CN101522926B

CN101522926B - Copper alloy plate for electrical and electronic components

Info

Publication number: CN101522926B
Application number: CN200780036755.5A
Authority: CN
Inventors: 有贺康博; 尾崎良一; 三轮洋介
Original assignee: Kobe Steel Ltd
Current assignee: Kobe Steel Ltd
Priority date: 2006-10-02
Filing date: 2007-09-26
Publication date: 2011-12-21
Anticipated expiration: 2027-09-26
Also published as: CN101522926A; JP2008088499A; JP4157898B2

Abstract

Provided is a highly strong Cu-Fe-P based copper alloy plate having improved oxide film adhesiveness to solve the problems of package cracks and peeling. The copper alloy plate for electrical and electronic components contains Fe of 0.01-0.50% and P of 0.01-0.15% in mass %, and the rest is composed of Cu and unavoidable impurities. The copper alloy plate has a center line average roughness Ra of 0.2[mu]m or less in surface roughness measurement conforming to the JIS B0601 Standards, a maximum height Rmax of 1.5[mu]m or less, and a kurtosis RKu of a roughness curve of 5.0 or less.

Description

Copper alloy plate for electric and electronic parts

Technical field

The present invention relates to: (1) high strength and in order to handle the encapsulation crack and to peel off problem and improved Cu-Fe-P series copper alloy plate, (2) high strength of oxide film adaptation and possessed the Cu-Fe-P series copper alloy plate, (3) high strength of good bendability and good Cu-Fe-P series copper alloy plate and (4) high strength and the good Cu-Fe-P series copper alloy plate of plating of stampability when the punch process.Copper alloy plate of the present invention, be suitable as the starting material of semiconductor device with lead frame, except that semiconductor device with the lead frame, the various electrical and electronic parts such as mechanism components such as electrical and electronic parts material, switch block, bus, terminal connector that also are suitable as other semiconductor device, printed-wiring board (PWB) etc. use.But in the following description, as representational purposes, being that the employed situation of lead frame is that the center describes at semiconductor device.

Background technology

In the past, as the semiconductor lead frame copper alloy plate, be extensive use of the copper alloy plate of the Cu-Fe-P system of containing Fe and P usually.As the copper alloy plate of these Cu-Fe-P system, but for example illustration contains the copper alloy (C19210 alloy) of Fe:0.05～0.15%, P:0.025～0.040% and contains the copper alloy (CDA194 alloy) of Fe:2.1～2.6%, P:0.015～0.15%, Zn:0.05～0.20%.The copper alloy of these Cu-Fe-P system, if separate out the intermetallic compound of Fe-P etc. in the copper parent phase, even then in copper alloy, intensity, electroconductibility and heat conductivity are good, thereby are used widely as the international standard alloy.

In recent years,, and advanced the employed lead frame of semiconductor device to be made as the small section area, required higher intensity, electroconductibility, heat conductivity along with high capacity, miniaturization, the high performance of the employed semiconductor device of electronics.Accompany therewith, also require the copper alloy plate that uses in the employed lead frame of these semiconductor devices, further high strength, heat conductivity are arranged.

On the other hand, owing to come its economy of encapsulation of sealing semiconductor chips good with the property produced in batches with thermosetting resin, thereby the plastic package of semiconducter device has become main flow.These encapsulation slimmings day by day along with the requirement of the miniaturization of nearest electronic unit.

In the installation of these encapsulation, use Ag cream that the semi-conductor chip heating is bonded in lead frame, perhaps the plating layer by Au, Ag etc. carries out soldering or carries out Ag brazing.And, carry out then resin-sealed, carried out resin-sealed after, usually on outer lead, carry out the outer packaging of plating.

The problem of the maximum relevant with the reliability of these encapsulation is encapsulation crack that produces when surface mounting and the problem of peeling off.Peeling off of encapsulation is that semiconductor packages has been carried out after the assembling, and the thermal stresses under the situation that the adaptation of resin and pad (part of the loading semi-conductor chip of lead frame) reduces during because of later heat treated produces.

Relative therewith, the encapsulation crack is after assembling semiconductor packages, because casting resin moisture absorption from atmosphere, thereby if adding of surface mounting afterwards pines for making the moisture gasification, have the crack in encapsulation inside, then water vapour accumulates in release surface and works as interior pressure.Because of should in press or in encapsulation, produce and expand, perhaps make not internal pressure-resistant and produce the crack of resin.Corrode chip owing to moisture and impurity being entered, thereby harm is as semi-conductive function as if generation crack in the encapsulation after surface mounting.In addition, cause bad order to lose commodity value because of the encapsulation expansion.In recent years, along with the progress of the slimming of above-mentioned encapsulation, such encapsulation crack and the problem of peeling off are particularly evident.

At this, encapsulation crack and the problem peeled off are to cause because of the adaptation of resin and pad is bad, but maximum effect that the adaptation of resin and pad is brought, be the oxide film of lead frame mother metal.The lead frame mother metal passes through various heating processes because of the manufacturing and the lead frame making of plate.Therefore, before plating Ag, be formed with the oxide film of tens of～hundreds of nanometer thickness on the surface of mother metal.Owing to via this oxide film copper alloy plate and resin are joined on the surface of pad, thereby, can cause peeling off of resin and pad with the peeling off certainly of lead frame mother metal of this oxide film, make in adaptation and obviously reduce because of the resin of line plate mother metal.

Therefore, encapsulation crack and peel off this problem with relevant with the adaptation of the lead frame of this oxide film.Therefore, for as the carrying out of lead frame mother metal the copper alloy plate of Cu-Fe-P system of above-mentioned high strength, the adaptation of oxide film that requires to be formed at the surface is still very high through various heating processes.

And, in order to enhance productivity and high efficiency, in the Heating temperature of the various above-mentioned heating processes of the making that is used for copper alloy plate and lead frame, high temperatureization just day by day.For example, in the lead frame production process, require to carry out the heat treated of grade after punch process in the higher temperature short period of time.Along with the high temperature of such Heating temperature, exist the oxide film that is created on the lead frame mother metal because of problems such as densityizations, compared with the oxide film with the low-temperature heat generation in the past, easier and lead frame mother metal is peeled off this new problem.

Still there was in the past motion to propose to improve the problem of oxide film adaptation although quantity is few.What for example, propose in the patent documentation 1 is the crystal orientation on control copper alloy top layer.That is, patent documentation 1 proposes, in the crystal orientation of the extexine that carries out with the membrane process of the XRD of lead frame mother metal copper alloy, will with respect to the 111} peak strength { 100} peak strength ratio is made as below 0.04, with raising oxide film adaptation.In addition, in this patent documentation 1, though comprise so-called lead frame mother metal copper alloy, the content that actual illustrative Cu-Fe-P series copper alloy is a kind of Fe is the Cu-Fe-P series copper alloy more than 2.4% nearly.

In addition, be conceived to the surfaceness of Cu-Fe-P series copper alloy plate in the patent documentation 2,3, proposition is by being made as the center line average roughness Ra in the surface roughness measurement below the 0.2 μ m, and maximum height Rmax is made as below the 1.5 μ m, to improve the oxide film adaptation.Particularly, in this patent documentation 2,3, the control of these surfacenesses is to control by the kind of cold rolling Rolling roller (surfaceness).

In addition, in recent years,, also require these copper alloys that higher intensity and electroconductibility, good bendability are arranged along with the purposes of Cu-Fe-P series copper alloy enlarges and the lightweight of electric, electronics, slimming, miniaturization etc.As such bendability, require to have 90 ° of characteristics that wait the bending machining of strictness carrying out behind stacked bending or the local stamping-out.

Relative therewith, known by making the crystal grain miniaturization or the dispersion state of crystal precipitate being controlled in the past, can improve bendability (with reference to patent documentation 4,5) to a certain extent.

In addition, be in the alloy at Cu-Fe-P, in order to improve all characteristics such as bendability, also have motion to propose the pair set tissue and control.Particularly, the ratio of X-ray diffraction intensity I (200) crystal face of (200) face of motion proposition or copper alloy plate and the X-ray diffraction intensity I (220) of (220) crystal face is that I (200)/I (220) is more than 0.5 below 10, perhaps the orientation density in Cube orientation: D (Cube orientation) is more than 1 below 50, the perhaps ratio of the orientation density in the orientation density in Cube orientation: D (Cube orientation) and S orientation: D (S orientation), promptly D (Cube orientation)/D (S orientation) is (with reference to a patent documentation 6) below 5 more than 0.1.

Moreover, also have motion to propose, the ratio of X-ray diffraction intensity I (311) sum of the X-ray diffraction intensity I (200) of (200) crystal face of copper alloy plate and (311) face and the X-ray diffraction intensity I (220) of (220) crystal face, promptly [I (200)+I (311)]/I (220) is (with reference to a patent documentation 7) more than 0.4.

On the other hand, these copper alloy plates that carried out high strength are also required processibility at the lead frame that has carried out above-mentioned little cross sectionization.Particularly, for the lead frame to copper alloy plate carries out punch process, require copper alloy plate to have good stamping-out.No matter this requirement is the purposes outside the lead frame, still the purposes that copper alloy plate is carried out punch process all is the same.

In Cu-Fe-P series copper alloy plate, in the past, the method that improves stampability was extensive use of the method that trace to Pb, Ca etc. adds and makes method that the chemical ingredients of the compound dispersion etc. of the starting point that constitutes fracture controls, size of microcrystal etc. is controlled.

But these methods exist or control self comparatively difficulty, perhaps cause the deterioration of other characteristic, perhaps therefore make problems such as manufacturing cost rising.

Relative therewith, there is motion to be conceived to the tissue of Cu-Fe-P series copper alloy plate, improve the technology of stampability and bendability.For example, patent documentation 8 disclosed technology are, contain Fe:0.005～0.5wt%, P:0.005～0.2wt%, also contain a side or both sides among Zn:0.01～10wt%, the Sn:0.01～5wt% as required, surplus is the Cu-Fe-P series copper alloy plate of being made up of Cu and unavoidable impurities.And, patent documentation 8, the integrated level of the crystal orientation by controlling this copper alloy plate improves stampability (with reference to patent documentation 8).

More particularly, in the patent documentation 8, what the control of this integrated level utilized is, along with making copper alloy plate carry out the crystal particle diameter of recrystallize, augmenting tissue, and increase to the plate surface { 200}, { the integrated ratio of 311} face then increases { the integrated ratio of 220} face if be rolled.And, it is characterized in that, with respect to 200}, the 311} face, and the plate surface of increase { the integrated ratio of 220} face improves stampability.More particularly, exactly establish leisure should the surface the X-ray diffraction intensity of 200} face is I[200], establish from the X-ray diffraction intensity of 311} face is I[311], establish from the X-ray diffraction intensity of 220} face is I[220] time, make and satisfy relational expression [I[200]+I[311]]/I[220]＜0.4.

In addition, in above-mentioned patent documentation 6 and the patent documentation 7 also publicity improve the copper alloy plate of stampability) with reference to patent documentation 6,7).

Moreover patent documentation 9 proposes, and for the bendability that improves Cu-Fe-P series copper alloy plate I (200)/I (110) is made as (with reference to patent documentation 9) below 1.5.

In addition, the known copper alloy that also has other, but in order to improve the bendability of Cu-Ni-Si series copper alloy (steel nickel silicon alloy) plate, and the ratio of uniform elongation in the tensile properties of copper alloy plate and percentage of total elongation is made (with reference to patent documentation 10) more than 0.5.

In addition, these have carried out the copper alloy plate of high strength, after having implemented stamping machine stamping-out processing (punch process), bending machining etc., implement the plating of Ag etc. again and make semiconductor lead frame.

But in the plating surface of this Ag etc., part (part) occurs on Fig. 3 (the SEM photo that accompanying drawing substitutes amplifies 500 times) with such the separating out unusually as the plating of the projection of plating layer with microscopic examination of the point shown in the arrow sometimes.If separating out unusually of this plating taken place, then will cause rack of fusion etc. and can not use as semiconductor lead frame.

Separating out unusually certainly of this plating neither can take place on whole of plating surface, also can not produce in a large number on the semiconductor lead frame of each making.But, by the high efficiency production in enormous quantities line of semiconductor lead frame, on the semiconductor lead frame of made, be only ppm level even for example number takes place, taking place under the situation about separating out unusually of plating, also be difficult to avoid great effect Production Line speed and production efficiency.

Now by inference, separating out unusually of this plating is in the remaining reason that reach the surface imperfection such as macrocrystalline through hole that by hydrogen caused of the macrocrystalline inclusion (oxide compound and crystallisate) of casting the melting process generation on the finished product plate surface.On the finished product plate surface of separating out unusually under the plating part that plating is arranged, in most cases, exist, remaining the surface imperfection such as macrocrystalline through hole that caused by macrocrystalline inclusion (oxide compound and crystallisate) or hydrogen are arranged.

Be difficult to avoid containing in this Cu-Fe-P series copper alloy melting process stage such as to a certain degree hydrogen and oxygen etc. in casting, the macrocrystalline inclusion (oxide compound and crystallisate) that generates in the melt-casting operation is remaining to the finished product, just is difficult to avoid the through hole by hydrogen causes to occur as surface imperfection.

Be used for semiconductor lead frame had proposed much with the motion of the high formabilityization of the high strength of copper alloy and stampability, bendability etc. in the past.But, almost do not have to propose to the plating of semiconductor lead frame with copper alloy, particularly to the plating in the Cu-Fe-P series copper alloy, and above-mentioned plating separated out the technology that improves unusually.

Wherein, there is motion to propose in copper alloy plate, to contain Fe:1.5～2.3 weight % or P:0.015～0.045 weight % and contain Fe, P more, to improve the technology (patent documentation 11) of plating.In addition, patent documentation 11 also propose to make C reach 10～100ppm and contain more to prevent that grain-boundary crack is made as technology.

Patent documentation 1: the spy of Japan opens the 2001-244400 communique

Patent documentation 2: the spy of Japan opens flat 2-122035 communique

Patent documentation 3: the spy of Japan opens flat 2-145734 communique

Patent documentation 4: the spy of Japan opens flat 6-235035 communique

Patent documentation 5: the spy of Japan opens the 2001-279347 communique

Patent documentation 6: the spy of Japan opens the 2002-339028 communique

Patent documentation 7: the spy of Japan opens the 2000-328157 communique

Patent documentation 8: the spy of Japan opens the 2000-328158 communique

Patent documentation 9: the spy of Japan opens the 2006-63431 communique

Patent documentation 10: the spy of Japan opens the 2002-266042 communique

Patent documentation 11: No. 2962139 communiques of United States Patent (USP)

But, in these prior aries, also do not reach the high-caliber oxide film adaptation of guarantee that the present invention proposes.That is the oxide film on the lead frame mother metal surface that, can not comprehensive treating process generates under the pyritous Heating temperature is easier to produce this new problem of peeling off with the lead frame mother metal.

At first, the content of the substantial Fe of Cu-Fe-P series copper alloy in the patent documentation 1, as mentioned above, the minimum 2.4 quality % that also nearly surpass.In this, the technology of patent documentation 1 is perhaps effective really aspect the oxide film adaptation raising of the many Cu-Fe-P series copper alloys of Fe content.In fact, in patent documentation 1, the oxide film adaptation of Cu-Fe-P series copper alloy that with Fe content has been 2.41% embodiment 1 is increased to 633K (360 ℃) under the stripping limit temperature of oxide film.

But if Fe content nearly surpasses 2.4 quality %, the oxide film on the lead frame mother metal surface that then generates under the pyritous Heating temperature becomes and is easier to peel off with the lead frame mother metal.In addition, also produce the other problem that not only makes the material behavior of electroconductibility but also make the obvious reductions of productivity such as castibility.

In addition,, then will cause thickization of growth of precipitation particles, reduce intensity and stable on heating problem because the undue electric conductivity that improves also for example exists if increase the amount of separating out of above-mentioned precipitation particles.In other words, the technology of patent documentation 1 can not have both desired high strength of Cu-Fe-P series copper alloy and oxide film adaptation.

Therefore, by Fe content being reduced to the composition below 0.5% in fact,, can not obtain above-mentioned desired oxide film adaptations such as lead frame even the technology of this patent documentation 1 is directly applied to the Cu-Fe-P series copper alloy that has carried out high strength.

In addition, as described in patent documentation 2,3, above-mentioned center line average roughness Ra is being made as below the 0.2 μ m, maximum height Rmax is made as under the situation below the 1.5 μ m, compare than this big Cu-Fe-P series copper alloy plate with surfaceness, improved the oxide film adaptation really.

But, discovery according to present inventors, for in above-mentioned the present invention as the heating under high temperature more of purpose and the oxide film adaptation of the oxide film that generates, as described below, even be made as below the 0.2 μ m and maximum height Rmax be made as under the situation of 1.5 μ m, still can unexpectedly on oxide film driving fit performance, produce big difference at center line average roughness Ra with identical (equating).

Key element (essential factor) outside this expression center line average roughness Ra and the maximum height Rmax has very big relation.And this situation means, only otherwise control this key element (essential factor), just can not improve in the present invention the oxide film adaptation as the oxide film that generates of purpose under higher temperature.

In addition, the method of up to now copper alloy high strength add promptly that the solution strengthening element of Sn and Mg and cold rolling working (machining) efficiency increase by forcing during work hardening amount that the worker brings increases, will certainly be along with the deterioration of bendability, be difficult to make necessary strength and bendability and deposit.But, for above-mentioned compactization that obtain adapting to electric, electronic component in recent years be that high strength Cu-Fe-P more than the 500MPa is an alloy such as tensile strength, must increase by so cold rolling work hardening amount that the worker brings of forcing.

For such high strength Cu-Fe-P is alloy, only with the grain refining of above-mentioned patent documentation 4,5 etc. and the organizational controls methods such as dispersion state control of crystallization precipitate, the set Microstructure Control method that also has above-mentioned patent documentation 6,7 etc., with respect to strict bending machining such as 90 ° of bendings behind above-mentioned stacked bending or the local stamping-out, can not fully improve bendability.

In addition, in the above-mentioned patent documentation 6 and 8, increase { 220} face and { the integrated ratio of 200} face is to improve stampability to the plate surface.By increasing the integrated ratio of these certain surface, improved the stampability of Cu-Fe-P series copper alloy plate really.

But, the little transverse sectionization of above-mentioned lead frame is more and more advanced, going between, wide ((0.25mm → 0.15mm) also become more and more littler, the requirement of the punch process raising during to the punch process of the Cu-Fe-P series copper alloy plate that carried out high strength becomes strict more for 0.5mm → 0.3mm) and thickness of slab.Therefore, as the punch process raising effect that the integrated ratio control by tissue of above-mentioned patent documentation 6 and 8 is brought, can't satisfy the stampability of this requirement.

In addition, in the raising method of the bendability of the copper alloy plate of above-mentioned patent documentation 10, can not improve desired stampability.Patent documentation 10 as object be that 0.2% yielding stress is that 800MPa level, electric conductivity are the Cu-Ni-Si series copper alloy (Corson alloy) of 40%IACS level, with Cu-Fe-P series copper alloy of the present invention, alloy system and characteristic are different fully.In addition, so-called bendability and stampability are the diverse characteristics of mechanism, as patent documentation 10, under the ratio of establishing uniform elongation and percentage of total elongation is situation more than 0.5, as described later, will reduce the stampability of Cu-Fe-P series copper alloy of the present invention.

In addition, as patent documentation 11, containing under the more situation of Fe, P, because also many in the amount of the macrocrystalline inclusion (oxide compound and crystallisate) of casting the melting process generation, and make them residue in final finished plate surface in a large number, thereby instead bring out separating out unusually of above-mentioned plating.

In addition, in patent documentation 11, the surface imperfection such as through hole that do not have to be caused by the hydrogen as the reason of separating out unusually of above-mentioned plating are as problem, thereby can not be able to prevent separating out unusually of the plating that causes thus.

Moreover, in patent documentation 11,, in the molten metal fluid, add the Fe-C mother alloy in the manufacturing process of copper coin, make and contain nearly 10～100ppm of C.But C is highly susceptible to dissipation, owing to just carry out dissipation in the moment of adding molten metal to, thereby to be difficult to make molten metal to contain C usually be more than the 10ppm.In addition, as described below, according to present inventors' discovery, in the Cu-Fe-P series copper alloy, under the situation that contains C in a large number, instead promoted separating out unusually of plating.

Therefore, separate out otherwise effective technique unusually, also almost do not propose up to now for what prevent above-mentioned plating.Therefore,, comprise the Cu-Fe-P series copper alloy,, will reduce content more energetically as the hydrogen of the reason of separating out unusually of plating and oxygen etc. generally at casting melting process etc. in order to prevent separating out unusually of above-mentioned plating.

But, in the manufacturing process of copper coin particularly in casting melting process etc., with the near more energetically denier of content of hydrogen and oxygen etc., even also will become the major cause that promotes manufacturing cost, reduces production efficiency in the manufacturing process of copper coin.Therefore, the Cu-Fe-P series copper alloy in the casting melting process stage, is difficult to avoid containing to a certain degree hydrogen and oxygen etc.

Therefore, in the Cu-Fe-P series copper alloy, the macrocrystalline inclusion (oxide compound and crystallisate) that generates in the melt-casting operation to production board, is difficult to avoid the through hole by hydrogen causes to occur as surface imperfection remaining.

Therefore, in the casting melting process stage, even contain to a certain degree hydrogen and oxygen etc., also requirement can prevent the Cu-Fe-P series copper alloy plate that separating out unusually of above-mentioned plating is such.

Summary of the invention

The present invention sets up in order to solve such problem, and its purpose is, a kind of Cu-Fe-P series copper alloy plate is provided, and makes high strength and oxide film adaptation that the oxide film that generates because of the heating under the higher temperature is good and depositing.

In addition, another object of the present invention is to, a kind of Cu-Fe-P series copper alloy plate that has both high strength and good bendability is provided.

In addition, another object of the present invention is to, a kind of Cu-Fe-P series copper alloy plate that makes high strength and stampability and deposit is provided.

Another object of the present invention is to, provide a kind of and make high strength and prevent the reasonable plating of separating out unusually of plating and the Cu-Fe-P series copper alloy plate of depositing.

To achieve these goals, will being intended to of copper alloy plate for electric and electronic parts of the present invention, do not contain Fe:0.01～0.50%, P:0.01～0.15% with quality % score, surplus is made of Cu and unavoidable impurities, with JIS B0601 method is that the center line average roughness Ra in the surface roughness measurement of this copper alloy plate of benchmark is below the 0.050 μ m, maximum height Rmax is below the 1.5 μ m, and the standout of roughness curve (kurtosis value) Rku is below 3.1.

Preferably, in the copper alloy plate for electric and electronic parts of the present invention, be that the r value of parallel direction is more than 0.3 with respect to the rolling direction of above-mentioned copper alloy plate.

Preferably, electric and electronic of the present invention is with in the copper alloy plate, the passing through of above-mentioned copper alloy plate adopts the modulus in tension of obtaining as the tension test of the test film of length direction with respect to the orthogonal plate width direction of rolling direction to surpass 120GPa, and the ratio of uniform elongation and percentage of total elongation is uniform elongation/percentage of total elongation less than 0.50.

Preferably, in the copper alloy plate for electric and electronic parts of the present invention, above-mentioned copper alloy plate also contains C:3～15ppm, and is restricted to respectively below the O:40ppm, below the H:1.0ppm.

Copper alloy plate of the present invention for realizing high strength, also can also contain 0.005～5.0% Sn in quality %, and perhaps the heat-resisting separability for solder and plating Sn improves, and also can also contain 0.005～3.0% Zn in quality %.

Preferably, in the copper alloy plate of the present invention, be restricted to respectively below the S:20ppm, below the Pb:20ppm.

Preferably, in the copper alloy plate of the present invention, tensile strength is more than the 500MPa, and hardness is more than the 150Hv.

Copper alloy plate of the present invention also can also contain a kind of or two or more among Mn, Mg, the Ca in quality %, adds up to 0.0001～1.0%.

Copper alloy plate of the present invention also contains a kind of or two or more among Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au, the Pt in quality %, adds up to 0.001～1.0%.

Copper alloy plate of the present invention, also can also contain in quality % and to add up to a kind of or two or more among 0.0001～1.0% Mn, Mg, the Ca, with add up to a kind of or two or more among 0.001～1.0% Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au, the Pt, and, the total content of these elements that contain is made as below 1.0%.

Preferably, in the copper alloy plate of the present invention, the content of Hf, Th, Li, Na, K, Sr, Pd, W, S, Si, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B, norium is made as below the 0.1 quality % by the overall total of these elements.

In addition, to achieve these goals, will being intended to of copper alloy plate for electric and electronic parts of the present invention, do not contain Fe:0.01～0.50%, P:0.01～0.15% with quality % score, surplus is made of Cu and unavoidable impurities, tensile strength is more than the 500MPa, and hardness is more than the 150Hv, is that the r value of parallel direction is more than 0.3 with respect to the rolling direction of copper alloy plate.

In addition, to achieve these goals, will being intended to of copper alloy plate for electric and electronic parts of the present invention, do not contain Fe:0.01～0.50%, P:0.01～0.15% with quality % score, surplus is made of Cu and unavoidable impurities, the modulus in tension of obtaining as the tension test of the test film of length direction with respect to the orthogonal plate width direction of rolling direction by employing surpasses 120GPa, and the ratio of uniform elongation and percentage of total elongation is uniform elongation/percentage of total elongation less than 0.50.

In addition, to achieve these goals, will being intended to of copper alloy plate for electric and electronic parts of the present invention, do not contain Fe:0.01～0.5%, P:0.01～0.15%, C:3～15ppm with quality % score, surplus is Cu and unavoidable impurities, in this unavoidable impurities, be restricted to respectively that O:40ppm is following, H:1.0ppm following, S:20ppm is following, below the Pb:20ppm.

Copper alloy plate of the present invention can be fit to various electrical and electronic parts usefulness, and especially preferably being used in semiconductor device is the semiconductor lead frame purposes.

Copper alloy plate of the present invention is made as tensile strength more than the 500MPa as the target of high strength, and hardness is made as more than the 150Hv.In addition, the electric conductivity of copper alloy plate and the intensity of plate are interrelated, in the present invention, though the high-strength conductive rate certainly will be low more, do not hinder practicability.Therefore, said in the present invention high conductivity, its implication is for than higher degree according to high-intensity ratio electric conductivity.

In the present invention, to high strength and standout (kurtosis value) Rku of roughness curve with Cu-Fe-P series copper alloy plate of the oxide film that the heating under higher temperature generates control, to improve the oxide film adaptation.

As everyone knows, as described later shown in the mathematical formula, the standout of roughness (kurtosis value) Rku is by the JIS B0601 definition of surface roughness measurement, the standout situation of concavo-convex (curve of cycloid generation circular bending curve Z (x)) of presentation surface roughness.

For example shown in Fig. 1 (a), Rku up to 5.0 the situation of surpassing under, the concavo-convex curve of surfaceness (curve of cycloid generation circular bending curve Z (x)) be sharp or steep curve.Relative therewith, little under the situation below 5.0 at Rku in mode of the present invention shown in Fig. 1 (b), the concavo-convex curve of surfaceness (curve of cycloid generation circular bending curve Z (x)) is relatively circle or level and smooth curve.

Discovery according to present inventors, like this Rku is made as below 5.0, will make the concavo-convex curve (curve of cycloid generation circular bending curve Z (x)) of surfaceness become relatively circle or level and smooth curve, and on the other hand, then can improve the oxide film adaptation of the oxide film of the heating generation of Cu-Fe-P series copper alloy plate under higher temperature.

At this, can think that also on the contrary the concavo-convex situation for point or steep curve of the surfaceness as Rku surpasses Fig. 1 (a) of 5.0 has been brought into play the cementation effect, and improve the oxide film adaptation.In this, why the concavo-convex of the surfaceness shown in Fig. 1 (b) is the situation of relatively circle or more level and smooth curve, can improve the oxide film adaptation of the oxide film that because of heating generate of Cu-Fe-P series copper alloy plate under higher temperature, not clear at present.

But, in the present invention, can as prior art, not making the problem that produces other quantitative change that contains of Fe more, the easy method of using standout (kurtosis value) Rku to roughness curve with copper alloy plate that Cu-Fe-P system forms to control simultaneously can improve the oxide film adaptation of the oxide film that because of heating generate of Cu-Fe-P series copper alloy plate under higher temperature.

In addition, the standout of the roughness curve of the copper alloy plate among the present invention (kurtosis value) Rku is and center line average roughness Ra and the independently technical mutually key element of maximum height Rmax.Promptly, mode with above-mentioned existing patent documentation 2,3, even carried out under the level and smooth situation center line average roughness Ra being made as below the 0.2 μ m and maximum height Rku is made as below the 1.5 μ m and to the copper alloy plate surface, also be that existing Rku surpasses 5.0 situation, also have Rku to become situation below 5.0.

In other words, even carried out under the level and smooth situation center line average roughness Ra being made as below the 0.2 μ m and maximum height Rku is made as below the 1.5 μ m and to the copper alloy plate surface, be not that Rku is become below 5.0 yet, have yet and depart from and even become than this bigger possibility.Therefore, even under center line average roughness Ra being made as below the 0.2 μ m and maximum height Rku being made as situation below the 1.5 μ m, whether the Rku on copper alloy plate surface becomes below 5.0, if do not see that then all are unknown to practical measurement Rku.

This fact as described later, be confirmed by the following fact, promptly, even center line average roughness Ra is identical with maximum height Rku, by standout (kurtosis value) Rku of roughness curve, also can contrast the heating under the Cu-Fe-P series copper alloy plate higher temperature and the oxide film adaptation of the oxide film that produces produces big difference.In addition, as described later, also confirm from the following fact, on the processing rank of the Roughness Surface on Control physical property of the such Rolling roller of above-mentioned existing patent documentation 2,3, Rku can not be controlled at below 5.0, the clean processing that is attended by chemical milling just may be controlled at Rku below 5.0 afterwards.

In addition, according to the present invention, will be relative with the rolling direction of Cu-Fe-P series copper alloy plate for the r value of parallel direction is set as more than the above-mentioned steady state value more than 0.3, even be high strength copper alloy plate more than the 500MPa, also can improve bendability in tensile strength.

At this, well-known, the r value is improved in steel plate beyond copper and aluminium alloy plate field, even high-intensity steel plate and aluminium alloy plate can improve bendability.But copper alloy focuses on that particularly at Cu-Fe-P series copper alloy plate it may not be known that the r value improves bendability.

As described in above-mentioned prior art, this reason is owing to guess, in Cu-Fe-P series copper alloy plate field in order to improve bendability, the dispersion state of crystal grain miniaturization and crystallization precipitate control, and the control of the crystal orientation distribution density of copper alloy plate such as the control of structure etc. is main flow.Also guess in addition, in Cu-Fe-P series copper alloy plate, in order to improve bendability, the influence of the key element beyond the r value is very big, and the r value may not effectively be a general knowledge improving on the bendability.

As mentioned above, different with other steel nickel silicon alloy etc., content at the solution strengthening element has in the Cu-Fe-P series copper alloy plate of very big limit, and high strength must be to have to implement by the increase work hardening amount of forcing the worker of cold rolling increase working modulus.

Cold rolling forcing among the worker, crystal particle diameter is had in the rolling direction big anisotropy of crystal orientation of (elongation) elongation significantly.Therefore, particularly known will making with respect to rolling direction is that the bendability of parallel direction obviously reduces.Therefore, in order to improve this bendability, control is as the big anisotropy of the above-mentioned crystal orientation of the reason of bendability reduction certainly, that is, the crystal orientation distribution density of control copper alloy plate becomes the thing of very being concerned about between the practitioner.

But the crystal orientation control of such copper alloy plate is being controlled at desired distribution density in order to obtain desired bendability with each crystal orientation, and promptly actual the manufacturing is very difficult.

Relative therewith, in the present invention, improve the r value of Cu-Fe-P series copper alloy plate, even the high strength copper alloy plate has also improved bendability.The r value viscous deformation ratio that is otherwise known as is illustrated in the ratio of the minimizing of the wide and thickness of the plate of the material in the tension test of materials such as Cu-Fe-P series copper alloy plate.If the more little then r of the ratio value of the minimizing of the thickness of slab relative with the wide minimizing of the plate of material is big more.Because this point, the more little bendability of ratio of the minimizing of the thickness of slab relative with the wide minimizing of the plate of material is also good more, thereby as the material of Cu-Fe-P series copper alloy plate etc., just becomes big more being difficult to more of r value to rupture, thereby has improved bendability.

The mutual relationship of such bendability and r value and even conclusion, from another aspect, the r value is expression plastic anisotropy's index as known in the art, verified and above-mentioned crystal orientation distribution density is by confidential relation.

But, even like this in Cu-Fe-P series copper alloy plate illustration bendability and r relation to value, but as mentioned above, the effect in fact whether r value just has the raising bendability then is another problem fully.In addition, whether also be another problem to this r value if whether just improving bendability, can improve.That is,, improve the r value and be actually the problem of not understanding to improve bendability to Cu-Fe-P series copper alloy plate.

This point in the present invention as described later, carry out low-temperature annealing after cold rolling with continuous annealing, to with respect to the rolling direction of Cu-Fe-P series copper alloy plate be that the r value of parallel direction be made as steady state value 0.3 or more by the plate in connecting being applied this special method (means) of suitable tension force etc. this moment.And, even the above high strength copper alloy plate of tensile strength 500MPa has also improved bendability.

In addition, find in the present invention, with the tensile strength high strength in the Cu-Fe-P series copper alloy plate more than the 500MPa, not only patent documentation 6 and 8 etc. set organizational controls, and the modulus in tension of being obtained by tension test and the tensile properties such as ratio of uniform elongation and percentage of total elongation also have very big influence to stampability.

The big more stampability of obtaining by tension test of modulus in tension is high more.In addition, the ratio of uniform elongation and percentage of total elongation is more little, and then stampability is high more.But, not clear now, these tensile properties of defined in the present invention, with the tissue of Cu-Fe-P series copper alloy plate be the clear and definite mutual relationship of the state (amount of precipitate and the size of precipitate etc.) of precipitate or structure etc.Therefore, in the present invention, as the prerequisite that improves stampability, qualitative still is quantitatively all to be difficult to the tissue of Cu-Fe-P series copper alloy plate is stipulated.

In addition, these tensile properties of defined one-tenth of being subjected to Cu-Fe-P series copper alloy plate certainly is grouped into very big influence in the present invention, but also is subjected to the very big influence of manufacture method and condition, is not only to depend on to become to be grouped into.Promptly, as described below, these tensile properties of defined in the present invention, manufacture method and the very big influences of condition such as threading speed when being subjected to homogenize heat treated or heat treated, the water cooling starting temperature after the hot rolling, the process annealing temperature before the hot rolling of Cu-Fe-P series copper alloy plate, final continuous annealing.

And these tensile properties of defined are difficult to obtain in the intermittent type final annealing in the present invention, be difficult to just with as with plate (coiled material) Yi Bian Yi Bian obtain connecting the continuous annealing handling in the stove continuously.

Therefore, in the present invention, in order to guarantee the good stampability of Cu-Fe-P series copper alloy plate, be grouped into one-tenth, as mentioned above, the tensile properties such as ratio by modulus in tension and uniform elongation and percentage of total elongation come Cu-Fe-P series copper alloy plate is stipulated.

Maximum of the present invention is characterised in that, contains carbon (C) in Cu-Fe-P series copper alloy plate, though be the above content of amount that nature is sneaked into, is denier as absolute magnitude.

In the present invention,, suppress to be present in the oxygen (O) in the Cu-Fe-P series copper alloy plate, the aggegation of hydrogen (H), to increase the starting point of inclusion and through hole by this effect that contains carbon.And, make the inclusion that generated and the size miniaturization of through hole, prevent the starting point (reason) that these inclusiones and through hole become above-mentioned plating and separate out unusually.Consequently, make in the Cu-Fe-P series copper alloy plate high strength and prevent the good plating that plating is separated out unusually and deposit.

But,,, stipulate to be limited to prerequisite on the O of Cu-Fe-P series copper alloy plate, the H content with the content of C in order to guarantee the action effect of this C.

Description of drawings

Fig. 1 is the explanatory view that is illustrated in by standout (kurtosis value) Rku of the roughness curve in the copper alloy plate surfaceness given to this invention;

Fig. 2 is the explanatory view of the measuring method of expression shear surface rate;

Fig. 3 is that the accompanying drawing on the expression plating copper alloy plate surface of separating out unusually substitutes photo.

Nomenclature

1: copper alloy plate

2: punching hole

3: place of incision

Embodiment

Below, specify as meaning and the embodiment of semiconductor lead frame with each prerequisite of the Cu-Fe-P series copper alloy plate of the present invention that waits the characteristic that is used for satisfied necessity.

＜the first embodiment: high strength and in order to tackle the encapsulation crack and to peel off problem and improved the Cu-Fe-P series copper alloy plate of oxide film adaptation

(surfaceness)

In the present invention, prerequisite as the prerequisite of the surfaceness of Cu-Fe-P series copper alloy plate, be being in the surface roughness measurement of benchmark, center line average roughness Ra be made as below the 0.2 μ m, and maximum height Rmax is made as below the 1.5 μ m with JIS B0 601 methods.Preferably center line average roughness Ra is made as below the 0.1 μ m, and maximum height Rmax is made as below the 1.0 μ m.

If center line average roughness Ra surpasses 0.2 μ m, perhaps maximum height Rmax surpasses 1.5 μ m, and then the surface of Cu-Fe-P series copper alloy plate will not be level and smooth but become coarse, hinders the desired fundamental characteristics of lead frame.That is, with hinder Ag cream etc. to the lead frame semi-conductor chip add thermo-welding or plating and solder or Ag solderings etc. such as plating Au, Ag.In addition, by following the clean processing of chemical milling, the control that the Rku on Cu-Fe-P series copper alloy plate surface is made as below 5.0 also is very difficult.

(Rku)

In the present invention, according to above-mentioned prerequisite, for the oxide film adaptation of the oxide film that generates under the heating under the higher temperature that improves Cu-Fe-P series copper alloy plate, and standout (kurtosis value) Rku that makes the roughness curve in the surface roughness measurement that with JIS B0601 method is benchmark is below 5.0.Rku surpasses at 5.0 o'clock, can not improve the oxide film adaptation of the oxide film that generates under the heating under the higher temperature of Cu-Fe-P series copper alloy plate.Preferred Rku is below 4.5.

In JIS B0601, the standout of roughness curve (kurtosis value) Rku is defined as in the mode of following mathematical formula, and removing datum length on determination object thing surface with the biquadratic of quadratic power rootmean-square Rq is that the biquadratic of generating circle buckling curve Z (x) of lr is average.

Mathematical expression 1

Rku = \frac{1}{R q^{4}} [\frac{1}{lr} {&Integral;}_{o}^{lr} z^{4} (x) dx]

As shown in Figure 1, the mean parameter of the feature of the short transverse of the concavo-convex curve of this Rku presentation surface roughness (generating circle buckling curve Z (x)).

This short transverse be characterized as kurtosis value, surpass under 5.0 the situation at Rku, shown in Fig. 1 (a), the concavo-convex curve of surfaceness (generating circle buckling curve Z (x)) be sharp or steep curve.Relative therewith, little under the situation below 5.0 at Rku as shown in the present shown in Fig. 1 (b), the concavo-convex curve of surfaceness is for comparing the curve garden or level and smooth.

Relative therewith, as the concavo-convex curve of the widely used above-mentioned center line average roughness Ra of the index of surfaceness with the surfaceness of Fig. 1, the mean parameter of the height of the amplitude of short transverse, above-mentioned maximum height Rmax are the parameters of maximum height of the amplitude of short transverse.Therefore, can be understood as, Rku of the present invention is and the irrelevant independently value of these center line average roughness Ra and maximum height Rmax, and shown in the figure (a) and (b), even for example Ra and Rmax are identical, Rku also differs widely.

In addition, in JIS B06010, as the parameter of mean parameter of the feature of this short transverse of expression, except that Rku, Pku in addition: the standout of cross section curve (kurtosis value), Wku: the standout of buckling curve (kurtosis value) etc.But these Pku, Wku be as Rku of the present invention, and be not close with the cognation of the oxide film adaptation of the oxide film that generates than the heating under the higher temperature of Cu-Fe-P series copper alloy plate.Therefore, in the present invention, within the mean parameter of the feature of the short transverse of surfaceness (curve), select Rku to stipulate.

In the present invention, control for Cu-Fe-P series copper alloy plate surface, the physical treatment rank by as the Roughness Surface on Control of Rolling roller at first is controlled at center line average roughness Ra below the 0.2 μ m and with maximum height Rmax and is controlled at below the 1.5 μ m.In addition, Rku is such as described later, by the clean processing of following chemical milling Rku is made below 5.0.

(r value)

In addition, in the present invention, be that the r value of parallel direction is more than 0.3 preferably with respect to the rolling direction of copper alloy plate.Like this, because the r value is more than 0.3, thereby except that above-mentioned characteristic, also obtained the copper alloy plate of has excellent bending properties.The aftermentioneds such as measuring method of r value.

(modulus in tension uniform elongation/percentage of total elongation)

In addition, in the present invention, preferably making by adopting rolling direction with respect to copper alloy plate is that vertical plate width direction is that the modulus in tension that the tension test of the test film of length direction is obtained surpasses 120GPa, and the ratio of uniform elongation and percentage of total elongation, uniform elongation/percentage of total elongation are less than 0.50.Owing to also possess such feature, thereby except that above-mentioned characteristic, also obtained the good copper alloy plate of stampability.About the detailed item aftermentioned relevant with modulus in tension uniform elongation/percentage of total elongation.

(one-tenth of copper alloy plate is grouped into)

In the present invention, use etc. as semiconductor lead frame, preferably having tensile strength is that 500MPa above high strength and hardness are that 150Hv is with first-class fundamental characteristics.And, satisfying on the basis of these fundamental characteristics, be prerequisite perhaps not reduce these fundamental characteristics, have the good plating of separating out unusually that prevents plating.Therefore, as Cu-Fe-P series copper alloy plate, made following essentially consist, that is, in quality %, the content of Fe has been made 0.01～0.50% scope, the content of P is made 0.01～0.15% scope, surplus is made up of Cu and unavoidable impurities.

Relative with this essentially consist, also can also contain elements such as following Zn, Sn selectively.In addition, also allow to contain element (impurity element) outside above-mentioned in the scope that does not hinder characteristic of the present invention.In addition, the demonstration % of the content of these alloying elements and impurity element all is meanings of quality %.

(Fe)

Fe is intensity and a stable on heating principal element of separating out and improve copper alloy as Fe or Fe base intermetallic compound.If the content of Fe is very few, then compound separate out insufficient, the therefore help deficiency that intensity is improved, though even satisfying the raising of electric conductivity carries out finally cold rollingly in strong process side, intensity is also insufficient.On the other hand, if the content of Fe is crossed electric conductivity is descended.Intensity and thermotolerance are all reduced.Therefore, the content of Fe is made as 0.01～0.50% scope, preferably is made as 0.15～0.35% scope.

(P)

P still forms Fe and compound and makes the principal element of copper alloy high strength except that having desoxydatoin.If P content is very few, then compound separate out insufficient, thereby the help deficiency that intensity is improved, though even satisfying the raising of electric conductivity carries out finally cold rollingly in strong process side, intensity is also insufficient.On the other hand, if P content is too much, electric conductivity is descended, and the hot rolling processibility is reduced, be easy to generate crackle.Therefore, the content of P is made as 0.01～0.15% scope, preferably is made as 0.05～0.12% scope.

(C、O、H)

In addition, in the present invention, also preferably contain C:3～15ppm, and be limited in respectively below the O:40ppm, below the H:1.0ppm.By C, O and H are made as above-mentioned scope, except that above-mentioned characteristic, also obtained the good copper alloy plate of plating.About the detailed item aftermentioned relevant with C, O and H.

(Zn)

Zn improves the solder of needed copper alloy such as lead frame and the selectivity of heat-resisting separability under the situation of these effects of needs of plating Sn added element.If 0.005% of the quantity not sufficient that contains of Zn can not get desired effect.On the other hand, if surpass 3.0% not only solder wetting quality reduction, also will reduce electric conductivity greatly.Therefore, according to the heat-resisting equilibrium from property (considering balanced) of the desired electric conductivity of purposes and solder and plating Sn, the content of the Zn under the situation about containing selectively contains selectively from 0.005～3.0% scope.

(Sn)

Sn helps the intensity of copper alloy to improve and the interpolation of the selectivity under the situation of these effects of needs element.If 0.001% of the quantity not sufficient that contains of Sn is helpless to high strength.On the other hand, if the content of Sn is too much, then make the saturated reduction that instead causes electric conductivity of its effect.Therefore, according to the equilibrium (considering balanced) of desired intensity of purposes (hardness) and electric conductivity, the content of the Zn under the situation about containing selectively contains selectively from 0.001～5.0% scope.

(S、Pb)

In copper alloy plate of the present invention, also preferably be restricted to respectively below the S:20ppm, below the Pb:20ppm.S, Pb hinder fundamental characteristics such as intensity as semiconductor lead frame purposes etc., hardness, electric conductivity, also hinder plating Ag etc. simultaneously.

(Mn, Mg, Ca amount)

Because Mn, Mg, Ca help the raising of the hot rolling processibility of copper alloy, thereby contain Mn, Mg, Ca selectively under the situations of these effects of needs.Containing under the situation of quantity not sufficient 0.0001%, can not get desired effect by total Mn, Mg, Ca one or more kinds of.On the other hand, if surpass 1.0%, generate then that macrocrystalline crystallisate and oxide compound not only reduce intensity and thermotolerance also makes the reduction of electric conductivity become violent by its content of total.Therefore, the content that contains these elements by total amount in 0.0001～1.0% scope selectively.

(Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au, Pt amount)

Because these compositions have the effect of the intensity that improves copper alloy, thereby contain these compositions under the situation of these effects of needs selectively.Containing under the situation of quantity not sufficient 0.001%, can not get desired effect by these compositions of total one or more kinds of.On the other hand,, then generate macrocrystalline crystallisate and oxide compound, not only reduce the reduction that intensity and thermotolerance also make electric conductivity and become acutely, so will not be preferably if surpass 1.0% by its content of total.Therefore, the content that contains these elements by total amount in 0.001～1.0% scope selectively.In addition, containing under the situation of these compositions with above-mentioned Mn, Mg, Ca element, the total content of the element that these are contained is made as below 1.0%.

(Hf, Th, Li, Na, K, Sr, Pd, W, Si, Nb, Al, V, Y, Mo, In, Ga, Ge, As, Sb, Bi, Te, B, norium)

These compositions are impurity element, surpass under 0.1% the situation in the total of the content of these elements, will generate macrocrystalline crystallisate and oxide compound and make intensity and thermotolerance reduction.Therefore, preferably be made as below 0.1% by the content of total with these elements.

(creating conditions)

Below, preferably the creating conditions of tissue that is used for the copper alloy plate tissue is made the invention described above regulation is described.Copper alloy plate of the present invention does not need common manufacturing process self is become big except Ra, the Rmax that is used to control above-mentioned surface, following preferred cold rolling the reaching the condition of cleaning of Rku, and uses the operation identical with usual method just can make.

That is, at first, cast being adjusted to the copper alloy molten metal that above-mentioned preferred one-tenth is grouped into.And, after ingot casting is carried out building up by welding, heat again or the heat treated that homogenizes, carry out hot rolling afterwards, the plate after the hot rolling is carried out water cooling.This hot rolling gets final product with common condition.

Then, carry out the once cold rolling of so-called half finish rolling system, annealing, clean after, make with extra care again that (finally) is cold rolling, low-temperature annealing (final annealing, refining annealing), make the copper alloy plate of finished product thickness of slab etc.Also can repeat these annealing and cold rolling.For example, under as the situation of semi-conductors such as lead frame with the copper alloy plate of material, the finished product thickness of slab is about 0.1～0.4mm.

In addition, also can before once cold rolling, carry out the solution treatment of copper alloy plate and the quench treatment of carrying out with water-cooled.At this moment, solid solution temperature is for example selected from 750～1000 ℃ scope.

(finally cold rolling)

The final cold rolling usual method of also using.Have for content and obtain on the Cu-Fe-P series copper alloy plate of big boundary that tensile strength is more than the 500MPa, hardness is the high strength more than the 150Hv at the solution strengthening element, according to the relation of present cold rolling working modulus, come the final cold rolling working modulus of strong process side decision.

The minimum draft (cold rolling rate) of each in addition, preferably will be final cold rolling mill train is made as more than 20%.If finally the minimum draft of each cold rolling mill train is lower than 20%, then make the thickness of slab distortion become greatly and reduce bendability.

But, final when cold rolling at this, be controlled at below the 1.5 μ m for the center line average roughness Ra with Cu-Fe-P series copper alloy plate surface is controlled at below the 0.2 μ m and with maximum height Rmax, and the surfaceness of employed Rolling roller is controlled.

Particularly, make the Rolling roller surfaceness with rolling after the copper alloy plate surface identical, carefully arrive center line average roughness Ra:0.2 μ m is following and maximum height Rmax:1.5 μ m is following high-gloss finish roller mill (surface grinding roller) etc.

(final annealing)

Preferably, by finally cold rolling,, carry out final annealing under the low temperature with successive heat treated stove to the surface to be controlled to be center line average roughness Ra be below the 0.2 μ m and maximum height Rmax is a Cu-Fe-P series copper alloy plate below the 1.5 μ m.Preferably will be made as at 100～400 ℃ of following cold condition below 300 minutes more than 0.2 minute with the final annealing condition of this successive heat treated stove.In the manufacture method of the copper alloy plate that is used for common lead frame,, except being used for aligned annealing (about 350 ℃ * 20 seconds), do not carry out final annealing after cold rolling final because the reduction of intensity therefore.But, in the present invention, use above-mentioned cold rolling condition, use the low temperatureization of final annealing to control this strength degradation again.And, improve bendability by carrying out final annealing at low temperatures.

In annealing temperature is to be lower than 100 ℃ temperature, 0.2 minute time conditions of annealing time less than, does not perhaps carry out under this stress relief annealed condition, and the tissue characteristics of copper alloy plate is almost indeclinable possibility height in final state after cold rolling.On the contrary, if anneal above 300 minutes time, then produce recrystallize with the temperature and the annealing time of annealing temperature above 400 ℃, and excessively produce the permutatation of dislocation and recover phenomenon, also make the precipitate coarse-grainization, therefore, the possibility height that stampability and intensity reduce.

(clean and handle)

Behind this final annealing, utilize the clean processing of following chemical milling, Cu-Fe-P series copper alloy plate is carried out surface control, Rku is controlled to be below 5.0.Clean processing for this,, then just can use the detergent of market sale as one sees fit if Rku can be made the clean processing of following chemical milling below 5.0.

In addition, as can be, be preferably in concentration is the aqueous sulfuric acid (room temperature) of 5～50 quality % and make the clean processing of following acid etching in 1～60 second of copper alloy plate dipping reliably to Rku being made the method below 5.0.If 1 second of sulfuric acid concentration less than 5 quality %, dipping time less than, the parent phase surface clean so that etching with insufficient, Rku can not be made the possibility height below 5.0.On the other hand, even sulfuric acid concentration surpasses 50 quality %, dipping time surpassed for 60 seconds, the clean and even etching on parent phase surface will become inhomogeneous, still Rku can not be made the possibility height below 5.0.

＜the second embodiment: the Cu-Fe-P series copper alloy plate that possesses high strength and good bendability 〉

(r value)

Among the present invention, as mentioned above, be more than the 500MPa in order to improve tensile strength, hardness is the bendability of the Cu-Fe-P series copper alloy plate more than the 150Hv, will be that the r value of parallel direction is made as more than 0.3 with respect to the rolling direction of copper alloy plate.Preferred r value is more than 0.35 below 0.5.

As mentioned above, increase in the work hardening amount that the worker brings by forcing of being increased by cold rolling working modulus and to carry out in the Cu-Fe-P series copper alloy plate of high strength, have and make crystal grain in rolling direction (growth) big anisotropy of crystal orientation of extending significantly.

Consequently, in the Cu-Fe-P series copper alloy plate after cold rolling, certainly will make that to be with respect to rolling direction that the r value of right angle orientation becomes higher than the r value that with respect to rolling direction is horizontal direction.

In the purposes of above-mentioned lead frame of Cu-Fe-P series copper alloy plate of the present invention etc., its bending machining mainly carries out being the bending machining of horizontal direction, promptly carrying out GoodWay (bending axis is the right angle in rolling direction) bending with respect to rolling direction.

Therefore, in the present invention, be the r value of parallel direction side mainly to the rolling direction with respect to copper alloy plate that must reduce the r value in order to improve this Good Way bending.In other words, need only the r value (rolling direction with respect to copper alloy plate is parallel direction) of a side that must reduce, then certainly will make the r value (is right angle orientation with respect to rolling direction) of a side that uprises become higher equally by the cold rolling raising that is used for above-mentioned high strength.

For example, as long as will be that the r value of horizontal direction is made as more than 0.3, certainly will be that the r value of right angle orientation is brought up to more than 0.4 then with respect to rolling direction with respect to the rolling direction of copper alloy plate.

(r pH-value determination pH)

For the rolling direction with respect to copper alloy plate is the r value of parallel direction, according to being that parallel direction is that the mode of the longitudinal direction of test film is made into the JIS5 test film and carries out tension test with respect to rolling direction.For reproducibility, tension test is installed extensometer by the JIS5 test film being fixed in after the tension test instrument, is stabilized in 10m/min with draw speed and carries out.

The r value for basis was tried to achieve with minimizing ratio thickness of slab to the plate of the material between 0.5% distortion is wide from 0 o'clock, and is used longitudinal elasticity normal value L (initial value L as the viscous deformation ratio ₀) and transverse elasticity normal value W (initial value W ₀) etc., calculate by following formula.

R value=In (W/W ₀)/[In (L/L ₀)-In (W/W ₀)]

(one-tenth of copper alloy plate is grouped into)

Among the present invention, use etc. as semiconductor lead frame, must have tensile strength is that 500MPa above high strength and hardness are that 150Hv is with first-class fundamental characteristics.And, satisfying on the basis of these fundamental characteristics, be prerequisite perhaps not reduce these fundamental characteristics, have the good plating of separating out unusually that prevents plating.Therefore, as Cu-Fe-P series copper alloy plate, made following essentially consist, that is, in quality %, the content of Fe has been made as 0.01～0.50% scope, the content of P is made as 0.01～0.15% scope, surplus is made up of Cu and unavoidable impurities.

With respect to this essentially consist, also can also contain elements such as following Zn, Sn selectively.In addition, also allow to contain element (impurity element) outside the record in the scope that does not hinder characteristic of the present invention.In addition, the demonstration % of the content of these alloying elements and impurity element is the meaning of all quality %.

(Fe)

Fe is intensity and a stable on heating principal element of separating out and improve copper alloy as Fe or Fe base intermetallic compound.If the content of Fe is very few, the help deficiency that intensity is improved then, though even satisfying the raising of electric conductivity carries out finally cold rollingly in strong process side, intensity is also insufficient.On the other hand, if the content of Fe is crossed electric conductivity is descended.Moreover, owing to increase the starting point that the crystallisate amount becomes fracture,, bendability is descended in the ratio of intensity instead the intensity of making and thermotolerance all reduce.Therefore, the content of Fe is made as 0.01～0.50% scope, preferably is made as 0.15～0.35% scope.

(P)

P still forms Fe and compound and makes the principal element of copper alloy high strength except that having desoxydatoin.If P content is very few, then compound separate out insufficient, thereby the help deficiency that intensity is improved, though even satisfying the raising of electric conductivity carries out finally cold rollingly in strong process side, intensity is also insufficient.On the other hand, if P content is too much, electric conductivity is descended, and the hot rolling processibility is reduced, be easy to generate crackle.Therefore, the content of P is made as 0.01～0.15% scope, preferably sets 0.05～0.12% scope.

(other element)

About content of Zn, Sn, Mn, Mg, Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au, Pt, S, Pb, Hf, Th, Li, