amount is 0.4～4.0% scope.

Si：0.05～1.0％

Compound (the Ni with Ni is separated out in the Si crystallization ₂Si etc.), improve the intensity and the electric conductivity of copper alloy.In addition, also form compound with P.Under the situation of the very few less than 0.05% of the content of Si, because the generation of crystallization-precipitate is insufficient, thus not only can not get desirable intensity, but also make thickization of crystal grain.In addition, the ratio that the crystalline substance that segregation easily takes place goes out thing uprises, thereby strengthens the deviation of end article characteristic.On the other hand, when the content of Si surpasses 1.0% and too much the time, the number of precipitate is too much, bendability descends, and the atomicity of P that contains in the precipitate and Si is lower excessively than number P/Si simultaneously.Therefore, establishing Si content is 0.05～1.0% scope.

P：0.005～0.5％

P contains the P precipitate for being used for generating, and the P atomic percent that will contain in the P precipitate is controlled at the interior important element of above-mentioned specified range.Contain P precipitate (phosphide, phosphorus compound) by formation, improve intensity, electric conductivity, the formation by phosphide simultaneously makes the crystal grain miniaturization, improves bendability.But, within these effects, especially bendability improves effect and brings into play at above-mentioned specified range by the P atomic percent that control contains the P precipitate.

Under the situation of the very few less than 0.005% of P content, can not effectively bring into play these effects, effect.On the other hand, surpass 0.5% and too much the time, the precipitate chap is big, is unfavorable for bendability, and the atomic percent of the P that contains in the precipitate is too high when P content.Therefore the content of establishing P is 0.005～0.5% scope.

At this, the said P of containing precipitate is meant that Ni-Si-P's in Ni-Si-P essentially consist contains the P precipitate among so-called the present invention.When in this essentially consist, containing Fe or Mg etc., with Ni-Si-P contain the P precipitate, or replace its generation (Fe, Mg)-P, (Fe, Mg)-Ni-P, Ni-Si-(Fe, Mg)-P etc. to contain the P precipitate.In addition, when containing Cr, Ti, Co, Zr etc., these Fe or Mg etc. partly generate a part in addition all metathetical contain the P precipitate.

Cr, Ti, Fe, Mg, Co, Zr: add up to 0.01～3.0%

As mentioned above, these elements improve intensity, electric conductivity by forming phosphide, also have the effect that makes the crystal grain miniaturization simultaneously.Under the situation of these effects of performance, selectivity contains one or more among the Cr, the Ti that add up to more than 0.01%, Fe, Mg, Co, the Zr.But when the total content (total amount) of these elements surpassed 3.0%, the precipitate chap was big, is unfavorable for bendability, and the atomic percent of the P that contains in the precipitate is low excessively.Therefore, establishing content that selectivity contains Cr, Ti under there is something special, Fe, Mg, Co, Zr, to add up to (total amount) be 0.01～3.0% scope.

Zn：0.005～3.0％

Zn be to improvement be used for Sn coating that electronic product engages or scolding tin heat-resisting separability, suppress hot soarfing from effective elements.Effectively bringing into play under the situation of such effect, selectivity contains more than 0.005%.But,, cause the wetting expansion deterioration that dissolves Sn or scolding tin on the contrary when surpassing 3.0% and surplus contains sometimes.In addition, when content increased, electric conductivity also descended significantly.Therefore, considering that heat-resisting separability improves on the basis of effect and electric conductivity decline effect, selectivity contains Zn, establishes Zn content under this situation and be 0.005～3.0% scope, is preferably 0.005～1.5% scope.

Sn：0.01～5.0％

The Sn solid solution helps intensity and improves in copper alloy.Effectively bringing into play under the situation of such effect, selectivity contains more than 0.01%.But when surpassing 5.0% and surplus contains sometimes, its effect is saturated.In addition, when content increases, electric conductivity will be descended significantly.Therefore, considering that intensity improves on the basis of effect and electric conductivity decline effect, selectivity contains Sn, establishes Sn content under this situation and be 0.01～5.0% scope, is preferably 0.01～1.0% scope.

The content of other elements

Other elements are essentially impurity, and are preferably few as much as possible.For example impurity elements such as Al, Be, V, Mo, W generate thick crystallization precipitate easily, and bendability is worsened, and cause the decline of electric conductivity easily.Therefore, preferably these element total amounts are few content below 0.5%.In addition, B, C, Na, S, Ca, As, Se, Cd, In, Sb, Bi, the MM elements such as (noriums) that trace also contains in the copper alloy also causes the decline of electric conductivity easily, therefore it is desirable to, the total amount of these elements is suppressed to few content below 0.1%.But, in order to reduce these elements, give birth to manufacturing costs such as gold use or refinement and rise, in order to suppress the rising of manufacturing cost, allow the total amount of these elements to contain to the above-mentioned separately upper limit.

(copper alloy tissue)

The present invention is that alloy structure is a prerequisite with above-mentioned Cu-Ni-Si-P, designs the tissue of this copper alloy, makes average crystal grain footpath miniaturization below 10 μ m, improves the bendability of copper alloy.

And, realize this tissue design by control (control contains the amount of P precipitate) to the average atom concentration that is present in the P that contains in the precipitate in the copper alloy tissue.If do not carry out the control of the average atom concentration of the P that contains in this precipitate, just can not guarantee to suppress the big P precipitate that contains of effect of embolization that crystal grain-growth suppresses in the copper alloy tissue is appropriate amount.Consequently, be difficult to the footpath miniaturization of the average crystal grain of copper alloy tissue below 10 μ m.

(number density of precipitate)

But,, must guarantee to be present in the number density of the precipitate in the copper alloy tissue as this prerequisite.The number density of the precipitate in being present in the copper alloy tissue is too small, or when excessive, even controlled the average atom concentration of the P that contains in these precipitates or the average atom concentration of P and Si, certainly also can cause the situation that the raising effect of bendability can not be given full play to.Therefore, the present invention is in order to guarantee the crystal grain footpath micronized effect of precipitate, and the number density of establishing the precipitate of specific dimensions is a certain limit.

That is, number density above-mentioned copper alloy tissue, by above-mentioned electric field emission type transmission electron microscope and energy dispersion type analytical equipment precipitate that determine, 50～200nm size is 0.2～7.0/μ m ²At this, whether the precipitate of the specific dimensions that is limited no matter contain P, but serve as the benchmark of classifying with the size of each precipitate (maximum through) all.

When the number density of this precipitate less than 0.2/μ m ²The time, precipitate is very few.Therefore,, can not give full play to crystal grain footpath micronized effect even control the P that contains in this precipitate or the average atom concentration of P and Si, thickization of crystal grain, bendability might descend.

On the other hand, when the number density of this precipitate greater than 7.0/μ m ²The time, precipitate is too much, when bending machining, promotes the formation of shear zone, and bendability descends on the contrary.Therefore, the number density of establishing the precipitate of 50～200nm size is 0.2～7.0/μ m ²Scope, be preferably 0.5～5.0/μ m ²Scope.

(the average atom concentration of the P that contains in the precipitate)

On the basis of the number density that has guaranteed precipitate, the present invention for the average crystal grain footpath miniaturization that makes the copper alloy tissue below 10 μ m, the average atom concentration of the P that contains in electric field emission type transmission electron microscope this copper alloy tissue, by 30000 times of multiplying powers and the energy dispersion type analytical equipment precipitates such as nickel silicide that determine, 50～200nm size is controlled in the scope of 0.1～50at%.

As mentioned above, the present invention does not directly limit the amount that contains the P precipitate be present in the copper alloy tissue, but (the average atom concentration of the P in whole precipitates of 50～200nm) is controlled the amount that contains the P precipitate by being present in above-mentioned specific dimensions in the copper alloy tissue.

When the average atom concentration of the P that contains when above-mentioned precipitate is crossed low not enough 0.1at%, thickization of crystal grain of copper alloy tissue, bendability decline.On the other hand, too much to the solid solution element of copper alloy tissue except that P when the average atom excessive concentration of the P that contains when above-mentioned precipitate surpasses 50at%, electric conductivity decline.The average atom concentration of therefore establishing the P that precipitate contains is the scope of 0.1～50at%, is preferably the scope of 0.5～40at%.

(average crystal grain footpath)

Among the present invention, crystal grain after the miniaturization, the copper alloy tissue directly becomes the target that improves bendability in practice by the precipitate of these copper alloy tissues is controlled, and limits the average crystal grain footpath of copper alloy tissue.Promptly, at the number of establishing by 350 times of multiplying powers that has loaded the crystal grain that the backscattering electron diffraction determines as the crystal orientation method of analysis of system at the electric field emission type transmission electron microscope is n, if when the crystal grain that determines separately directly is x, directly be below the 10 μ m with the average crystal grain that (∑ x)/n represents.

When average crystal grain directly becomes big above 10 μ m, can not get the bendability that the present invention will obtain.Therefore establishing average crystal grain directly is below the 10 μ m, below the preferred 7 μ m.

Then, to for one of other best mode of the present invention, second mode of the present invention describes.

(one-tenth of copper alloy is grouped into)

As above-mentioned various uses, at first satisfy necessary intensity or electric conductivity to being used to, the copper nisiloy that also has second mode of the present invention of high bendability or proof stress damping characteristics is that the chemical ingredients of alloy is formed, and describes following.

In order to realize high strength, high conductivity, also has high bendability, second mode of the present invention is in quality %, for containing Ni:0.4～4.0%, Si:0.05～1.0% respectively, the copper alloy that Cr:0.005～1.0%, surplus are made up of copper and unavoidable impurities and the essentially consist formed.This consists of the crystal grain miniaturization that is used to make the copper alloy tissue, and control precipitate (Ni ₂Si) the average atom concentration of the Cr that contains in, be grouped into the important precondition that the aspect is considered from one-tenth.In addition, the % that puts down in writing in explanation of following each element is total mass %.

With respect to this essentially consist, can also contain Zn:0.005～3.0%.In addition, also can contain Sn:0.01～5.0%.In addition, can also contain and add up among 0.01～3.0% Ti, Fe, Mg, Co, the Zr one or more.

