CN102666889A

CN102666889A - Copper alloy sheet and process for producing same

Info

Publication number: CN102666889A
Application number: CN201080053384.3A
Authority: CN
Inventors: 金子洋; 佐藤浩二; 江口立彦
Original assignee: Furukawa Electric Co Ltd
Current assignee: Furukawa Electric Co Ltd
Priority date: 2009-12-02
Filing date: 2010-12-01
Publication date: 2012-09-12
Also published as: WO2011068126A1; KR20120087985A; EP2508633A1; JPWO2011068126A1; JP2014029031A; KR101747475B1; JP5503791B2; JP5400877B2; EP2508633A4

Abstract

Provided is a copper alloy sheet which has excellent bendability and excellent strength and is suitable for use in lead frames, connectors, and terminal materials for electric/electronic appliances, connectors or terminal materials for vehicular mounting, relays, switches, and the like. Also provided is a process for producing the copper alloy sheet. The copper alloy sheet, when analyzed for crystal orientation by EBSD (electron back scatter diffraction), shows accumulation of atomic planes facing in the transverse direction (TD) of the rolled sheet, wherein the areal proportion of regions having an atomic plane in which the angle between the normal line to the (111) plane and the TD is within 20 is 50% or less. The sheet has a proof strength of 500 MPa or greater and a conductivity of 30% IACS or higher.

Description

Copper alloy plate and method of manufacture thereof

Technical field

The present invention relates to copper alloy plate and method of manufacture thereof, in more detail, relate to be applicable to on-vehicle parts with or electric, electronic machine with the copper alloy plate and the method for manufacture thereof of lead frame, junctor, terminal material, rly., switch, socket etc.

Background technology

For be used for on-vehicle parts with or electric, electronic machine with the desired characteristic project of copper alloy plate of purposes such as lead frame, junctor, terminal material, rly., switch, socket; Comprise for example electric conductivity; Ys (yielding stress); Tensile strength, bendability, proof stress relaxation property etc.In recent years, be accompanied by the high temperatureization of miniaturized, lightweight, multifunction, high-density installationization and the environment for use of electric, electronic machine, the level that requires of these characteristics is improved.

Therefore, under the situation of using copper alloy plate, can enumerate following variation.

The first, be accompanied by automobile and electric, electronic machine multifunction, the multipolarization of junctor is developed, and therefore, the miniaturized separately of terminal and contact component also is developed.For example, carrying out the terminal that joint (tab) width is about 1.0mm is reduced to the work of 0.64mm.

The second, turn to background with the minimizing of mineral wealth and the light weight of parts, carrying out the thin-walled property of body material, and, in order to guarantee the spring contact pressure, use than the more high-intensity body material of current material.

The 3rd, the high temperatureization of environment for use develops.For example, in trolley part,, seeking the car body lightweight in order to reduce carbon dioxide production.Therefore, present dynamically is: such engine control that will be arranged at car door is arranged in the nacelle with electronic machines such as ECU or near the mover, to shorten the wirning harness between electronic machine and the mover.

And, being accompanied by above-mentioned variation, copper alloy plate can produce following problem.

The first, be accompanied by the miniaturized of terminal, the radius-of-curvature of the bending machining that docking point part and spring section are implemented reduces, and material is implemented than stricter in the past bending machining.Therefore, be created in the problem that occurs crackle or fold on the material.

The second, be accompanied by the high strength of material, be created in the problem that occurs crackle on the material.Its reason is that in general, the bendability of material and intensity have the relation of compromise selection.

The 3rd, if crackle occurs in the bending machining portion of docking point part and spring section enforcement, then the contact pressure of contact portions reduces; Thereby the contact resistance of contact portions is risen, and electrical connection is insulated, and has lost the function as junctor; Therefore, become great problem.

To the requirement that improves this bendability, several kinds of schemes that solve the problems referred to above through the control crystalline orientation have been proposed.Patent documentation 1 has been found following content: in the Cu-Ni-Si series copper alloy, at crystal particle diameter with from { 311}, { 220}, { X-ray diffraction intensity of 200} face satisfies under the situation of various crystalline orientations of a certain condition, excellent in bending workability.In addition, patent documentation 2 has been found following content: in the Cu-Ni-Si series copper alloy, from { 200} face and { X-ray diffraction intensity of 220} face satisfies under the situation of crystalline orientation of a certain condition, excellent in bending workability.In addition, patent documentation 3 has been found following content: in the Cu-Ni-Si series copper alloy, through suitable control Cube orientation 100}＜001＞ratio, excellent in bending workability.In addition, in patent documentation 4 ~ 8, proposed the X-ray diffraction intensity of various atomic planes has been carried out the material of the excellent in bending workability of regulation.Patent documentation 4 has been found following content: in the Cu-Ni-Co-Si series copper alloy; From { X-ray diffraction intensity of 200} face is with respect to from { 111} face, { 200} face, { 220} face and { X-ray diffraction intensity of 311} face satisfies under the situation of crystalline orientation of a certain condition, excellent in bending workability.Patent documentation 5 has been found following content: in the Cu-Ni-si series copper alloy, from { 420} face and { X-ray diffraction intensity of 220} face satisfies under the situation of crystalline orientation of a certain condition, excellent in bending workability.Patent documentation 6 has been found following content: in the Cu-Ni-Si series copper alloy, in that { 123}＜412＞orientation satisfies under the situation of crystalline orientation of a certain condition, excellent in bending workability.Patent documentation 7 has been found following content: in the Cu-Ni-Si series copper alloy, from { 111} face, { 311} face and { X-ray diffraction intensity of 220} face satisfies under the situation of crystalline orientation of a certain condition, the excellent in bending workability of Bad Way (afterwards stating).In addition, patent documentation 8 has been found following content: in the Cu-Ni-si series copper alloy, from { 200} face, { 311} face and { X-ray diffraction intensity of 220} face satisfies under the situation of crystalline orientation of a certain condition, excellent in bending workability.

The regulation of X-ray diffraction intensity is that (rolling normal direction, gathering ND) is stipulated to plate face direction to specific crystal face in the

patent documentation

1,2,4,5,7,8.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2006-009137 communique

Patent documentation 2: TOHKEMY 2008-013836 communique

Patent documentation 3: TOHKEMY 2006-283059 communique

Patent documentation 4: TOHKEMY 2009-007666 communique

Patent documentation 5: TOHKEMY 2008-223136 communique

Patent documentation 6: TOHKEMY 2007-092135 communique

Patent documentation 7: TOHKEMY 2006-016629 communique

Patent documentation 8: japanese kokai publication hei 11-335756 communique

Summary of the invention

The problem that invention will solve

But the invention of record is based on by the mensuration from the crystalline orientation of the X-ray diffraction of specific crystal face and obtains in patent documentation 1 or the patent documentation 2, only relates to a fraction of certain surface in the distribution of the crystalline orientation with a certain scope.And, nothing but the crystal face of only having measured plate face direction (ND), can not control towards rolling direction (RD) or plate width direction (TD) which crystal face.Therefore, for controlling bendability fully, remain inadequate method.In addition, in the invention of in patent documentation 3, being put down in writing, pointed out the validity of Cube orientation, but can not control that the improvement of bendability is insufficient sometimes to other crystalline orientation composition.In addition, in patent documentation 4 ~ 8, only inquired into respectively above-mentioned specific crystal face or orientation are measured, controlled, identical with patent documentation 1 ~ 3, the improvement of bendability is insufficient sometimes.

In view of above-mentioned such problem; The objective of the invention is to; A kind of copper alloy plate and method of manufacture thereof are provided; The excellent in bending workability of this copper alloy plate has excellent intensity, and is suitable for electric, electronic machine with lead frame, junctor, terminal material etc., the automobile mounted junctor of using etc. or terminal material, rly., switch etc.

The method of dealing with problems

The inventor etc. have carried out research repeatedly; Study being fit to copper alloy electric, the electronic unit purposes; The result finds that the crackle in the time of can suppressing bending machining is found in addition through reducing (111) face towards the zone of the width (TD) of milled sheet; Area occupation ratio through should the zone is made as below the SP, can significantly improve bendability.Also find in addition, except above-mentioned characteristic,, can improve intensity and proof stress relaxation property and can not damage electric conductivity and bendability through in this alloy system, using specific interpolation element.The inventor etc. have accomplished the present invention based on these opinions.

That is, the present invention provides following solution.

(1) a kind of copper alloy plate; Wherein, (Electron Back Scatter Diffraction: during the crystalline orientation of EBSD) measuring was analyzed, about the gathering towards the atomic plane of the width (TD) of milled sheet, the angle with angle that the normal of (111) face become with TD was that 20 ° of area occupation ratios with the zone of interior atomic plane are below 50% at EBSD; Ys is more than the 500MPa, and electric conductivity is more than the 30%IACS.

(2) above-mentioned (1) described copper alloy plate, wherein, alloy composition comprises: total amount is the Ni of 0.5 ~ 5.0 quality % and any or two kinds among the Co, and the Si of 0.1 ~ 1.5 quality %, and surplus is Cu and unavoidable impurities.

(3) above-mentioned (1) or (2) described copper alloy plate wherein, also contain and are selected from least a among Sn, Zn, Ag, Mn, B, P, Mg, Cr, Fe, Ti, Zr and the Hf, and its total amount is 0.005 ~ 2.0 quality %.

(4) each described copper alloy plate in above-mentioned (1) ~ (3), it uses material for junctor.

(5) a kind of method of manufacture of copper alloy plate; It is a method of making each described copper alloy plate in above-mentioned (1) ~ (4); This method comprises: the copper alloy of the alloy composition that obtains said copper alloy plate is implemented casting [operation 1] successively; Homogenizing thermal treatment [operation 2]; Hot-work [operation 3]; Cold rolling [operation 6]; Thermal treatment [operation 7]; Cold rolling [operation 8]; Middle recrystallize thermal treatment [operation 9]; [operation 10] handled in final solution heat-transmission; Implement timeliness then and separate out thermal treatment [operation 11]

Wherein, when the complete solid solubility temperature with solute atoms is made as P ℃, said in the middle of recrystallize thermal treatment [operation 9] be that temperature below more than (P-200) ℃ and (P-10) ℃ keeps 1 second ~ 20 hour; [operation 10] handled in said final solution heat-transmission is to keep 1 second ~ 10 minute below more than (P+10) ℃ and (P+150) ℃.

(6) method of manufacture of above-mentioned (5) described copper alloy plate wherein, is separated out thermal treatment [operation 11] afterwards in said timeliness, implements cold rolling [operation 12] and modified annealing [operation 13] successively.

The effect of invention

The excellent in bending workability of copper alloy plate of the present invention, and have excellent intensity is suitable for electric, electronic machine with lead frame, junctor, terminal material etc., the automobile mounted junctor of using etc. or terminal material, rly., switch etc.

In addition; The method of manufacture of copper alloy plate of the present invention is preferred as the method for making following copper alloy plate; The excellent in bending workability of said copper alloy plate; And have excellent intensity, be suitable for electric, electronic machine with lead frame, junctor, terminal material etc., the automobile mounted junctor of using etc. or terminal material, rly., switch etc.

Description of drawings

Fig. 1 is the explanatory view of the TP of proof stress relaxation property, and wherein, what Fig. 1 (a) illustrated is the state before the thermal treatment, and what Fig. 1 (b) illustrated is the state after the thermal treatment.

Fig. 2 illustrates that electric conductivity rises along with thermal treatment temp and the graphic representation of the typical case of the variation that takes place, schematically shows the method for the temperature (P) ℃ of the complete solid solution of decision solute atoms thus.

Fig. 3 (a) illustrates is that the angle at the angle that become with TD of the normal of (111) face is 20 ° of examples with interior atomic plane; Fig. 3 (b) illustrates is the example that the angle at the angle that become with TD of the normal of (111) face surpasses 20 ° atomic plane.In Fig. 3 (a) and (b) the conical area shown in the dotted line represent with the angle at the angle that normal became of (111) face be 20 ° with interior zone.

Shown in Fig. 4 be the angle at the angle that normal in the representational set tissue orientating composition, (111) face is become with TD in FCC (face-centered cubic lattice) metal be 20 ° with the example of interior atomic plane towards the set tissue orientating composition of milled sheet width (TD).

Nomenclature

1 test film when applying initial stress

2 remove the test film behind the load

3 test films under the situation of load stress not

4 testing tables

Embodiment

Preferred implementation in the face of copper alloy plate of the present invention is elaborated down.At this, " Cu alloy material " is meant the copper alloy raw material is processed into the material to shaped (for example, plate, bar, paper tinsel, rod, line etc.).Wherein, sheet material is meant to have specific thicknesses, dimensionally stable, on the face direction, have the material of width, broadly comprises web.At this, in sheet material, " material surface " is meant " plate top layer ", and " depth location of material " is meant " position of thickness of slab direction ".The thickness of sheet material is not special to be limited, and still, considers more remarkable effect of the present invention, also is fit to practical application, is preferably 8 ~ 800 μ m, more preferably 50 ~ 70 μ m.

In addition; Copper alloy plate of the present invention is stipulated its characteristic with the integrated rate (aggregation rate) of the atomic plane of milled sheet on assigned direction; But, in the present invention, as long as have above-mentioned characteristic as copper alloy plate; The shape of copper alloy plate is not limited to sheet material or web, and tubing also can be used as the sheet material explanation and treats as sheet material.

(regulation that EBSD measures)

In order to find out copper alloy plate crack reason when the bending machining, the metal structure of the material after to flexural deformation such as the inventor studies in great detail.It is not to be out of shape equably that the result observes body material, and distortion only concentrates on the zone of particular crystal orientation, and what carry out is uneven distortion.And, can know: because its nonaffine deformation, produce several microns dark folds, fine crackle on the substrate material surface after the bending machining.But; The result that the inventor etc. further investigate finds; Reduce measure regulation by EBDS (111) face under the situation in the zone of the atomic plane of milled sheet width (TD) (, being described in detail below) for this zone, uneven distortion is inhibited; The fold that on the surface of body material, produces reduces, and crackle is inhibited.

As the mechanism of this phenomenon, can think that (111) face is that one of processing solidified orientation takes place the most easily under the effect of tensile stress, also be the orientation that dislocation (translocation position) increases easily under the stress in flexural deformation.The dislocation of highly denseization can become the generation source of micropore (マイ Network ロボイ De), thereby becomes the reason of crackle.Can think that particularly in the bent axle BW bending parallel with respect to rolling direction, bendability is improved through reducing the ratio of (111) face of being somebody's turn to do towards the zone of the atomic plane of TD.

Shown in Fig. 4 be the angle at the angle that become with TD of the normal of (111) face be 20 ° with the representational example of interior atomic plane in the orientation component of the set tissue of TD.Be equivalent to P orientation 011}＜111＞, the SB orientation 186}＜211＞, the S orientation 132}＜643＞, the Z orientation 111}＜110＞, the twin crystal orientation of Cube orientation 122}＜221＞, the Brass orientation 110}＜112＞etc.Comprise these orientation components, (111) face is the set tissue with given area occupation ratio that the present invention stipulates towards the state that the set tissue orientating components in proportions of TD is comprehensively suppressed.Up to the present, it is unknown having the technology that the area occupation ratio of the atomic plane of above-mentioned orientation is inhibited simultaneously.

At the width (TD) of milled sheet, angle with angle that the normal of (111) face become with TD is that 20 ° of area occupation ratios with the zone of interior atomic plane are 50% when following, can obtain above-mentioned effect.Preferred above-mentioned area occupation ratio is below 45%, more preferably more than 1% and below 40%, is preferably more than 30% especially and below 35%.Through defining this area occupation ratio and it is specific for above-mentioned scope, as stated, can seek to improve bendability.

It is that X axle, plate width direction (TD) are that Y axle, rolling normal direction (ND) are the rectangular coordinate system of Z axle that the method for expressing of the crystalline orientation in this specification sheets adopts the rolling direction (RD) with material, and stipulates the ratio of (111) face towards the zone of TD with its area occupation ratio.Calculate the normal of (111) face of measuring each crystal grain in the zone and the angle at two angles that vector became of TD; For having this angle is that 20 ° of zones with interior atomic plane add up to its area; And adding up to area divided by total area of measuring with this, the angle at the angle that the value that obtains is become with TD as the normal with (111) face is 20 ° of area occupation ratios with the zone of interior atomic plane (%).

Promptly; In the present invention; The said angle that relates to towards the gathering of the atomic plane of the width (TD) of milled sheet and have an angle that the normal of (111) face become with TD is that 20 ° of zones with interior atomic plane are meant; Relate to towards the width (TD) of milled sheet, the i.e. gathering of the atomic plane relative, and will be 20 ° of summations for (111) face of normal itself with the angle that has comprised the angle that the normal that owns (111) faces is become with TD as the width (TD) of the milled sheet of ideal orientation with the zone of the existing planar orientation of atomic plane of each interior atomic plane with the TD direction.Below, also abbreviate these zones the zone of (111) face as towards the atomic plane of TD.

Fig. 3 illustrates foregoing.Fig. 3 (a) illustrates is that the angle at the angle that become with TD of the normal of (111) face is 20 ° of examples with interior atomic plane; In this manual; Owing to used simultaneously the atomic plane shown in this example simply turned to and had of the record of (111) face towards the atomic plane of the orientation of milled sheet width (TD); Therefore; Be recited as and have (111) face under the situation of the atomic plane of the orientation of milled sheet width (TD), also the angle at the angle that become with TD of the normal of expression (111) face is 20 ° of summations with the planar orientation of interior atomic plane.

Fig. 3 (b) illustrates is the example that the angle at the angle that become with TD of the normal of (111) face surpasses 20 ° atomic plane, and the atomic plane shown in this example is meant to have (111) face not towards the atomic plane of the orientation of milled sheet width (TD).In copper alloy, have 8 (111) faces, but only for wherein normal line vector and nearest (111) face of TD, use in the drawings circular cone (dotted line) show with the angle at the angle that normal became of (111) face be 20 ° with interior vector region.

Adopt the information that obtains in the orientation analysis of EBSD to comprise that electron rays penetrates the orientation information of the degree of depth of severals 10nm of sample, enough little for measuring width, so in this manual, be recited as area occupation ratio.

The EBSD method is used in the analysis of the above-mentioned crystalline orientation among the present invention.EBSD is the abbreviation of Electron BackScatter Diffraction (EBSD), is meant the crystalline orientation analytical technology that is utilized in the reflection electronic Kikuchi lines diffraction (Kikuchi pattern) that produces when sem (Scanning Electron Microscope:SEM) is interior shines electron rays to sample.In the present invention, to the square sample area of the 500 μ m that comprise 200 above crystal grain, scan, orientation is analyzed with 0.5 μ m step-length.

Through in the analysis of crystalline orientation, using EBSD to measure; In the gathering of plate face direction (ND) a great difference is arranged with the specific atoms face that utilizes X-ray diffraction method to measure in the past; Can obtain the approaching crystalline orientation information more fully on the three-dimensional with higher resolving power; Therefore, for the crystalline orientation of domination bendability, can obtain brand-new opinion.

Need to prove that when carrying out the EBSD measurement, in order to obtain distinct Kikuchi lines diffraction image, preferably after mechanical mill, the abrasive particle of use colloid silica carries out matrix surface measuring after the mirror ultrafinish again.In addition, measuring the slave plate surface begins to carry out.

(alloy composition etc.)

·Ni、Co、Si

Use material as junctor of the present invention, use copper or copper alloy.As having the desired electroconductibility of junctor, physical strength and stable on heating material outside the copper removal, are preferably phosphor bronze, brass, German silver, beryllium copper, and the gloomy copper nisiloy of section is alloy copper alloys such as (Cu-Ni-Si systems).Particularly satisfy the specific crystalline orientation of the present invention and assemble under the situation of area occupation ratio of relation going for, be preferably the material of fine copper system and comprise beryllium copper, the gloomy copper nisiloy of section the precipitation type alloy that is alloy.In addition, in order to have both desired HS of small-sized terminal material and high conductivity foremost, be preferably the precipitation type copper alloy of Cu-Ni-Si system, Cu-Ni-Co-Si system and Cu-Co-Si system.

This be because, for solid solution type alloys such as phosphor bronze, brass, become the nuclear of Cube orientation crystal grain-growth in the crystal grain-growth in thermal treatment, the tiny area with Cube orientation in the cold rolling material reduces.The reason lies in phosphor bronze, brass and other stacking fault energy (laminated Defects Line Energy Hikaru ギ a) low system, cold rolling shear bands easily extensible.

In the present invention, for adding nickel (Ni), cobalt (Co) and the silicon (Si) that first in the copper (Cu) adds element set to,, the compound of Ni-Si, Co-Si, Ni-Co-Si is separated out, thereby improve the intensity of copper alloy through control addition separately.Its addition is following: in the total amount of any or two kinds among Ni and the Co, be preferably 0.5 ~ 5.0 quality %, more preferably 0.6 ~ 4.5 quality %, further be preferably 0.8 ~ 4.0 quality %.The addition of Ni is preferably 1.5 ~ 4.2 quality %, 1.8 ~ 3.9 quality % more preferably, and on the other hand, the addition of Co is preferably 0.3 ~ 1.8 quality %, 0.5 ~ 1.5 quality % more preferably.Particularly wanting to improve under the situation of electric conductivity, preferably must add Co.Total addition level through not making these elements is too much, can guarantee electric conductivity fully, and is very few through the total addition level that does not make these elements in addition, can guarantee intensity fully.In addition, the content of Si is preferably 0.1 ~ 1.5 quality %, 0.2 ~ 1.2 quality % more preferably.

Other element

Then, the effect that is used for making the interpolation element that characteristics (quadratic behavior) such as proof stress relaxation property improve is described.As preferred interpolation element, can enumerate out Sn, Zn, Ag, Mn, B, P, Mg, Cr, Fe, Ti, Zr and Hf.In order to make full use of additive effect, and electric conductivity is reduced, its total amount is preferably 0.005 ~ 2.0 quality %, and more preferably 0.01 ~ 1.5 quality % further is preferably 0.03 ~ 0.8 quality %.Total amount through not making these add element is too much, can guarantee electric conductivity fully, and is very few through the total amount that does not make these add element in addition, can bring into play the effect of adding these elements fully.

Below, the additive effect of each element is shown.Mg, Sn, Zn can improve the proof stress relaxation property through adding in Cu-Ni-Si system, Cu-Ni-Co-Si system, the Cu-Co-Si series copper alloy.Compare with the situation of adding separately respectively, under the situation that combination is added, can further improve the proof stress relaxation property through synergistic effect.In addition, has the remarkable effect of improving the scolding tin embrittlement.

If add Mn, Ag, B, P, hot workability is improved, improve intensity simultaneously.

Cr, Fe, Ti, Zr, Hf separate out with simple substance form or with the form as the compound of Ni, Co or the Si of main adding elements imperceptibly, thereby help to separate out curing.In addition,, separate out,, have the effect that makes crystal particle diameter fine, thereby make bendability good through suppressing crystal grain-growth with the size of 50 ~ 500nm as compound.

(method of manufacture etc.)

Then, the method for manufacture of copper alloy plate of the present invention (method that its crystalline orientation is controlled) is described.At this, enumerate precipitation type copper alloy plate (web) and describe as an example, but can expand to solid solution type alloy material, thin system (uncommon thin system) alloy material, fine copper based material.

In general; The precipitation type copper alloy is made as follows: the ingot bar after the homogenizing thermal treatment carry out thin plateization through hot rolling and each cold rolling step; Carrying out final solution heat-transmission 700 ~ 1020 ℃ TRs handles; Make solute atoms solid solution again, separate out the intensity that thermal treatment and pinch pass are satisfied the demand it through timeliness then.Timeliness is separated out the condition of thermal treatment and pinch pass and is adjusted according to characteristics such as desired intensity and electroconductibility.The recrystallize that the set tissue of copper alloy takes place in handling through the final solution heat-transmission in this a series of step roughly determines, and the final decision through the rotation of the orientation that takes place in the finish rolling.

Method of manufacture as copper alloy plate of the present invention; For example can enumerate through carrying out following [operation 1] ~ [operation 13] successively and obtain the method for copper alloy plate of the present invention; Said [operation 1] ~ [operation 13] carried out as follows: [operation 1]; To comprise copper alloy starting material that given alloying constituent forms through the high-frequency melting furnace fusion, and it is cast and obtains ingot bar; [operation 2] implemented 10 minutes ~ 10 hours homogenizing thermal treatment to this ingot bar under 700 ~ 1020 ℃; [operation 3] is that the working modulus of carrying out under 500 ~ 1020 ℃ is 30 ~ 98% hot rolling in processing temperature; [operation 4], water-cooled; [operation 5], the face cutting; [operation 6], 50 ~ 99% cold rolling; [operation 7] keeps the thermal treatment of 10 second ~ 5 minute under 600 ~ 900 ℃; [operation 8], the cold working of 5 ~ 55% working moduluses; [operation 9] keeps the middle recrystallize thermal treatment of 1 second ~ 20 hour below more than (P-200) ℃ and (P-10) ℃; [operation 10] keeps below more than (P+10) ℃ and (P+150) ℃ the final solution heat-transmission of 1 second ~ 10 minute to handle; Carry out following operation then: [operation 11], in 350 ~ 600 ℃, carry out 5 minutes ~ 20 hours timeliness and separate out thermal treatment; [operation 12], the finish rolling of 2 ~ 45% working moduluses; [operation 13] keeps the modified annealing of 10 second ~ 2 hour under 300 ~ 700 ℃.

Copper alloy plate of the present invention is the method for manufacture manufacturing through above-mentioned embodiment preferably; But, then may not stick to all process steps that carries out above-mentioned [operation 1] ~ [operation 13] in order as long as the crystalline orientation in EBSD measures satisfies above-mentioned given area occupation ratio in resolving.In above-mentioned [operation 1] ~ [operation 13], can be that final operation finishes also for example with [operation 11], this is also contained in the aforesaid method.Perhaps can also carry out more than twice one or two operation in above-mentioned [operation 11]～[operation 13] repeatedly.For example, can also carry out cold rolling [operation 12 '] of 2 ~ 45% working moduluses before in enforcement [operation 11].

Under the lower situation of the end temp of hot rolling [operation 3],, therefore may not need water-cooled [operation 4] because speed of separating out is slack-off.At which kind of finish hot rolling below the temperature and need not to carry out water-cooled,, can suitably select because of the difference of the amount of separating out in alloy concentrations and the hot rolling is different.The situation of the rust deposite of the material surface after the also with good grounds hot rolling and omission face cutting [operation 5].In addition, can also remove rust deposite through the dissolving that utilizes acid to clean etc.

Sometimes will the high temperature rolling that carries out more than the dynamic recrystallization temperature be called hot rolling, will more than the room temperature and the high temperature rolling that carries out under the high temperature below the dynamic recrystallization temperature be called warm-rolling, this term is separately used, but usually both is generically and collectively referred to as hot rolling.In the present invention, both are closed be called hot rolling.

For the method for manufacture of copper alloy plate of the present invention, in above-mentioned final solution heat-transmission was handled, in order to reduce the ratio towards (111) of plate width face, following method of manufacture was effective.

As the common method of manufacture of in the past precipitation type copper alloy, because when the solution heat-transmission is handled also recrystallize can take place, so can realize solid solution and these two purposes of recrystallize of solute atoms simultaneously.On the other hand, in the method for manufacture of copper alloy plate of the present invention, above-mentioned two purposes realize one by one, and control sets is set up the crystalline orientation of knitting jointly simultaneously, therefore, carry out through thermal treatment separately respectively.That is,, at first carry out centre recrystallize thermal treatment [operation 9], carry out final solution heat-transmission then and handle [operation 10] to the material that is provided.

And this centre recrystallize thermal treatment is stipulated with the form of the specific TR of temperature P ℃ of regulation of the complete solid solution of use solute atoms with final solution heat-transmission treatment temperature.

The heat treated temperature of middle recrystallize be more than (P-200) ℃ and (P-10) ℃ below.This temperature is crossed when low, and recrystallize is insufficient, on the contrary, when this temperature is too high, can fully not reduce towards the ratio of TD (111) face.The heat treated temperature of middle recrystallize is preferably (P-170) ℃ ~ (P-20) ℃, more preferably (P-140) ℃ ~ (P-30) ℃.

Final solution heat-transmission treatment temperature be more than (P+10) ℃ and (P+150) ℃ below.This temperature is crossed when hanging down, and the solid solution of solute atoms is insufficient, on the contrary, when this temperature is too high, thickization of crystal grain.Final solution heat-transmission treatment temperature is preferably (P+20) ℃ ~ (P+130) ℃, more preferably (P+30) ℃ ~ (P+100) ℃.

The temperature P of the complete solid solution of solute atoms (℃) obtain through the usual method that is described below.With ingot bar after carrying out 1 hour homogenizing under 1000 ℃; Implement hot rolling and cold rolling and process sheet material; Then in salt bath in 700 ~ 1000 ℃ TR per 10 ℃ kept for 30 seconds, heat-treat, carry out shrend then; The state that freezes the solid solution in each temperature and separate out has been measured electric conductivity.Use the substitute characteristic of electric conductivity as the solid solution element amount, with electric conductivity descend along with the rising of thermal treatment temp the temperature that reaches capacity be set at complete solid solubility temperature P (℃).Illustrate that typical electric conductivity changes Fig. 2 model utility and confirm thus said temperature P (℃) method.For the complete solid solubility temperature P of specific components (℃) for, it is according to the difference of the kind of alloy and processing, treatment condition etc. and difference, but as typical case, is generally about 720 ~ 980 ℃.

The middle heat treated treatment time of recrystallize is 1 second ~ 20 hour, more preferably 5 second ~ 10 hour.The middle heat treated treatment time of recrystallize, recrystallize did not carry out when too short, and in addition, the heat treated treatment time of middle recrystallize is when long, thickization of crystal grain, and plasticity reduces.

The treatment time that final solution heat-transmission is handled is 1 second ~ 10 minute, more preferably 5 second ~ 5 minute.The treatment time that final solution heat-transmission is handled, the solid solution of solute atoms was insufficient when too short, in addition, when finally the treatment time of solution heat-transmission processing is long, thickization of crystal grain, plasticity reduces.

In the present invention, because intermediate heat treatment (operation 7) also has special technical meaning, therefore, set forth at this.Through than the thermal treatment under complete solid solubility temperature P ℃ low slightly temperature and the more cryogenic condition, can obtain the tissue that recrystallize does not take place whole face.That is, in the crystalline orientation in rolling stock, reply fast crystalline orientation and reply slower crystalline orientation, therefore, form the tissue of inhomogeneous recrystallize owing to its difference owing to exist.The ununiformity that forms based on this intention can promote the recrystallize in the middle recrystallize thermal treatment [operation 9] to gather first developing of tissue.Become recrystallized structure though reply the part of slower orientation, reply and organize crystalline orientation recrystallize can not take place faster.

Copper alloy plate of the present invention can satisfy the for example desired characteristic of copper alloy for connector use sheet material.Particularly, copper alloy plate of the present invention can be realized following superperformance: 0.2% ys satisfies 500MPa above (be preferably more than the 600MPa, be preferably more than the 700MPa especially); For bendability, with thickness of slab (t:mm) divided by can flawless ground in the pliability test of 90 ° of W carrying out the minimum profile curvature radius (r:mm) of bending machining and the value (r/t) that obtains is below 1; And electric conductivity satisfies, and 30%IACS is above (to be preferably more than the 35%1ACS; Be preferably more than the 40%IACS especially); In addition; For the proof stress relaxation property, through after the stress relaxation rates of measuring at 150 ℃ of measuring methods that kept down 1000 hours (SR) stated satisfy and (be preferably below 25%) below 30%.

Embodiment

Below, the present invention will be described in more detail based on embodiment, but the present invention is not limited to these embodiment.

Embodiment 1

Utilize that high-frequency melting furnace will be shown in the composition on alloying constituent one hurdle of table 1-1, contain among Ni and the Co one or both at least and amount to 0.5 ~ 5.0 quality %, and the Si of 0.1 ~ 1.5 quality %; Surplus is that the alloy that Cu and unavoidable impurities form fuses; Again it is cast, obtained ingot bar.Then; Carry out successively the homogenizing thermal treatment of carrying out 10 minutes ~ 10 hours under 700 ℃ ~ 1020 ℃, processing temperature be carry out under 500 ℃ ~ 1020 ℃ working modulus be 30 ~ 98% hot rolling, water-cooled, and 50 ~ 99% cold rolling; This state as feed, is made the confession examination material of the copper alloy plate of the present invention example 1-1 ~ 1-19 and comparative example 1-1 ~ 1-9 through arbitrary operation among following A ~ F.

(operation A)

Carry out in 600 ~ 900 ℃ of thermal treatments that keep down 10 second ~ 5 minute, 5 ~ 55% working moduluses cold working, keep middle the recrystallize thermal treatment of 1 second ~ 20 hour below more than (P-200) ℃ and (P-10) ℃, keep the final solution heat-transmission processing of 1 second ~ 1 minute below more than (P+10) ℃ and (P+150) ℃.Then, carry out separating out the finish rolling of thermal treatment, 2 ~ 45% working moduluses 350 ~ 600 ℃ of timeliness that kept 5 minutes ~ 20 hours down, 300 ~ 700 ℃ of modified annealing that keep 10 second ~ 2 hour down.

(process B)

Carry out in 600 ~ 900 ℃ of thermal treatments that keep down 10 second ~ 5 minute, 5 ~ 55% working moduluses cold working, keep middle the recrystallize thermal treatment of 1 second ~ 20 hour below more than (P-200) ℃ and (P-10) ℃, keep the final solution heat-transmission processing of 1 second ~ 1 minute below more than (P+10) ℃ and (P+150) ℃.The timeliness rolling, that in 350 ~ 600 ℃, carried out 5 minutes ~ 20 hours of then, carrying out 2 ~ 40% working moduluses separates out the finish rolling of thermal treatment, 2 ~ 45% working moduluses, 300 ~ 700 ℃ of modified annealing that keep 10 second ~ 2 hour down.

(operation C)

Carry out in 600 ~ 900 ℃ of thermal treatments that keep down 10 second ~ 5 minute, 5 ~ 55% working moduluses cold working, keep middle the recrystallize thermal treatment of 1 second ~ 20 hour below more than (P-200) ℃ and (P-10) ℃, keep the final solution heat-transmission processing of 1 second ~ 1 minute below more than (P+10) ℃ and (P+150) ℃.Then, separate out thermal treatment 350 ~ 600 ℃ of timeliness of carrying out 5 minutes ~ 20 hours.

(step D)

Carry out in 600 ~ 900 ℃ of thermal treatments that keep down 10 second ~ 5 minute, 5 ~ 55% working moduluses cold working, keep middle the recrystallize thermal treatment of 1 second ~ 20 hour below more than (P-200) ℃ and (P-10) ℃, keep the final solution heat-transmission processing of 1 second ~ 1 minute below more than (P+10) ℃ and (P+150) ℃.The timeliness rolling, that in 350 ~ 600 ℃, carried out 5 minutes ~ 20 hours of then, carrying out 2 ~ 45% working moduluses is separated out thermal treatment.

(operation E)

Carry out more than (P-200) ℃ and (P-10) ℃ below keep middle the recrystallize thermal treatment of 1 second ~ 20 hour, keep the final solution heat-transmission processing of 1 second ~ 1 minute below more than (P+10) ℃ and (P+150) ℃.Then, 350 ~ 600 ℃ of timeliness of carrying out 5 minutes ~ 20 hours separate out thermal treatment, again carry out the finish rolling of 2 ~ 45% working moduluses, 300 ~ 700 ℃ of modified annealing that keep down 10 second ~ 2 hour.

(operation F)

Carry out in 600 ~ 900 ℃ of thermal treatments that keep down 10 second ~ 5 minute, 5 ~ 55% working moduluses cold working, keep below more than (P+10) ℃ and (P+150) ℃ the final solution heat-transmission of 1 second ~ 1 minute to handle.Then, 350 ~ 600 ℃ of timeliness of carrying out 5 minutes ~ 20 hours separate out thermal treatment, again carry out the finish rolling of 2 ~ 45% working moduluses, 300 ~ 700 ℃ of modified annealing that keep down 10 second ~ 2 hour.

In addition, each thermal treatment and rolling after, carry out according to the state of the oxidation of material surface and roughness that acid is cleaned, surface grinding, and utilize tension level(l)er to proofread and correct according to shape.

This confession examination material is carried out following characteristic investigation.At this, supplying the thickness of examination material is 0.15mm.The result of the present invention's example is shown in table 1-1, and the result of comparative example is shown in table 1-2.

A. (111) face is towards the area occupation ratio in the zone of the atomic plane of TD:

Adopting the EBSD method, in the square mensuration zone of about 500 μ m, is that the condition of 0.5 μ m is measured with scanning step.Measuring area is that benchmark is adjusted with the crystal grain that comprises more than 200.As stated; About comprised as each ideal orientation with TD be normal (111) face, and the angle at the angle that become with TD of the normal of (111) face be 20 ° of zones (these faces lump together and are the zone of above-mentioned (111) face towards the atomic plane of TD) with each interior atomic plane, calculate their total area occupation ratio according to following formula.

Area occupation ratio (%)={ (angle at the angle that the normal of (111) face is become with TD is 20 ° of total areas with interior atomic plane)/always measure area } * 100

In each following table, it only is expressed as " area occupation ratio (%) ".

Need to prove,, used the OIM5.0HIKARI of TSL manufactured as the EBSD determinator.

B. bendability:

Vertically be cut into wide 10mm, long 25mm with rolling direction; To carry out the crooked form of W with the rectangular mode of rolling direction according to the axle of bending and be made as GW (Good Way); Will the mode parallel have carried out the crooked form of W and be made as BW (Bad Way) with rolling direction; Through 50 times observation by light microscope bend, investigation has flawless.

With bending machining portion flawless, the also slight test portion of fold is judged to be " good (◎) "; With flawless but fold is big in practicality no problem test portion be judged to be " can (zero) "; To there be the test portion of crackle to be judged to be " can not (*) ".The angle of bend of each bend is 90 °, and the inner radius of bend is 0.15mm.

C.0.2% ys [YS]

According to JIS Z2241 benchmark, measure three JIS Z2201-13B test films that cut out from rolling parallel direction, and its MV is shown.

D: electric conductivity [EC]

In the thermostatic bath that keeps 20 ℃ (± 0.5 ℃), adopt four-terminal method instrumentation resistivity, calculate electric conductivity.Need to prove that terminal pitch is from being made as 100mm.

E. stress relaxation rate [SR]

Stretch the JCBA T309:2001 standard (this is a tentative standard, and old standard is " the material industry meeting standard specifications EMAS-3003 of NEC ") of copper association based on Japan, as follows, measure 150 ℃ of conditions after keeping 1000 hours down.Through the cantilever method load ys be 80% initial stress.

Fig. 1 is the explanatory view of the TP of proof stress relaxation property, and Fig. 1 (a) is the state before the thermal treatment, and Fig. 1 (b) is the state after the thermal treatment.Shown in Fig. 1 (a), the position of the test film 1 when to apply ys be 80% initial stress to the test film 1 that on testing table 4, keeps through cantilever is apart from benchmark δ ₀Distance.It is kept 1000 hours (thermal treatment under the state of above-mentioned test film 1) in 150 ℃ thermostatic bath, shown in Fig. 1 (b), the position of removing the test film 2 behind the load is the distances apart from benchmark Ht.The 3rd, the test film during load stress not, its position is the distance apart from benchmark H1.Calculating stress relaxation rate (%) by this relation is (H _t-H ₁)/(δ ₀-H ₁) * 100.In the formula, δ ₀Be 1 distance from the benchmark to the test film, H ₁Be 3 distance from the benchmark to the test film, H _tBe 2 distance from the benchmark to the test film.

[table 1-1]

[table 1-2]

As show shown in the 1-1, bendability, ys, electric conductivity, the proof stress relaxation property of the present invention's example 1-1 ~ 1-19 are excellent.

On the other hand, shown in table 1-2, under the situation of discontented unabridged version invention regulation, obtain the relatively poor result of characteristic.

That is, comparative example 1-1 is because the total amount of Ni and Co is few, and the density that therefore helps to separate out solidified compound (precipitate) reduces intensity difference.In addition, do not form Si excessive solid solution in metal structure of compound, the conduction rate variance with Ni or Co.Comparative example 1-2 is because the total amount of Ni and Co is many, so conducts electricity rate variance.Comparative example 1-3 is because Si is few, so intensity difference.Therefore comparative example 1-4 is because Si is many, conducts electricity rate variance.

(111) face of comparative example 1-5 ~ 1-9 is high towards the ratio of TD, and bendability is poor.Particularly in the BW bending, observe tangible crackle.

Embodiment 2

For composition and surplus shown in one hurdle of the alloying constituent with table 2 is the copper alloy of Cu and unavoidable impurities; The confession of likewise making the copper alloy plate of the present invention example 2-1 ~ 2-17 and comparative example 2-1 ~ 2-3 with embodiment 1 tries material, likewise characteristic is investigated with embodiment 1.The result is as shown in table 2.

As shown in table 2, bendability, ys, electric conductivity, the proof stress relaxation property of the present invention's example 2-1 ~ the present invention's example 2-17 are excellent.

On the other hand, under the situation of discontented unabridged version invention regulation, characteristic is relatively poor.That is, comparative example 2-1,2-2,2-3 (being the comparative example of the invention of above-mentioned (3) item) are because the addition of other element beyond Ni, Co and the Si is more, so electric conductivity is relatively poor.

Embodiment 3

For having composition shown in the table 3 and surplus is the copper alloy of Cu and unavoidable impurities; With ingot bar after carrying out 10 minutes ~ 10 hours homogenizing thermal treatment under 700 ℃ ~ 1020 ℃; After likewise carrying out hot rolling with embodiment 1, carry out successively water-cooled, 50 ~ 99% cold rolling, keep the thermal treatment of 10 second ~ 5 minute, the cold working of 5 ~ 55% working moduluses down at 600 ~ 900 ℃.

Then, that kind as shown in table 4 is carried out centre recrystallize thermal treatment and is handled with final solution heat-transmission.Then, the timeliness of carrying out 5 minutes ~ 20 hours at 350 ~ 600C separate out thermal treatment, again carry out the finish rolling of 2 ~ 45% working moduluses, 300 ~ 700 ℃ of modified annealing that keep 10 second ~ 2 hour down, made and supplied the examination material.Likewise characteristic is investigated with embodiment 1.The result is as shown in table 4.

[table 3]

The composition element	Ni	Co	Si	Sn	Zn	Mg	Cr
								Quality %	2.71	0.32	0.76	0.17	0.31	0.07	0.17

As shown in table 4, bendability, ys, electric conductivity, the proof stress relaxation property of the present invention's example 3-1 ~ the present invention's example 3-6 are excellent.

On the other hand, under the situation of discontented unabridged version invention regulation, characteristic is relatively poor.That is, comparative example 3-1 is because the heat treated temperature of middle recrystallize is lower, and therefore (111) face increases towards the zone of TD, and toughness is poor.Comparative example 3-2 is because the heat treated temperature of middle recrystallize is higher, and therefore (111) face increases towards the zone of TD, and toughness is poor.Comparative example 3-2 is longer owing to the heat treated treatment time of middle recrystallize, and solute atoms becomes thick precipitate, solid solution fully when final solution heat-transmission is handled, and ys is poor.Comparative example 3-4 is because the treatment temp that final solution heat-transmission is handled is lower, so the solid solution of solute atoms is insufficient, and ys is poor.Comparative example 3-5 is because the treatment temp that final solution heat-transmission is handled is higher, so thickization of crystal grain, and ys is poor.The treatment time that comparative example 3-6 handles owing to final solution heat-transmission is longer, so thickization of crystal grain, and ys is poor.In addition, because the crystal particle diameter of comparative example 3-5,3-6 is big, so flexural fold is bigger, and is not good.

Like this, through the present invention, for example can realize being suitable as very much the characteristic of the material (particularly its body material) of vehicle-mounted parts such as connector material and electric, electronic machine.

Then, for the copper alloy plate of creating conditions and making through in the past, the copper alloy plate of inventing for clear and definite and the application different are made copper alloy plate under its condition, and have carried out the evaluation with above-mentioned same characteristic project.In addition, the short of special instruction of the thickness of each sheet material is adjusted working modulus with the mode of thickness same as the previously described embodiments.

(comparative example 101) ... The condition of TOHKEMY 2009-007666 communique

Adopt high-frequency melting furnace to fuse being combined with the alloy that is Cu and unavoidable impurities with same metallic element of the invention described above example 1-1 and surplus, this alloy of speed of cooling casting with 0.1 ~ 100 ℃/second has obtained ingot bar.It after keeping 3 minutes to 10 hours under 900 ~ 1020 ℃, is carried out hot-work, carry out shrend then, carry out the face cutting again to remove the deoxidation rust deposite.Thereafter operation is to have made copper alloy c01 through the processing of implementing following operation A-3, B-3.

Comprise above once or twice solution heat-transmission processing in the manufacturing process; At this; Operation is classified in front and back so that last solution heat-transmission is wherein handled, will turn to operation only as the A-3 operation up to middle solution, and the operation that middle solutionization is later is as the B-3 operation.

Operation A-3: implementing the cross section decrement is the cold working 20% or more, 350 ~ 750 ℃ of thermal treatments of implementing 5 minutes ~ 10 hours down, implements the cross section decrement and be 5 ~ 50% cold working, 800 ~ 1000 ℃ of solution heat-transmission processing of implementing 5 second ~ 30 minute down.

Process B-3: implementing the cross section decrement is the cold working 50% below, and 400 ~ 700 ℃ of thermal treatments of implementing 5 minutes ~ 10 hours down, implementing the cross section decrement is the cold working 30% below, the modified annealing of enforcement 5 second ~ 10 hour under 200 ~ 550 ℃.

The test body c01 that obtains and the foregoing description are different on recrystallize thermal treatment [operation 9 among the application] this point in the middle of having or not in creating conditions; (111) face of this test body c01 is high towards the area occupation ratio of TD, and the result does not satisfy the characteristic that requires of bendability.

(comparative example 102) ... The condition of TOHKEMY 2006-283059 communique

Adopt electric furnace with the copper alloy of the composition of the invention described above example 1-1 in atmosphere, under charcoal coats, fuse, judgement could be cast.Ingot bar after the hot rolling melting, finish rolling become thickness 15mm.Then, implement cold rolling and thermal treatment (cold rolling 1 → solution continuous annealing → cold rolling 2 → ageing treatment → cold rolling 3 → short period of time annealing) to this hot-finished material, manufacturing has the copper alloy thin plate (c04) of given thickness.

The test body c02 that obtains and the foregoing description 1 in creating conditions thermal treatment [operation 7 among the application] and have or not in the middle of different on recrystallize thermal treatment [operation 9 among the application] this point; (111) face of this test body c02 is high towards the area occupation ratio of TD, and the result does not satisfy bendability.

(comparative example 103) ... The condition of TOHKEMY 2006-152392 communique

In cryptol furnace, will have alloy that the invention described above example 1-1 forms in atmosphere, charcoal fuses under coating, and is cast as the cast iron book mold, obtains the ingot bar of thick 50mm, wide 75mm, long 180mm.And, surfacing is carried out on the surface of ingot bar, under 950 ℃ temperature, be rolled into thickness 15mm then, from the quenching water of the temperature more than 750 ℃.Then, remove the deoxidation rust deposite after, carry out cold rollingly, obtain the plate of given thickness.

Then, the use molten salt furnace after the quenching, through latter half of pinch pass, is processed the cold-reduced sheet of each thickness after having carried out under temperature, heating the solution processing in 20 seconds in water.At this moment, as follows, these cold rolling working moduluses (%) are carried out various changes, process cold-reduced sheet (c03).As followsly to the temperature of these cold-reduced sheets (℃) and the time (hr) carry out various changes, carry out ageing treatment.

Cold working rate: 95%

Solution treatment temp: 900 ℃

Artificial aging solidification treatment temperature * time: 450 ℃ * 4 hours

Thickness of slab: 0.6mm

The test body c03 that obtains and the foregoing description 1 in creating conditions thermal treatment [operation 7 among the application] and have or not in the middle of different on recrystallize thermal treatment [operation 9 among the application] this point; (111) face of this test body c03 is high towards the area occupation ratio of TD, and the result does not satisfy bendability.

(comparative example 104) ... The condition of TOHKEMY 2008-223136 communique

Copper alloy to shown in the embodiment 1 carries out melting, and uses vertical continuous casting machine to cast.Cut out the sample of thickness 50mm by the casting sheet that obtains (thickness 180mm), take out after being heated 950 ℃, begin to carry out hot rolling.At this moment, be to set the passage programsheet more than 60% and being lower than the mode that also is rolled under 700 ℃ the temperature province with the rolling rate under 950 ℃ ~ 700 ℃ the temperature province.The final passage temperature of hot rolled is between 600 ℃ ~ 400 ℃.Total hot rolling rate of casting sheet is about 90%.After the hot rolling, remove the zone of oxidation on (surfacing) top layer through mechanical mill.

Then, carry out cold rollingly, offer the solution processing then.Temperature variation when keeping watch on the solution processing through the thermopair that is installed on specimen surface is obtained in the temperature-rise period TRT from 100 ℃ to 700 ℃.In 700 ~ 850 ℃ scope, adjust the arrival temperature according to alloy composition; Make that the average crystalline particle diameter (twin boundary not being regarded as crystal boundary) after the solution processing is 10 ~ 60 μ m, be adjusted at the hold-time under 700 ~ 850 ℃ the temperature province in the scope of 10 second ~ 10 minute.Then, the sheet material after the above-mentioned solution processing with cold rolling in the middle of the rolling rate enforcement, is implemented ageing treatment then.Aging temperature is 450 ℃ of material temperature, for aging time, is adjusted into according to alloy composition that hardness is the time of peak value under 450 ℃ the timeliness.According to such alloy composition, hold best solution treatment condition and timeliness treatment time through preliminary experiment.Then, carry out pinch pass with rolling rate.For the test portion that carries out after the pinch pass, 5 minutes low-temperature annealing in 400 ℃ the stove of further implementing then to pack into.Obtain supplying examination material c04 thus.Need to prove, as required, carry out surfacing halfway, make to supply the thickness of slab of examination material neat, be 0.2mm.Main creating conditions is described below.

[condition of TOHKEMY 2008-223136 embodiment 1]

Hot rolling rate under 700 ℃ ~ 400 ℃ of the less thaies: 56% (a time)

Cold rolling rate before the solution processing: 92%

Middle cold rolling rate: 20%

The cold rolling rate of pinch pass: 30%

From 100 ℃ to 700 ℃ TRT: 10 seconds

The test body c04 that obtains and the foregoing description 1 in creating conditions thermal treatment [operation 7 among the application] and have or not on centre recrystallize thermal treatment [operation 9 among the application] this point different; (111) face of this test body c04 is high towards the area occupation ratio of TD, and the result does not satisfy bendability.

Claims (according to the modification of the 19th of treaty)

1. copper alloy plate; It has alloy composition; Said alloy composition comprises: total amount is that the Ni of 0.5 ~ 5.0 quality % and any or two kinds among the Co and Co are 0.5 ~ 1.5 quality %, and the Si of 0.1 ~ 1.5 quality %; Surplus is Cu and unavoidable impurities, wherein, and at EBSD (Electron Back Scatter Diffraction: during the crystalline orientation of EBSD) measuring is analyzed; About gathering towards the atomic plane of the width (TD) of milled sheet; Angle with angle that the normal of (111) face become with TD is that 20 ° of area occupation ratios with the zone of interior atomic plane are below 50%, and ys is more than the 500MPa, and electric conductivity is more than the 30%IACS.

2. copper alloy plate according to claim 1 wherein, also contains total amount and is at least a among Sn, Zn, Ag, Mn, B, P, Mg, Cr, Fe, Ti, Zr and the Hf of being selected from of 0.005 ~ 2.0 quality %.

3. copper alloy plate according to claim 1 and 2, it uses material for junctor.

4. the method for manufacture of a copper alloy plate; It is a method of making each described copper alloy plate in the claim 1 ~ 3; This method comprises: the copper alloy of the alloy composition that obtains said copper alloy plate is implemented casting [operation 1] successively; Homogenizing thermal treatment [operation 2]; Hot-work [operation 3]; Cold rolling [operation 6]; Thermal treatment [operation 7]; Cold rolling [operation 8]; Middle recrystallize thermal treatment [operation 9]; [operation 10] handled in final solution heat-transmission; Implement timeliness then and separate out thermal treatment [operation 11]

5. the method for manufacture of Cu alloy material according to claim 4 wherein, is separated out thermal treatment [operation 11] afterwards in said timeliness, implements cold rolling [operation 12] and modified annealing [operation 13] successively.

Claims

1. copper alloy plate; Wherein, (Electron Back Scatter Diffraction: during the crystalline orientation of EBSD) measuring was analyzed, about the gathering towards the atomic plane of the width (TD) of milled sheet, the angle with angle that the normal of (111) face become with TD was that 20 ° of area occupation ratios with the zone of interior atomic plane are below 50% at EBSD; Ys is more than the 500MPa, and electric conductivity is more than the 30%IACS.

2. copper alloy plate; It has alloy composition, and said alloy composition comprises: total amount is the Ni of 0.5 ~ 5.0 quality % and any or two kinds among the Co, and the Si of 0.1 ~ 1.5 quality %, and surplus is Cu and unavoidable impurities; Wherein, (Electron Back Scatter Diffraction: during the crystalline orientation of EBSD) measuring was analyzed, about the gathering towards the atomic plane of the width (TD) of milled sheet, the angle with angle that the normal of (111) face become with TD was that 20 ° of area occupation ratios with the zone of interior atomic plane are below 50% at EBSD; Ys is more than the 500MPa, and electric conductivity is more than the 30%IACS.

3. copper alloy plate; It has alloy composition; Said alloy composition comprises: total amount is the Ni of 0.5 ~ 5.0 quality % and any or two kinds among the Co, and the Si of 0.1 ~ 1.5 quality %, also contains total amount and be at least a among Sn, Zn, Ag, Mn, B, P, Mg, Cr, Fe, Ti, Zr and the Hf of being selected from of 0.005 ~ 2.0 quality %, and surplus is Cu and unavoidable impurities; Wherein, (Electron Back Scatter Diffraction: during the crystalline orientation of EBSD) measuring was analyzed, about the gathering towards the atomic plane of the width (TD) of milled sheet, the angle with angle that the normal of (111) face become with TD was that 20 ° of area occupation ratios with the zone of interior atomic plane are below 50% at EBSD; Ys is more than the 500MPa, and electric conductivity is more than the 30%IACS.

4. according to each described copper alloy plate in the claim 1 ~ 3, it uses material for junctor.

5. the method for manufacture of a copper alloy plate; It is a method of making each described copper alloy plate in the claim 1 ~ 4; This method comprises: the copper alloy of the alloy composition that obtains said copper alloy plate is implemented casting [operation 1] successively; Homogenizing thermal treatment [operation 2]; Hot-work [operation 3]; Cold rolling [operation 6]; Thermal treatment [operation 7]; Cold rolling [operation 8]; Middle recrystallize thermal treatment [operation 9]; [operation 10] handled in final solution heat-transmission; Implement timeliness then and separate out thermal treatment [operation 11]

6. the method for manufacture of Cu alloy material according to claim 5 wherein, is separated out thermal treatment [operation 11] afterwards in said timeliness, implements cold rolling [operation 12] and modified annealing [operation 13] successively.