Ni：0.4～4.0％。

Ni has by crystallization to go out or separate out compound (Ni with Si ₂Si etc.), guarantee the effect of the intensity and the electric conductivity of copper alloy.In addition, also form compound with Cr.When the very few less than 0.4% of the content of Ni, because the growing amount of precipitate is insufficient, thus not only can not get desirable intensity, but also make thickization of crystal grain of copper alloy tissue.In addition, the ratio that the crystalline substance that segregation easily takes place goes out thing increases, and the deviation of the characteristic of end article increases.On the other hand, when the content of Ni surpasses 4.0% and too much the time, not only electric conductivity descends, and the number of thick precipitate is too much, bendability descends.Therefore, establishing Ni amount is 0.4～4.0% scope.

Si：0.05～1.0％

Si makes the compound (Ni with Ni ₂Si etc.) crystallization is separated out, and improves the intensity and the electric conductivity of copper alloy.In addition, also form compound with Cr.Under the situation of the very few less than 0.05% of the content of Si, because the generation of precipitate is insufficient, thus not only can not get desirable intensity, but also make thickization of crystal grain.In addition, the ratio that the crystalline substance that segregation easily takes place goes out thing increases, thereby strengthens the characteristic deviation of end article.On the other hand, when the content of Si surpasses 1.0% and too much the time, the number of thick precipitate is too much, bendability descends, and the atomicity of Cr that contains in the precipitate and Si is lower excessively than number Cr/Si simultaneously.Therefore, establishing Si content is 0.05～1.0% scope.

Cr：0.005～1.0％

Cr contains the Cr precipitate for being used for generating, and control contains the important element of atomic percent in above-mentioned specified range of the Cr in the Cr precipitate.Contain the Cr precipitate by formation, improve intensity, electric conductivity, make the crystal grain miniaturization by the formation that contains the Cr precipitate simultaneously, improve bendability.But, within these effects, especially the effect that improves of the bendability atomic percent that contains the Cr of Cr precipitate by control is brought into play at above-mentioned specified range.

Under the situation of the very few less than 0.005% of Cr content, can not effectively bring into play these effects, effect.On the other hand, surpass 1.0% when the content of Cr is too much, surpass at 0.6% o'clock more strictly speaking, the precipitate chap is big, is unfavorable for bendability, and the atomic percent of the Cr that contains in the precipitate is too high.Therefore the content of establishing Cr is 0.005～1.0% scope, is preferably 0.005～0.6% scope.

At this, the said Cr of containing precipitate is meant that the Ni-Si-Cr etc. in the essentially consist of Ni-Si-Cr contains the Cr precipitate among so-called the present invention.When in this essentially consist, containing Fe or Mg etc., contain the Cr precipitate with Ni-Si-Cr, or replace its generation (Fe, Mg)-Si-Cr, Ni-Si-(Fe, Mg)-Cr etc. to contain the Cr precipitate.In addition, when containing Ti, Co, Zr etc., these Fe or Mg etc. partly generate a part in addition all replaced contain the Cr precipitate.

Ti, Fe, Mg, Co, Zr: add up to 0.01～3.0%

As mentioned above, these elements contain the Cr precipitate by formation and improve intensity, electric conductivity, also have the effect that makes the crystal grain miniaturization simultaneously.Under the situation that makes the performance of these effects, selectivity contains one or more among the Ti, the Fe that add up to more than 0.01%, Mg, Co, the Zr.But when the total content (total amount) of these elements surpassed 3.0%, the precipitate chap was big, is unfavorable for bendability, and the atomic percent of the Cr that contains in the precipitate is low excessively.Therefore, establishing content that selectivity contains Ti, Fe under there is something special, Mg, Co, Zr, to add up to (total amount) be 0.01～3.0% scope.

Zn：0.005～3.0％

Zn be to improvement be used for Sn coating that electronic product engages or scolding tin heat-resisting separability, suppress hot soarfing from effective elements.Under the situation that such effect is effectively brought into play, selectivity contains more than 0.005%.But, when surpassing 3.0% and surplus contains sometimes, cause the wetting expansion deterioration that dissolves Sn or scolding tin on the contrary, in addition, when content increased, electric conductivity also descended significantly.Therefore, considering that heat-resisting separability improves on the basis of effect and electric conductivity decline effect, selectivity contains Zn, establishes Zn content under this situation and be 0.005～3.0% scope, is preferably 0.005～1.5% scope.

Sn：0.01～5.0％

The content of other elements

Other elements are essentially impurity, and are preferably few as much as possible.For example impurity elements such as Mn, Ca, Ag, Cd, Be, Au, Pt, S, Pb, P generate thick crystallization precipitate easily, and it not only makes bendability worsen, and cause the decline of electric conductivity easily.Therefore, preferably these element total amounts are few content below 0.5%.In addition, elements such as Hf, the Th that trace contains in the copper alloy, Li, Na, K, Sr, Pd, W, Nb, Al, V, Y, Mo, In, Ga, Ge, As, Sb, Bi, Te, B, C, norium also cause the decline of electric conductivity easily, therefore it is desirable to, the total amount of these elements is suppressed to few content below 0.1%.But, in order to reduce these elements, give birth to manufacturing costs such as gold use or refinement and rise, in order to suppress the rising of manufacturing cost, allow the total amount of these elements to contain to the above-mentioned separately upper limit.

(copper alloy tissue)

The present invention is an alloy structure for prerequisite designs the tissue of this copper alloy with above-mentioned Cu-Ni-Si-Cr, makes average crystal grain footpath miniaturization below 30 μ m, and preferred miniaturization improves the bendability of copper alloy below 10 μ m.Among the present invention, realize this tissue design by control to the amount that contains the Cr precipitate.More particularly, the number density of precipitate of guaranteeing certain size by control in the copper alloy tissue for more than a certain amount of and guarantee that the average atom concentration of the Cr that contains in the precipitate of this size is a certain amount of the realization.

If not by such control, just can not guarantee that the big Cr precipitate that contains of effect of embolization that crystal grain-growth suppresses is appropriate amount in the copper alloy tissue.Consequently, the average crystal grain footpath miniaturization that is difficult to make the copper alloy tissue more is difficult to miniaturization below 10 μ m below 30 μ m.The Cr precipitate that contains of the present invention as mentioned above, even its solutionizing treatment temp is a high temperature, contains the Cr precipitate and crosses and also do not carry out solid solution, but exists (remaining) in tissue as precipitate, thus the big effect of embolization that the performance crystal grain-growth suppresses.But this contains the size of the effect of embolization of Cr precipitate, as mentioned above, is subjected to about the number density of precipitate of the average atom concentration of the Cr that contains in 50～200nm size precipitate and this size big.

(number density of precipitate)

But,, must guarantee to be present in the number density of the precipitate in the copper alloy tissue as this prerequisite.The number density of the precipitate in being present in the copper alloy tissue is too small, or when excessive, even controlled the average atom concentration of the Cr that contains in these precipitates or the average atom concentration of Cr and Si, certainly also can cause the situation that the raising effect of bendability can not be given full play to.Therefore, the present invention is in order to guarantee the crystal grain footpath micronized effect of precipitate, and the number density of establishing the precipitate of specific dimensions is a certain limit.

That is 0.2～20/μ of number density average out to m above-mentioned copper alloy tissue, by above-mentioned electric field emission type transmission electron microscope and energy dispersion type analytical equipment precipitate that determine, 50～200nm size, ²At this, whether the precipitate of the specific dimensions that is limited no matter contain Cr, but serve as the benchmark of classifying with the size (maximum diameter) of each precipitate all.

When this precipitate is that number density is less than 0.2/μ m ²The time, precipitate is very few.Therefore,, can not give full play to crystal grain footpath micronized effect even control the Cr that contains in this precipitate or the average atom concentration of Cr and Si, thickization of crystal grain, bendability might descend.

On the other hand, when the number density of this precipitate greater than 20/μ m ²The time, precipitate is too much, when bending machining, promotes the formation of shear zone, and bendability descends on the contrary.Therefore, the number density of establishing the precipitate of 50～200nm size is 0.2～20/μ m ²Scope, be preferably 0.5～15/μ m ²Scope.

(the average atom concentration of the Cr that contains in the precipitate)

On the basis of the number density that has guaranteed precipitate, the present invention for the average crystal grain footpath miniaturization that makes the copper alloy tissue below 30 μ m, the average atom concentration of the Cr that contains in electric field emission type transmission electron microscope this copper alloy tissue, by 30000 times of multiplying powers and the energy dispersion type analytical equipment Ni-Si-precipitates such as Cr that determine, 50～200nm size is controlled in the scope of 0.1～80at%.

As mentioned above, the present invention does not directly limit the amount that contains the Cr precipitate be present in the copper alloy tissue, but (the average atom concentration of the Cr in whole precipitates of 50～200nm) comes the amount that contains the Cr precipitate is controlled by being present in above-mentioned specific dimensions in the copper alloy tissue.Therefore, the present invention is the atomic percent that object is measured Cr with whole precipitates (no matter whether containing the precipitate of Cr) of these specific dimensions, according to the average atom concentration of the Cr in these precipitates, the amount that contains the Cr precipitate in the copper alloy tissue is controlled.

When the average atom concentration of the Cr that contains when above-mentioned precipitate is crossed low not enough 0.1at%, thickization of crystal grain of copper alloy tissue, bendability decline.On the other hand, when the average atom excessive concentration of the Cr that contains when above-mentioned precipitate surpassed 80at%, the solid solution element to copper alloy tissue beyond the Cr was too much, electric conductivity decline.The average atom concentration of therefore establishing the Cr that contains in the precipitate is the scope of 0.1～80at%, is preferably the scope of 0.5～50at%.

(average crystal grain footpath)

Among the present invention, crystal grain miniaturization, the copper alloy tissue directly becomes in the actual central target that improves bendability by the precipitate of these copper alloy tissues is controlled, and limits the average crystal grain footpath of copper alloy tissue.Promptly, establishing the number that electric field emission type transmission electron microscope by 10000 times of multiplying powers loaded the crystal grain that the backscattering electron diffraction determines as the crystal orientation method of analysis of system is n, when if the crystal grain that determines separately directly is x, with the average crystal grain that (∑ x)/n represents directly is below the 30 μ m, below the preferred 10 μ m.

When average crystal grain directly becomes big above 30 μ m, can not get the bendability that the present invention will obtain.Therefore reducing average crystal grain directly is below the 30 μ m, and preferably reducing average crystal grain directly is below the 10 μ m, makes crystal grain footpath miniaturization.

Then, to for one of other again best mode of the present invention, Third Way of the present invention describes.

(one-tenth of copper alloy is grouped into)

As above-mentioned various uses, at first satisfy necessary intensity or electric conductivity to being used to, the copper nisiloy that also has the Third Way of the present invention of high bendability or proof stress damping characteristics is that the chemical ingredients of alloy is formed, and describes following.

In order to realize high strength, high conductivity, also has high bendability, Third Way of the present invention is in quality %, for containing Ni:0.4～4.0%, Si:0.05～1.0% respectively, the copper alloy that Ti:0.005～1.0%, surplus are made up of copper and unavoidable impurities and the essentially consist formed.This consists of the crystal grain miniaturization that is used to make the copper alloy tissue, and control precipitate (Ni ₂Si) the average atom concentration of the Ti that contains in, be grouped into the important precondition that the aspect is considered from one-tenth.In addition, the % that puts down in writing in explanation of following each element is total mass %.

With respect to this essentially consist, can also contain Zn:0.005～3.0%.In addition, also can contain Sn:0.01～5.0%.In addition, can also contain and add up to 0.01～3.0% Fe, Mg, among Co, the Zr one or more.

Ni：0.4～4.0％。

Ni has by crystallization to go out or separate out compound (Ni with Si ₂Si etc.), guarantee the effect of the intensity and the electric conductivity of copper alloy.In addition, also form compound with Ti.When the very few less than 0.4% of the content of Ni, because the growing amount of precipitate is insufficient, thus not only can not get desirable intensity, but also make thickization of crystal grain of copper alloy tissue.In addition, the ratio that the crystalline substance that segregation easily takes place goes out thing uprises, thereby strengthens the characteristic deviation of end article.On the other hand, when the content of Ni surpasses 4.0% and too much the time, electric conductivity descends, and the number of thick precipitate is too much, bendability descends.Therefore, establishing Ni amount is 0.4～4.0% scope.

Si：0.05～1.0％

Si makes the compound (Ni with Ni ₂Si etc.) crystallization is separated out, and improves the intensity and the electric conductivity of copper alloy.In addition, also form compound with Cr.Under the situation of the very few less than 0.05% of the content of Si, because the generation of precipitate is insufficient, thus not only can not get desirable intensity, but also make thickization of crystal grain.In addition, the ratio that the crystalline substance that segregation easily takes place goes out thing uprises, thereby strengthens the characteristic deviation of end article.On the other hand, when the content of Si surpasses 1.0% and too much the time, the number of thick precipitate is too much, bendability descends, and the atomicity of Ti that contains in the precipitate and Si is lower excessively than number Ti/Si simultaneously.Therefore, establishing Si content is 0.05～1.0% scope.

Ti：0.005～1.0％

Ti contains the Ti precipitate and generates for being used to make, and the atomic percent that will contain the Ti in the Ti precipitate is controlled at the important element of above-mentioned specified range.Contain the Ti precipitate by formation, improve intensity, electric conductivity, make the crystal grain miniaturization by the formation that contains the Ti precipitate simultaneously, improve bendability.But, within these effects, especially the effect that improves of the bendability atomic percent that contains the Ti of Ti precipitate by control is brought into play at above-mentioned specified range.

Under the situation of the very few less than 0.005% of Ti content, can not effectively bring into play these effects, effect.On the other hand, surpass 1.0% when the content of Ti is too much, surpass at 0.6% o'clock more strictly speaking, the precipitate chap is big, is unfavorable for bendability, and the atomic percent of the Ti that contains in the precipitate is too high.Therefore the content of establishing Ti is 0.005～1.0% scope, is preferably 0.005～0.6% scope.

At this, the said Ti of containing precipitate is meant that the Ni-Si-Ti etc. in the essentially consist of Ni-Si-Ti contains the Ti precipitate among so-called the present invention.When in this essentially consist, containing Fe or Mg etc., contain the Ti precipitate with Ni-Si-Ti, or replace it to generate Ni-Si-(Fe, Mg)-Ti etc. containing the Ti precipitate.In addition, when containing Co, Zr etc., these Fe or Mg etc. partly generate a part in addition all metathetical contain the Ti precipitate.

Fe, Mg, Co, Zr: add up to 0.01～3.0%

As mentioned above, these elements contain the Ti precipitate by formation and improve intensity, electric conductivity, also have the effect that makes the crystal grain miniaturization simultaneously.Under the situation that makes the performance of these effects, selectivity contains the Fe, the Mg that add up to more than 0.01%, among Co, the Zr one or more.But when the total content (total amount) of these elements surpassed 3.0%, the precipitate chap was big, is unfavorable for bendability, and the atomic percent of the Ti that contains in the precipitate is low excessively.Therefore, establishing content that selectivity contains Fe, Mg under there is something special, Co, Zr, to add up to (total amount) be 0.01～3.0% scope.

Zn：0.005～3.0％

Sn：0.01～5.0％

The content of other elements

Other elements are essentially impurity, and are preferably few as much as possible.For example impurity elements such as Mn, Ca, Ag, Cd, Be, Au, Pt, S, Pb, P generate thick crystallization precipitate easily, and it not only makes bendability worsen, and cause the decline of electric conductivity easily.Therefore, preferably these element total amounts are few content below 0.5%.In addition, elements such as Hf, the Th that trace contains in the copper alloy, Li, Na, K, Sr, Pd, W, Nb, Al, V, Y, Mo, In, Ga, Ge, As, Sb, Bi, Te, B, C, norium also cause the decline of electric conductivity easily, therefore it is desirable to, these total amount is suppressed to few content below 0.1%.But, in order to reduce these elements, give birth to manufacturing costs such as gold use or refinement and rise, in order to suppress the rising of manufacturing cost, allow the total amount of these elements to contain to the above-mentioned separately upper limit.

(copper alloy tissue)

The present invention is an alloy structure for prerequisite designs the tissue of this copper alloy with above-mentioned Cu-Ni-Si-Ti, makes average crystal grain footpath miniaturization below 20 μ m, and preferred miniaturization improves the bendability of copper alloy below 10 μ m.Among the present invention, realize this tissue design by control to the amount that contains the Ti precipitate.More particularly, the number density of precipitate of guaranteeing certain size by control for more than a certain amount of, guarantees that simultaneously the average atom concentration of the Ti that contains in the precipitate of this size is a certain amount of the realization in the copper alloy tissue.

If not by such control, just the big Ti precipitate that contains of effect of embolization that crystal grain-growth suppresses can not be guaranteed appropriate amount in the copper alloy tissue.Consequently, the average crystal grain footpath miniaturization that is difficult to make the copper alloy tissue more is difficult to miniaturization below 10 μ m below 20 μ m.As mentioned above, the Ti precipitate that contains of the present invention even its solutionizing treatment temp is a high temperature, contains the Ti precipitate and does not also carry out solid solution, and exists (remaining) in tissue as precipitate, the big effect of embolization that the performance crystal grain-growth suppresses.But as mentioned above, this size that contains the effect of embolization of Ti precipitate is influenced greatly by the number density of the precipitate of the average atom concentration of the Ti that contains in the precipitate of 50～200nm size or this size.

(number density of precipitate)

But,, must guarantee to be present in the number density of the precipitate in the copper alloy tissue as this prerequisite.The number density of the precipitate in being present in the copper alloy tissue is too small, or when excessive, even controlled the average atom concentration of the Ti that contains in these precipitates or the average atom concentration of Ti and Si, certainly also can cause the situation that the raising effect of bendability can not be given full play to.Therefore, the present invention is in order to guarantee the crystal grain footpath micronized effect of precipitate, and the number density of establishing the precipitate of specific dimensions is a certain limit.

That is 0.2～20/μ of number density average out to m above-mentioned copper alloy tissue, by above-mentioned electric field emission type transmission electron microscope and energy dispersion type analytical equipment precipitate that determine, 50～200nm size, ²At this, whether the precipitate of the specific dimensions that is limited no matter contain Ti, but serve as the benchmark of classifying with the size of each precipitate (maximum through) all.

When this precipitate is that number density is less than 0.2/μ m ²The time, precipitate is very few.Therefore,, can not give full play to crystal grain footpath micronized effect even control the Ti that contains in this precipitate or the average atom concentration of Ti and Si, thickization of crystal grain, bendability might descend.

(the average atom concentration of the Ti that contains in the precipitate)

On the basis of the number density that has guaranteed precipitate, the present invention for the average crystal grain footpath miniaturization that makes the copper alloy tissue below 20 μ m, the average atom concentration of the Ti that contains in electric field emission type transmission electron microscope this copper alloy tissue, by 30000 times of multiplying powers and the energy dispersion type analytical equipment Ni-Si-precipitates such as Ti that determine, 50～200nm size is controlled in the scope of 0.1～50at%.

As mentioned above, the present invention does not directly limit the amount that contains the Ti precipitate be present in the copper alloy tissue, but (the average atom concentration of the Ti in whole precipitates of 50～200nm) comes the amount that contains the Ti precipitate is controlled by being present in above-mentioned specific dimensions in the copper alloy tissue.Therefore, the present invention is the atomic percent that object is measured Ti with whole precipitates (no matter whether containing the precipitate of Ti) of these specific dimensions, according to the average atom concentration of the Ti in these precipitates, the amount that contains the Ti precipitate in the copper alloy tissue is controlled.

When the average atom concentration of the Ti that contains when above-mentioned precipitate is crossed low not enough 0.1at%, thickization of crystal grain of copper alloy tissue, bendability decline.On the other hand, when the average atom excessive concentration of the Ti that contains when above-mentioned precipitate surpassed 50at%, the solid solution element to the copper alloy tissue except that Ti was too much, electric conductivity decline.The average atom concentration of therefore establishing the Ti that contains in the precipitate is the scope of 0.1～50at%, is preferably the scope of 0.5～40at%.

(average crystal grain footpath)

Among the present invention, crystal grain miniaturization, the copper alloy tissue directly becomes the target that improves bendability in practice by the precipitate of these copper alloy tissues is controlled, and limits the average crystal grain footpath of copper alloy tissue.Promptly, establishing the number that electric field emission type transmission electron microscope by 10000 times of multiplying powers loaded the crystal grain that the backscattering electron diffraction determines as the crystal orientation method of analysis of system is n, if when the crystal grain that determines separately directly is x, directly be 20 with the average crystal grain that (∑ x)/n represents

Below the μ m, below the preferred 10 μ m.

When average crystal grain directly becomes big above 20 μ m, can not get the bendability that the present invention will obtain.Therefore reducing average crystal grain directly is below the 20 μ m, and preferably reducing average crystal grain directly is below the 10 μ m, makes crystal grain footpath miniaturization.

(the number density measuring method of precipitate)

The number density measuring method of precipitate is the leading portion of the average atom concentration determination of described later, the M that contains in precipitate.Particularly, extract sample, make the tem observation film by electrolytic polishing from the final copper alloy (plate etc.) that manufactures.And (FE-TEM) times obtains bright field-of-view image with multiplying power * 30000 by Hitachi's system: HF-2200 electric field emission type transmission electron microscope for example with this sample.Oven dry and video picture this bright field-of-view image, by the diameter and the quantity of this photo mensuration precipitate, the maximum diameter of specific each precipitate is positioned at the precipitate of size of the scope of 50～200nm.It is (individual/μ m to calculate the number density of precipitate of size of the scope that is positioned at 50～200nm according to this mensuration ²).

(the average atom method for measurement of concentration of the M that precipitate contains)

Each precipitate of the same bright field-of-view image (same observation picture) of breaking forth with respect to the electric field emission type transmission electron microscope number density that determines above-mentioned precipitate, 30000 times of multiplying powers, for example, the composition of each precipitate is implemented quantitative analysis by Noran corporate system NSS energy dispersion type analytical equipment (EDX).Ray diameter during this analysis is to implement below the 5nm.Only each precipitate (all precipitates) of above-mentioned maximum diameter 50～200nm size is implemented this analysiss (the precipitate of in addition size not being implemented), and measure interior M of each precipitate (whole precipitate) visual field in and the atomic percent (at%) of Si respectively.And, calculate M in the bright field, that precipitate contains and the average atom concentration of Si.

(M that precipitate contains and the atomicity of Si are than measuring method)

The mensuration of M that contains according to (in the precipitate) in this precipitate and the average atom concentration of Si also can be calculated the atomicity of M that the precipitate of the size that is arranged in 50～200nm scope contains and Si average than M/Si.

For these the raising of mensuration and even reproducibility of calculating and precision, the mensuration sample that extracts from copper alloy is 10 of getting from 10 positions arbitrarily, the atomicity of average atom concentration, M and the Si of M that above-mentioned precipitate contains and Si than each numerical value such as number density of M/Si, precipitate for these 10 on average.

(average crystal grain footpath measuring method)

Why the present invention is defined as the crystal orientation method of analysis of having loaded backscattering electron diffraction picture [EBSP:Electron Back Scattering (Scattered) Pattern] system at electric field emission type transmission electron microscope (Field Emission Scanning Microscopel FESEM) with these average crystal grains measuring method directly, is owing to this measuring method because the high de-agglomeration ability is arranged so it is high-precision cause.

The EBSP method is shone the electronics line to the sample that is placed in the FESEM lens barrel, and EBSP is projected on the optical filtering.Utilize the photographic camera of high sensitivity that it is taken pictures, deposit computer in as image.This image of computer analyzing, and compare with the imitation sample that utilizes known crystal system, determine the crystalline orientation.The crystalline orientation that calculates is that cube is reined in the angle especially, is recorded with position coordinates (x, y) etc.This program can be carried out automatically to whole measuring points, therefore when measuring end, can obtain the crystal orientation data of tens thousand of～hundreds thousand of points.

Like this, the EBSP method has the following advantages, it is compared with the method for electron diffraction that utilizes X-ray diffraction method or transmission electron microscope, field of view is wide, a few hours with interior average crystal grain footpath, the standard deviation in average crystal grain footpath or the information of orientation parsing that obtains the crystal grain of hundreds of relatively above majorities.In addition, also have following advantage, owing to be not that each crystal grain is measured, but with certain intervals scanning arbitrarily and measure specified zone, so can access measuring point, above-mentioned each information that network is firmly measured the above-mentioned majority of regional integration.In addition, relevant with the EBSP system loading in the crystal orientation method of analysis of these FESEM in detail, at length be documented in Kobe system copper skill report in/Vol.52No.2 (sep.2002) P66-70 etc.

Utilization is the crystal orientation method of analysis of EBSP system loading in these FESEM, and the present invention measures the set tissue of surface element of the thickness of slab direction of goods copper alloy, carries out the mensuration in crystal grain footpath.

At this, under the situation of common copper alloy, main form by as shown below be known as Cube orientation, Goss orientation, Brass orientation (below, general designation is made the B orientation), Copper (below, general designation is made the Cu orientation), the set tissue formed of many steric factors in S orientation etc., and the existence crystal plane corresponding with it.These facts for example are recorded in Long Island Shanxi one and write " set tissue " (the kind Co., Ltd. of ball periodical) or explanation Vol.43,1993, the P285-293 of light metal association " light metal " etc.

Even under these the situation that forms identical crystal system of set tissue, its processing, heat treating method are also different.The situation of the set tissue of the sheet material of rolling formation represents with rolling surface and rolling direction, rolling surface with ABC} expresses, and rolling direction is with＜DEF〉expression (ABCDEF represents integer).Based on these expression, the following expression in each orientation.

The Cube orientation 001}＜100 〉

The Goss orientation 011}＜100 〉

Rotaced-Goss orientation 011}＜011 〉

Brass orientation (B orientation) 011}＜211 〉

Copper orientation (Cu orientation) 112}＜111 〉

Perhaps, the D orientation 4411}＜11118 〉

The S orientation 123}＜634 〉

The B/G orientation 011}＜511 〉

The B/S orientation 168}＜211 〉

The P orientation 011}＜111 〉

Among the present invention, basically from these crystal planes depart from ± 15 ° of crystal planes with interior orientation belong to identical crystal plane (steric factor).In addition, be that the boundary definition of the crystal grain more than 5 ° is a boundary or grain with the azimuth difference of adjacent crystal grain.

And, among the present invention, relative determination zone 300 * 300 μ m, pitch irradiation electronics line with 0.5 μ m, at the number of establishing the crystal grain that determines by above-mentioned crystal orientation method of analysis is n, establishes separately the crystal grain that determines directly when the x, calculates above-mentioned average crystal grain footpath by (∑ x)/n.

(creating conditions)

Then, to be used to establish copper alloy be organized as tissue that the invention described above limits, best creating conditions carry out following explanation.Copper alloy of the present invention is essentially copper alloy plate, width with the bar of its opening, and the copper alloy after these laths coilings is included in the scope of copper alloy of the present invention.

The present invention is also the same with common manufacturing process, by comprise casting, ingot bar surfacing, soaking, hot rolling to the copper alloy solution after being adjusted to special component and forming, operations such as (precipitation annealing), distortion annealing are handled in cold rolling and solution processing (recrystallization annealing), age hardening then, obtain finally (goods) plate.But, within above-mentioned manufacturing process,, also can access tissue, intensity high conductivity and bendability that the present invention limits by respectively creating conditions of combination and the following the best that illustrates of enforcement.

At first, preferably establishing the hot rolling end temp is 550～850 ℃.When the temperature field that is lower than 550 ℃ in this temperature carried out hot rolling, because recrystallize is incomplete, so become uneven tissue, bendability worsened.When the hot rolling end temp is higher than 850 ℃, thickization of crystal grain, bendability worsens.Preferably after this hot rolling, carry out water-cooled.

Then, after this hot rolling, preferably establishing the preceding cold rolling cold rolling rate of solution processing (recrystallization annealing) is 70～98%.When cold rolling rate is lower than 70%, owing to be the undersized of recrystallization nucleus, so must be bigger than the average crystal grain footpath that the present invention will obtain, might cause bendability to worsen.On the other hand, when cold rolling rate greater than 70% the time because the distribution bias of deflection strengthens, so the footpath of the crystal grain behind the recrystallize thereafter is inhomogeneous, the bendability that might cause the present invention to obtain worsens.

(solution processing)

The solution processing is the precipitate control by copper alloy tissue of the present invention, makes crystal grain footpath miniaturization, and improves the important operation of the bendability of copper alloy.Heat-up rate when especially, the solution processing begins and very important to the precipitate control of copper alloy tissue according to the control of the speed of cooling of the solution treatment temp after the solution processing.

About this point, first mode of the present invention establish respectively to 400 ℃ average heating speed of solution treatment temp be the scope of 5～100 ℃/h, if the average heating speed from 400 ℃ to the solution treatment temp be 100 ℃/more than the s, if the solution treatment temp is 700～900 ℃, establish average cooling rate after the solution processing and be 50 ℃/more than the s.

In the intensification of solution treatment process, process of cooling, at first, in room temperature～about more cryogenic zone below 600 ℃ nickel silicide precipitate (Ni takes place ₂Si) etc. separate out, at about high-temperature area more than 600 ℃ these precipitates of solid solution again.In addition, the recrystallization temperature scope of copper alloy of the present invention is approximately 500～700 ℃, and the dispersion state of the precipitate the when crystal grain of copper alloy directly is subjected to this recrystallize influences greatly.

Make from the heat up average heating speed in beginning time to 400 ℃ of solutionizing smallerly, be made as 5～100 ℃/h.But when average heating speed during less than this 5 ℃/h, thickization of precipitate that separates out, average crystal grain directly becomes greatly, and bendability descends.On the other hand, when average heating speed during greater than this 100 ℃/h, the growing amount of precipitate reduces.Therefore, the number density deficiency of precipitate, average crystal grain directly becomes greatly, and bendability descends.

Secondly, make from above-mentioned 400 ℃ of average heating speeds to the solution temperature bigger, be made as 100 ℃/more than the s.During as 100 ℃/s of heat-up rate less than, less than 100 ℃, promote the growth of crystal grain, average crystal grain directly becomes greatly again, and bendability descends.

If the solution treatment temp is to be lower than 900 ℃ more than 700.When the solution treatment temp was lower than 700 ℃, solutionization was insufficient, not only can not get the high strength that the present invention will obtain, and bendability descends.On the other hand, when the solution treatment temp is more than 900 ℃, when being higher than 900 ℃, the number density of precipitate is with too small, and the atomic percent of the P that contains in the precipitate is low excessively simultaneously, can not get bendability and high conductivity that the present invention will obtain.

If the average cooling rate after the solution processing be 50 ℃/more than the s.When speed of cooling during less than 50 ℃/s, promote the growth of crystal grain, the average crystal grain footpath that will obtain greater than the present invention, and bendability descends.

In addition, second mode of the present invention establish respectively to 400 ℃ average heating speed of solution processing be the scope of 5～100 ℃/h, if the average heating speed from 400 ℃ to the solution treatment temp be 100 ℃/more than the s, if the solution treatment temp is 700～950 ℃, establish average cooling rate after the solution processing and be 50 ℃/more than the s.

In the intensification of solution treatment process, process of cooling, at first, in the about more cryogenic zone below 600 ℃ of distance room temperature Ni takes place ₂Si etc. separate out, at about high-temperature area more than 600 ℃ these precipitates of solid solution again.In addition, the recrystallization temperature scope of copper alloy of the present invention is approximately 500～700 ℃, and the dispersion state of the precipitate the when crystal grain of copper alloy directly is subjected to this recrystallize influences greatly.

Secondly, make from above-mentioned 400 ℃ of average heating speeds to the solution temperature bigger, be made as 100 ℃/more than the s.When 100 ℃/s of heat-up rate less than, the precipitate regardless of the present invention limits all promotes the growth of crystal grain again, and average crystal grain directly becomes greatly, and bendability descends.

If the solution treatment temp is to be lower than 950 ℃ the higher temperature of ratio more than 700.When the solution treatment temp was lower than 700 ℃, solutionization was insufficient, not only can not get the high strength that the present invention will obtain, and bendability descends.On the other hand, when the solution treatment temp is more than 950 ℃ the time, the many Cr of containing precipitates carry out solid solution, and the number density of precipitate is too small, and the atomic percent of the Cr that contains in the precipitate is low excessively simultaneously.Therefore, can not bring into play the effect of embolization of the crystal grain-growth inhibition that contains the Cr precipitate, thickization of crystal grain.So, can not get high strength, bendability and high conductivity that the present invention will obtain.

If the solution treatment temp is above-mentioned high temperature.As mentioned above,, contain the Cr precipitate and also do not carry out solid solution, and exist (remaining) in tissue as precipitate even the solution treatment temp is a high temperature, thus the big effect of embolization that the performance crystal grain-growth suppresses.And, as mentioned above,, can increase considerably the solid solution capacity of Ni, Si by the high temperatureization of solution treatment temp, in age hardening is thereafter handled, can increase considerably the fine amount of separating out of Ni-Si.Consequently, can not make reductions such as bendability, can realize the more high strength of copper alloy owing to thickization in average crystal grain footpath.

The average cooling rate after if solutionizing is handled be 50 ℃/more than the s.When this speed of cooling during less than 50 ℃/s, no matter the precipitate that the present invention limits how, all promotes the growth of crystal grain, greater than the average crystal grain footpath that the present invention will obtain, bendability descends simultaneously.

In addition, Third Way of the present invention establish respectively to 400 ℃ average heating speed of solution treatment temp be the scope of 5～100 ℃/h, if the average heating speed from 400 ℃ to the solution treatment temp be 100 ℃/more than the s, if the solution treatment temp is to be lower than 950 ℃ more than 700, establish average cooling rate after the solution processing and be 50 ℃/more than the s.

Make from the heat up average heating speed in beginning time to 400 ℃ of solutionizing smallerly, be made as 5～100 ℃/h.But, when average heating speed during, will cause thickization of precipitate that separate out less than this 5 ℃/h, average crystal grain directly becomes greatly, and bendability descends.On the other hand, when average heating speed during, will cause the growing amount of precipitate to reduce greater than this 100 ℃/h.Therefore, the number density deficiency of precipitate, average crystal grain directly becomes greatly, and bendability descends.

Secondly, make from above-mentioned 400 ℃ of average heating speeds to the solution temperature bigger, be made as 100 ℃/more than the s.When 100 ℃/s of heat-up rate less than, no matter the precipitate that the present invention limits how, all promotes the growth of crystal grain again, average crystal grain directly becomes greatly, and bendability descends.

If the solutionizing treatment temp is to be lower than 950 ℃ more than 700.When the solution treatment temp was lower than 700 ℃, solutionizing was insufficient, not only can not get the high strength that the present invention will obtain, and bendability descends.On the other hand, when the solutionizing treatment temp became more than 950 ℃, the many Ti of containing precipitates carried out solid solution, and the number density of precipitate is too small, and the atomic percent of the Ti that contains in the precipitate is low excessively simultaneously.Therefore, can not bring into play the effect of embolization of the crystal grain-growth inhibition that contains the Ti precipitate, thickization of crystal grain.So, can not get high strength, bendability and high conductivity that the present invention will obtain.

If the solution treatment temp is above-mentioned high temperature.As mentioned above,, contain the Ti precipitate and also do not carry out solid solution, and exist (remaining) in tissue as precipitate even the solution treatment temp is a high temperature, thus the big effect of embolization that the performance crystal grain-growth suppresses.And, as mentioned above,, can increase considerably the solid solution capacity of Ni, Si by the high temperatureization of solution treatment temp, in age hardening is thereafter handled, can increase considerably the fine amount of separating out of Ni-Si.Consequently, can not reduce bendability, can realize the more high strength of copper alloy owing to thickization in average crystal grain footpath.

(processing after the solution processing)

Also can after the solution processing (after the recrystallization annealing), under about 300～450 ℃ range temperature, carry out precipitation annealing (process annealing, second annealing), form fine precipitate, improve the intensity and the electric conductivity (recovery) of copper alloy plate.In addition, also can be between solution processing and precipitation annealing, the scope 10～50% is carried out final cold rolling.

By suitable combination and implement above explanation these create conditions, can be met the high-strength high-conductivity of above-mentioned condition of the present invention and the copper alloy of has excellent bending properties.The copper alloy of the present invention that obtains like this is the copper alloy of high-strength high-conductivity and has excellent bending properties, wide and practical is used for household electrical appliances, semiconductor device, industry equipment, reaches the automobile electrical subassembly.

Below, enumerate embodiment, more specifically the present invention will be described, certainly, the present invention is not subjected to the restriction of following embodiment, much less, also can suitably increase change in the scope of the aim that can be suitable for front and back and implement, those all are contained in the technical scope of the present invention.

Embodiment

Below, embodiments of the invention 1 are described.Change Cu alloy composition and manufacture method, especially solution treatment condition, P average atom concentration in the precipitate in the Cu alloy structure etc. is carried out various changes, and the average crystal grain of the Cu latten that obtains is directly changed, thereby respectively characteristics such as intensity, electric conductivity, bendability are estimated.

Specifically, the copper alloy that the chemical ingredients shown in the following table 1,2 is formed in the kryptol stove, covers charcoal and dissolves respectively in atmosphere, cast in the cast iron multiple mould, obtains the ingot bar of thick 50mm, wide 75mm, long 180mm.And, after ingot bar is carried out surfacing, under 950 ℃ temperature, carry out hot rolling and become 20mm to thickness, water, carried out chilling but from the hot rolling end temp more than 750 ℃.Then,, carry out once cold rolling, obtain the plate of thickness 0.25mm except that behind the deoxidation scale.

Then, use salt bath furnace, shown in table 2,3, change various intensifications, cooling conditions carries out the solution processing.And the hold-time of the plate under the solution temperature 30 seconds have been set as jointly.Then, by finally cold rolling, make the cold-reduced sheet of thickness 0.20mm respectively.The artificial age-hardening who this cold-reduced sheet is carried out 450 ℃ * 4h handles, and obtains final copper alloy.

Each example is all used the test portion that scales off from above-mentioned final copper alloy plate, the copper alloy that manufactures has like this been implemented intensity (0.2% yield-point) mensuration, electric conductivity measuring, pliability test and the evaluation of survey of organization and tension test.Table 3,4 these results of expression.

At this, the copper alloy shown in the table 1,2, removing that the surplus of record after the amount of element form all be Cu, as table 1,2 records other elements in addition, total impurities such as Al, Be, V, Nb, Mo, W are below 0.5%.In addition, these total amount of B, C, Na, S, Ca, As, Sc, Cd, In, Sb, Bi, MM elements such as (noriums) also is below 0.1%.In addition, the expression of "-" shown in table 1, each constituent content of 2 detects submarginal amount.

The investigation of relevant these copper alloy test portion tissues, respectively by above-mentioned method, the average atom number that has determined the P that contains in the precipitate of the average atom concentration (at%) of the P that contains in the precipitate of 50～200nm size, identical 50～200nm size and Si is (more individual/μ m than the average number density of the precipitate of P/Si, identical 50～200nm size ²).

In addition, utilization has been loaded the backscattering electron diffraction in above-mentioned electric field emission type scanning electronic microscope and has been determined establishing copper alloy test portion number tissue, crystal grain as the crystal orientation method of analysis of system and be n, when if the crystal grain that determines separately directly is x, with the average crystal grain footpath (μ m) that (∑ x)/n represents.Specifically, prepare mechanical mill is carried out on the rolling surface surface of goods copper alloy, and then after polishing is ground, then carry out electrolytic polishing, the test portion of regulating has been carried out on the surface., utilize NEC society system FESEM (JEOL JSM5410), carried out crystal orientation mensuration and the crystal grain of EBSP and directly measured thereafter.Measuring the zone is the zone of 300 μ m * 300 μ m, and measuring step interval is 0.5 μ m.EBSP measures resolution system and has used EBSP:TCL society system (OIM).

(tension test)

Tension test is used the length direction of the establishing test film JIS13 B test film as rolling direction, by 5882 type イ Application ストコ Application societies system universal testing machine, under the condition of room temperature, trial speed 10.0mm/min, Gl=50mm, measured 0.2% yield-point (MPa).Under identical conditions, three test films are tested, adopted these mean value.

(electric conductivity measuring)

Relevant electric conductivity, the length direction of establishing test film is a rolling direction, by milling machine test film is processed into the short palisade of wide 10mm * long 300mm, utilizes compound bridge type resistance measurement device to measure resistance, and utilizes the average cross-section method to calculate.Under identical conditions, three test films are tested, adopted these mean value.

(evaluation test of bendability)

The pliability test of copper alloy test portion is stretched copper association technological standard according to Japan and is carried out.Sheet material is cut into wide 10mm, long 30mm, applies the load of 1000kgf, carry out the bending of GoodWay (bending axis and rolling direction meet at right angles), flawless is arranged with 50 times opticmicroscope visual observation bends with bending radius 0.15mm.What at this moment, do not have a crackle is evaluated as zero; Generated being evaluated as of crackle *.We can say that if this pliability test is good, the bendability of the strictnesses such as 90 ° of bendings behind then above-mentioned closed bending or the fluting is also good.

By table 1,3 as can be known, the copper alloy in the present invention forms, promptly example 1～18 is carried out the solution processing in the optimal conditions scope, has obtained the goods copper alloy.

Therefore, 0.2～7.0/μ of the number density average out to m that organizes its above-mentioned each measuring method precipitate that measure, 50～200nm size of example 1～18 ²Scope, the average atom concentration of the P that contains in the precipitate of this scope size is the scope of 0.1～50at%, average crystal grain directly is below the 10 μ m.In addition, the atomicity of P that contains in the precipitate of 50～200nm size and Si is than P/Si average out to 0.01～10.

Consequently, example 1～18 is more than the 0.2% yield-point 800MPa, high strength, high conductivity that electric conductivity 40%LACS is above, and the copper alloy of has excellent bending properties.

Relative with it, the one-tenth of the copper alloy of comparative example 19～27,33～35 is grouped into outside the scope of the invention.Therefore, though solution processing (manufacture method) is carried out in preferred condition and range, bendability is all inferior, and intensity and electric conductivity are also low.

The copper alloy of comparative example 19 does not contain P.Therefore, the average atom concentration of the P that contains in the precipitate is 0, and average crystal grain directly surpasses 10 μ m and thickization.So bendability and intensity are low.

The copper alloy Ni content of comparative example 20 is higher than outside the upper limit.Therefore, bendability and intensity are obviously low.

The content of the copper alloy Ni of comparative example 21 is lower than outside the lower limit.Therefore, though the average atom concentration of the P that contains in the precipitate of 50～200nm size is 4at%, average crystal grain directly surpasses 10 μ m and thickization.Consequently, bendability and intensity are obviously low.

The content of the copper alloy Si of comparative example 22 is higher than outside the upper limit.Therefore, though the average atom concentration of the P that contains in the precipitate of 50～200nm size is 1.5at%, average crystal grain directly surpasses 10 μ m and thickization.Consequently, bendability and intensity are obviously low.

The content of the copper alloy Si of comparative example 23 is lower than outside the lower limit.Therefore, though several concentration of the P of the precipitate of 50～200nm size are very few, it is 20at% that the average atom of the P that contains in the precipitate of this size is counted concentration, and average crystal grain directly surpasses 10 μ m and thickization.Consequently, bendability and intensity are obviously low.

The content of the copper alloy P of comparative example 24 exceeds outside the upper limit.Therefore, bendability and intensity are obviously low.

The P average atom concentration that contains in the precipitate of copper alloy 50～200nm size of comparative example 25 is very few, and the content of Fe exceeds outside the upper limit 3.0%.Therefore, average crystal grain directly surpasses 10 μ m and thickization.Consequently, bendability and intensity are obviously low.

The P average atom concentration that contains in the precipitate of copper alloy 50～200nm size of comparative example 26 is very few, and the content of Cr, Co exceeds outside the upper limit 3.0%.Therefore, average crystal grain directly surpasses 10 μ m and thickization.Consequently, bendability and intensity, electric conductivity are obviously low.

In addition, though the one-tenth of the copper alloy of comparative example 27～35 is grouped within the scope of the present invention, solution treatment condition (manufacture method) are outside the optimal conditions scope.Consequently, bendability is all inferior, and intensity and electric conductivity be step-down also.

Comparative example 27 is too small to 400 ℃ average heating speed of solution processing.Therefore, though the P average atom concentration that contains in the precipitate of 50～200nm size is 3.7at%, average crystal grain directly is 6 μ m, and bendability and intensity are low.

Comparative example 28 is excessive to 400 ℃ average heating speed of solution processing.Therefore, the number density deficiency of precipitate, average crystal grain directly becomes greatly, and bendability is low.

Comparative example 29 is too small from 400 ℃ of average heating speeds to the solution temperature.Therefore, average crystal grain directly becomes greatly, and bendability is low.

Comparative example 30 solution treatment temps are low excessively.Therefore, solutionization is insufficient, and intensity is low, and bendability is low.

Comparative example 31 solution treatment temps are too high.Therefore, the number density of the precipitate of 50～200nm size is too small, and the average atom concentration of the P that contains in the precipitate of this size is also little of 0.2at%, and average crystal grain directly surpasses 10 μ m and thickization.Consequently, bendability and electric conductivity are low.

Average cooling rate after the comparative example 32 solution processing is too small.Therefore, though the number density of the precipitate of 50～200nm size reaches, the average atom concentration of the P that wherein contains promotes the growth of crystal grain in scope, and the average crystal grain footpath is big, and bendability is low.In addition, intensity is also low.

The copper alloy of comparative example 33,35 does not contain P.In addition, the content of Cr, Co is higher than outside the upper limit 3.0%.And the solution treatment temp is too high, and the number density of the precipitate of 50～200nm size is too small.Therefore, all crystal grain directly surpasses 10 μ m and thickization, and bendability is low.In addition, electric conductivity is also low.

Though the number density of the precipitate of comparative example 34 50～200nm size is too small, the average atom concentration of the P that contains in the precipitate of this size in scope,, average crystal grain directly surpasses 10 μ m and thickization.Consequently, bendability and intensity are low.

According to above result, prove not only high strength, high conductivity, and be used to make one-tenth has excellent bending properties, copper alloy plate of the present invention to be grouped into, to organize, also be useful on the meaning of creating conditions of the best that obtains organizing.

*-below the expression limit of detection

[table 2]

*-below the expression limit of detection

[table 3]

[table 4]

Then, embodiments of the invention 2 are described.Change Cu alloy structure and manufacture method, especially solution treatment condition, Cr average atom concentration in the precipitate in the Cu alloy structure etc. is carried out many variations, the average crystal grain of the Cu latten that obtains is directly changed, respectively characteristics such as intensity, electric conductivity, bendability are estimated.

Specifically, the copper alloy that the chemical ingredients shown in the following table 5 is formed in the kryptol stove, covers charcoal and dissolves respectively in atmosphere, cast in the cast iron multiple mould, obtains the ingot bar of thick 50mm, wide 75mm, long 180mm.And after the surface of ingot bar was cut, under 950 ℃ temperature, hot rolling became 20mm to thickness, carried out chilling but from the hot rolling end temp more than 750 ℃ water.Then,, carry out once cold rolling, obtain the plate of thickness 0.25mm except that behind the deoxidation scale.

Then, use salt bath furnace, as shown in table 6, change various intensifications, cooling conditions carries out the solution processing.And, hold-time of the plate under the solution temperature has been set as 30 seconds jointly.Then, by finally cold rolling, make the cold-reduced sheet of thickness 0.20mm respectively.The artificial age-hardening who this cold-reduced sheet is carried out 450 ℃ * 4h handles, and obtains final copper alloy.

Each example is all used the test portion that scales off from above-mentioned final copper alloy plate, the copper alloy that manufactures has like this been implemented intensity (0.2% yield-point) mensuration, electric conductivity measuring, pliability test and the evaluation of survey of organization and tension test.These results of table 6 expression.

At this, the copper alloy shown in the table 5, removing that the surplus of record after the amount of element form all be Cu, as table 5 record other elements in addition, impurity element total amounts such as Mn, Ca, Ag, Cd, Be, Au, Pt, S, Pt, P are below 0.5%.In addition, these total amount of elements such as Hf, Th, Ll, Na, K, Sr, Pd, W, Nb, Al, V, Y, Mo, In, Ga, Gs, As, Bi, Te, B, C, norium also is below 0.1%.

(survey of organization)

The survey of organization of relevant these copper alloy test portions, respectively by above-mentioned method, the average atom number that has determined the Cr that contains in the precipitate of the average atom concentration (at%) of the Cr that contains in the precipitate of 50～200nm size, identical 50～200nm size and Si is (more individual/μ m than the average number density of the precipitate of Cr/Si, identical 50～200nm size ²).

In addition, utilization has been loaded the backscattering electron diffraction in above-mentioned electric field emission type scanning electronic microscope and has been determined establishing copper alloy test portion number tissue, crystal grain as the crystal orientation method of analysis of system and be n, when if the crystal grain that determines separately directly is x, with the average crystal grain footpath (μ m) that (∑ x)/n represents.Specifically, prepare mechanical mill is carried out on the rolling surface surface of goods copper alloy, and after polishing is ground, then carry out electrolytic polishing, the test portion of regulating has been carried out on the surface., utilize NEC society system FESEM (JEOL JSM5410), carried out crystal orientation mensuration and the crystal grain of EBSP and directly measured thereafter.Measuring the zone is the zone of 300 μ m * 300 μ m, and measuring step interval is 0.5 μ m.EBSP measures resolution system and has used EBSP:TCL society system (OIM).

(tension test)

(electric conductivity measuring)

(evaluation test of bendability)

As shown in Table 6, the copper alloy in the present invention forms, promptly example 36～47 is carried out the solution processing in the optimal conditions scope, has obtained the goods copper alloy.

Therefore, 0.2～20/μ of the number density average out to m that organizes its above-mentioned each measuring method precipitate that measure, 50～200nm size of example 36～47 ²Scope, the average atom concentration of the Cr that contains in the precipitate of this scope size is the scope of 0.1～80at%, average crystal grain directly is below the 3 μ m.In addition, the atomicity of Cr that contains in the precipitate of 50～200nm size and Si is than Cr/Si average out to 0.01～10.

Consequently, in the example 36～47, be that 0.2% yield-point is more than the 800MPa, electric conductivity 4 is above high strength, a high conductivity of 0%LACS, and the copper alloy of has excellent bending properties.

Relative with it, the copper alloy of comparative example 48～55, as shown in table 5, become to be grouped into outside the scope of the invention.Therefore, though solution processing (manufacture method) is carried out in the optimal conditions scope, bendability is all inferior, and intensity and electric conductivity be step-down also.

The copper alloy of comparative example 48 does not contain Cr.Therefore, the precipitate of 50～200nm size (number density) is little, and average crystal grain directly surpasses 30 μ m and thickization.So bendability and intensity are low.

The copper alloy Cr content of comparative example 49 is higher than outside the upper limit.Therefore, the precipitate chap is big, and bendability is inferior, and simultaneously, atomic percent and the Cr/Si of the Cr that contains in the precipitate are too high, so electric conductivity is low.

The content of the copper alloy Ni of comparative example 50 is higher than outside the upper limit.Therefore, bendability and electric conductivity are obviously low.

The content of the copper alloy Ni of comparative example 51 is lower than outside the lower limit.Therefore, the precipitate of 50～200nm size (number density) is little, and average crystal grain directly surpasses 30 μ m and thickization.Consequently, bendability and intensity are obviously low.

The content of the copper alloy Si of comparative example 52 is higher than outside the upper limit.Therefore, the Cr/P that contains in the precipitate of 50～200nm size is low excessively, and average crystal grain directly surpasses 30 μ m and thickization.Consequently, bendability and electric conductivity are obviously low.

The content of the copper alloy Ni of comparative example 53 is lower than outside the lower limit.Therefore, the number density of the precipitate of 50～200nm size is too small, and the Cr/Si that contains in this size precipitate is too high, and average crystal grain directly surpasses 30 μ m and thickization.Consequently, bendability and intensity are low.

The copper alloy Zr content of comparative example 54 is too much.Therefore, average crystal grain directly surpasses 30 μ m and thickization.Consequently, bendability and electric conductivity are obviously low.

The total amount of the Fe in copper alloy of comparative example 55, Mg content is too much.Therefore, average crystal grain directly surpasses 30 μ m and thickization.Consequently, bendability and electric conductivity are obviously low.

Though the copper alloy of comparative example 56～61 shown in the example 56～61 of table 5, becomes to be grouped within the scope of the present invention, solution treatment condition (manufacture method) are outside the optimal conditions scope.Consequently, bendability is all inferior, and intensity and electric conductivity be step-down also.

Comparative example 56 is too small to 400 ℃ average heating speed of solution processing.Therefore, promote the growth of crystal grain, average crystal grain directly surpasses 30 μ m and thickization.Consequently, bendability and intensity are obviously low.

Comparative example 57 is excessive to 400 ℃ average heating speed of solution processing.Therefore, the number density deficiency of precipitate, average crystal grain directly becomes greatly, and bendability is low.

Comparative example 58 is too small from 400 ℃ of average heating speeds to the solution temperature.Therefore, average crystal grain directly becomes greatly, and bendability is low.

Comparative example 59 solution treatment temps are low excessively.Therefore, solutionization is insufficient, and intensity is low, and bendability is low.

Comparative example 60 solution treatment temps are too high.Therefore, the number density of the precipitate of 50～200nm size is too small, and average crystal grain directly surpasses 30 μ m and thickization.Consequently, bendability and intensity are low.

Average cooling rate after the comparative example 61 solution processing is too small.Therefore promote the growth of crystal grain, the average crystal grain footpath is big, and bendability is low.In addition, intensity is also low.

Fig. 1 is that example 36, Fig. 2 are each copper alloy plates of comparative example 48, be illustrated in above-mentioned each solution processing of 900 ℃ after, 50000 times TEM (scanning electron microscope) photo of above-mentioned each final plate tissue before cold rolling.In the example 36 of Fig. 1, exist for the point that contains black Cr precipitate (with fixed), that represent with 1 arrow by above-mentioned EDX is specific.On the other hand, do not contain that such precipitate does not all exist in the comparative example 48 of Fig. 2 of Cr.

By these facts, above-mentioned, the effect of the Cr of containing precipitate of the present invention, effect have been proved.That is, contain the Cr precipitate and have following special character,, also do not carry out solid solution, but exist (remaining) in tissue as precipitate even the solution treatment temp is a high temperature, thus the effect of embolization that the performance crystal grain-growth suppresses.And, the effect of embolization that this crystal grain-growth that contains the Cr precipitate suppresses with do not contain Cr so that contain the Cr precipitate, be common (present) Ni ₂Si is that the effect of embolization of precipitate is compared, and is obviously big.

In addition, proved that also this size that contains the effect of embolization of Cr precipitate is subjected to about the number density of the average atom concentration of the Cr that contains in the precipitate of 50～200nm size and this size precipitate.

Therefore,, proved not only high strength, high conductivity, and be used to make one-tenth has excellent bending properties, copper alloy plate of the present invention to be grouped into, to organize, also be useful on the meaning of preferably creating conditions that obtains organizing according to above result.

[table 5]

[table 6]

Then, embodiments of the invention 3 are described.Change Cu alloy structure and manufacture method, especially solution treatment condition, Ti average atom concentration in the precipitate in the Cu alloy structure etc. is carried out many variations, the average crystal grain of the Cu latten that obtains is directly changed, thereby respectively characteristics such as intensity, electric conductivity, bendability are estimated.

Specifically, the copper alloy that the chemical ingredients shown in the following table 7 is formed in the kryptol stove, in atmosphere, covers charcoal and dissolves respectively, casts in the cast iron multiple mould, obtains the ingot bar of thick 50mm, wide 75mm, long 180mm.And after the surface of ingot bar was cut, under 950 ℃ temperature, hot rolling became 20mm to thickness, carried out chilling but from the hot rolling end temp more than 750 ℃ water.Then,, carry out once cold rolling, obtain the plate of thickness 0.25mm except that behind the deoxidation scale.

Then, use salt bath furnace, as shown in table 8, change various intensifications, cooling conditions carries out the solution processing.And, hold-time of the plate under the solution temperature has been set as 30 seconds jointly.Then, by finally cold rolling, make the cold-reduced sheet of thickness 0.20mm respectively.The artificial age-hardening who this cold-reduced sheet is carried out 450 ℃ * 4h handles, and obtains final copper alloy.

Each example is all used the test portion that scales off from above-mentioned final copper alloy plate, the copper alloy that manufactures has like this been implemented intensity (0.2% yield-point) mensuration, electric conductivity measuring, pliability test and the evaluation of survey of organization and tension test.These results of table 8 expression.

At this, the copper alloy shown in the table 7, removing that the surplus of record after the amount of element form all be Cu, as table 7 record other elements in addition, impurity element total amounts such as Mn, Ca, Ag, Cd, Be, Au, Pt, S, Pt, P are below 0.5%.In addition, these total amount of elements such as Hf, Th, Ll, Na, K, Sr, Pd, W, Nb, Al, V, Y, Mo, In, Ga, Gs, As, Bi, Te, B, C, norium also is below 0.1%.

(survey of organization)

The survey of organization of relevant these copper alloy test portions, respectively by above-mentioned method, the average atom number that has determined the Ti that contains in the precipitate of the average atom concentration (at%) of the Ti that contains in the precipitate of 50～200nm size, identical 50～200nm size and Si is (more individual/μ m than the average number density of the precipitate of Ti/Si, identical 50～200nm size ²).

In addition, utilization has been loaded the backscattering electron diffraction in above-mentioned electric field emission type scanning electronic microscope and has been determined establishing copper alloy test portion number tissue, crystal grain as the crystal orientation method of analysis of system and be n, when if the crystal grain that determines separately directly is x, with the average crystal grain footpath (μ m) that (∑ x)/n represents.Specifically, mechanical mill is carried out on the rolling surface surface of goods copper alloy, and after polishing is ground, then carried out electrolytic polishing, be ready to the test portion that the surface has been regulated., utilize NEC society system FESEM (JEOL JSM5410), carried out crystal orientation mensuration and the crystal grain of EBSP and directly measured thereafter.Measuring the zone is the zone of 300 μ m * 300 μ m, and measuring step interval is 0.5 μ m.EBSP measures resolution system and has used EBSP:TCL society system (OIM).

(tension test)

(electric conductivity measuring)

(evaluation test of bendability)

The pliability test of copper alloy test portion is stretched copper association technological standard according to Japan and is carried out.To be cut into wide 10mm, long 30mm on the sheet material, apply the load of 1000kgf, carry out the bending of Good Way (bending axis and rolling direction meet at right angles), flawless is arranged with 50 times opticmicroscope visual observation bends with bending radius 0.15mm.What at this moment, do not have a crackle is evaluated as zero; Generated being evaluated as of crackle *.We can say that if this pliability test is good, the bendability of the strictnesses such as 90 ° of bendings behind then above-mentioned closed bending or the fluting is also good.

As shown in Table 8, the copper alloy in the present invention forms, promptly example 62～72 is carried out the solution processing in the optimal conditions scope, has obtained the goods copper alloy.

Therefore, 0.2～20/μ of the number density average out to m that organizes its above-mentioned each measuring method precipitate that measure, 50～200nm size of example 62～72 ²Scope, the average atom concentration of the Ti that contains in the precipitate of this scope size is the scope of 0.1～50at%, average crystal grain directly is below the 2 μ m.In addition, the atomicity of Ti that contains in the precipitate of 50～200nm size and Si is than Ti/Si average out to 0.01～10.

Consequently, example 62～72 is more than the 0.2% yield-point 800MPa, high strength, high conductivity that electric conductivity 40%LACS is above, and the copper alloy of has excellent bending properties.

In contrast, the copper alloy of comparative example 73～80, as shown in table 7, become to be grouped into outside the scope of the invention.Therefore, though solution processing (manufacture method) is carried out in the optimal conditions scope, bendability is all inferior, and intensity and electric conductivity are also low.

The copper alloy of comparative example 73 does not contain Ti.Therefore, the precipitate of 50～200nm size (number density) is little, and average crystal grain directly surpasses 20 μ m and thickization.So bendability and intensity are low.

The copper alloy Ti content of comparative example 74 is higher than outside the upper limit.Therefore, the precipitate chap is big, and bendability is inferior, and simultaneously, atomic percent and the Ti/Si of the Ti that contains in the precipitate are too high, and electric conductivity is low.

The content of the copper alloy Ni of comparative example 75 is higher than outside the upper limit.Therefore, bendability and electric conductivity are obviously low.

The content of the copper alloy Ni of comparative example 76 is lower than outside the lower limit.Therefore, though the precipitate of 50～200nm size (number density) is little, average crystal grain directly surpasses 20 μ m and thickization.Consequently, bendability and intensity are obviously low.

The content of the copper alloy Si of comparative example 77 is higher than outside the upper limit.Therefore, the Ti/Si that contains in the precipitate of 50～200nm size is low excessively, and average crystal grain directly surpasses 20 μ m and thickization.Consequently, bendability and electric conductivity are obviously low.

The content of the copper alloy Si of comparative example 78 is lower than outside the lower limit.Therefore, the number density of the precipitate of 50～200nm size is too small, and the Ti/Si that contains in this size precipitate is too high, and average crystal grain directly surpasses 20 μ m and thickization.Consequently, bendability and intensity are low.

The copper alloy Zr content of comparative example 79 is too much.Therefore, average crystal grain directly surpasses 20 μ m and thickization.Consequently, bendability and electric conductivity are obviously low.

The total amount of the Fe in copper alloy of comparative example 80, Co content is too much.Therefore, average crystal grain directly surpasses 20 μ m and thickization.Consequently, bendability and electric conductivity are obviously low.

Though the copper alloy of comparative example 81～86 shown in the example 81～86 of table 7, becomes to be grouped within the scope of the present invention, solution treatment condition (manufacture method) are outside the optimal conditions scope.Consequently, bendability is all inferior, and intensity and electric conductivity be step-down also.

Comparative example 81 is too small to 400 ℃ average heating speed of solution processing.Therefore, promote the growth of crystal grain, average crystal grain directly surpasses 20 μ m and thickization.Consequently, bendability and intensity are obviously low.

Comparative example 82 is excessive to 400 ℃ average heating speed of solution processing.Therefore, the number density deficiency of precipitate, average crystal grain directly becomes greatly, and bendability is low.

Comparative example 83 is too small from 400 ℃ of average heating speeds to the solution temperature.Therefore, average crystal grain directly becomes greatly, and bendability is low.

Comparative example 84 solution treatment temps are low excessively.Therefore, solutionization is insufficient, and intensity is low, and bendability is low.

Comparative example 85 solution treatment temps are too high.Therefore, the number density of the precipitate of 50～200nm size is too small, and average crystal grain directly surpasses 20 μ m and thickization.Consequently, bendability and intensity are low.

Average cooling rate after the comparative example 86 solution processing is too small.Therefore, promote the growth of crystal grain, the average crystal grain footpath is big, and bendability is low.In addition, intensity is also low.

Fig. 3 is that example 62, Fig. 4 are each copper alloy plates of comparative example 73, be illustrated in above-mentioned each solution processing of 900 ℃ after, 50000 times TEM (scanning electron microscope) photo of above-mentioned each final plate tissue before cold rolling.In the example 62 of Fig. 3, specific for containing the some existence of Ti precipitate (with fixed) black by above-mentioned EDX.On the other hand, do not contain that such precipitate does not all exist in the comparative example 73 of Fig. 4 of Ti.

By these facts, above-mentioned, the effect of the Ti of containing precipitate of the present invention, effect have been proved.That is, contain the Ti precipitate and have following special character,, also do not carry out solid solution, but exist (remaining) in tissue as precipitate even the solution treatment temp is a high temperature, thus the effect of embolization that the performance crystal grain-growth suppresses.And, the effect of embolization that this crystal grain-growth that contains the Ti precipitate suppresses with do not contain Ti so that contain the Ti precipitate, be common (present) Ni ₂Si is that the effect of embolization of precipitate is compared, and is obviously big.

In addition, proved that also this size that contains the effect of embolization of Ti precipitate is subjected to about the number density of the average atom concentration of the Ti that contains in the precipitate of 50～200nm size and this size precipitate.

Therefore,, proved not only high strength, high conductivity, and be used to make one-tenth has excellent bending properties, copper alloy plate of the present invention to be grouped into, to organize, also be useful on the meaning of preferably creating conditions that obtains organizing by above result.

[table 7]

[table 8]

The present invention is had been described in detail with reference to specific mode, but only otherwise break away from aim of the present invention and scope, can carry out various changes and correction to it, this is self-explantory for a person skilled in the art.

In addition, the application further is incorporated in documents based on the Japanese patent application (special hope 2006-257534) of application on June 22nd, 2006 and the Japanese patent application (spy is willing to 2006-257535) of application on September 22nd, 2006 with its integral body.

The possibility of industrial utilization

As described above described, according to the present invention, can provide a kind of high strength, high conductivity, and have both the copper alloy of good bendability. Consequently, use as miniaturization and light-weighted electrical and electronic parts, except semiconductor device with the lead frame, also can be applicable to purposes lead frame, binding post, terminal, switch, relay etc., high-strength high-conductivity and strict bendability.

Claims

1. the copper alloy of a high strength, high conductivity and has excellent bending properties is characterized in that, contains Ni:0.4～4.0%, Si:0.05～1.0% in quality %, also contains P:0.005～0.5%, and surplus is made up of copper and unavoidable impurities,

The atomicity that is of a size of P contained in the precipitate of 50～200nm and Si in this copper alloy tissue that electric field emission type transmission electron microscope and energy dispersion type analytical equipment by 30000 times of multiplying powers determines is than P/Si average out to 0.01～10,

And, determine 0.2～7.0/μ of the number density average out to m of the precipitate that is of a size of 50～200nm by described electric field emission type transmission electron microscope and energy dispersion type analytical equipment ²The average atom concentration of the P that contains in the precipitate of size in this scope is 0.1～50at%, and, to use the electric field emission type transmission electron microscope that has loaded backscattering electron diffraction imaging system, the number of die that determines by the crystal orientation method of analysis is decided to be n, when separately the crystal grain that determines directly is decided to be x, directly be below the 10 μ m by the average crystal grain that (∑ x)/n represents.

2. copper alloy as claimed in claim 1 is characterized in that, described copper alloy also contains in quality % add up to 0.01～3.0% more than one the element of selecting from Cr, Ti, Fe, Mg, Co, Zr.

3. the copper alloy of a high strength, high conductivity and has excellent bending properties is characterized in that, contains Ni:0.4～4.0%, Si:0.05～1.0% in quality %, also contains Cr:0.005～1.0%, and surplus is made up of copper and unavoidable impurities,

The atomicity that is of a size of Cr contained in the precipitate of 50～200nm and Si in this copper alloy tissue that electric field emission type transmission electron microscope and energy dispersion type analytical equipment by 30000 times of multiplying powers determines is than Cr/Si average out to 0.01～10,

And, determine 0.2～20/μ of the number density average out to m of the precipitate that is of a size of 50～200nm by described electric field emission type transmission electron microscope and energy dispersion type analytical equipment ²The average atom concentration of the Cr that contains in the precipitate of size in this scope is 0.1～80at%, and, to use the electric field emission type transmission electron microscope that has loaded backscattering electron diffraction imaging system, the number of die that determines by the crystal orientation method of analysis is decided to be n, when separately the crystal grain that determines directly is decided to be x, directly be below the 30 μ m by the average crystal grain that (∑ x)/n represents.

4. copper alloy as claimed in claim 3 is characterized in that, described copper alloy also contains in quality % add up to 0.01～3.0% more than one the element of selecting from Ti, Fe, Mg, Co, Zr.

5. the copper alloy of a high strength, high conductivity and has excellent bending properties is characterized in that, contains Ni:0.4～4.0%, Si:0.05～1.0% in quality %, also contains Ti:0.005～1.0%, and surplus is made up of copper and unavoidable impurities,

The atomicity that is of a size of Ti contained in the precipitate of 50～200nm and Si in this copper alloy tissue that electric field emission type transmission electron microscope and energy dispersion type analytical equipment by 30000 times of multiplying powers determines is than Ti/Si average out to 0.01～10,

And, determine 0.2～20/μ of the number density average out to m of the precipitate that is of a size of 50～200nm by described electric field emission type transmission electron microscope and energy dispersion type analytical equipment ²The average atom concentration of the Cr that contains in the precipitate of size in this scope is 0.1～50at%, and, to use the electric field emission type transmission electron microscope that has loaded backscattering electron diffraction imaging system, the number of die that determines by the crystal orientation method of analysis is decided to be n, when separately the crystal grain that determines directly is decided to be x, directly be below the 20 μ m by the average crystal grain that (∑ x)/n represents.

6. copper alloy as claimed in claim 5 is characterized in that, described copper alloy also contains in quality % add up to 0.01～3.0% more than one the element of selecting from Fe, Mg, Co, Zr.

7. as each described copper alloy in the claim 1～6, it is characterized in that described copper alloy also contains Zn:0.005～3.0% in quality %.

8. as each described copper alloy in the claim 1～6, it is characterized in that described copper alloy also contains Sn:0.01～5.0% in quality %.

9. copper alloy as claimed in claim 7 is characterized in that described copper alloy also contains Sn:0.01～5.0% in quality %.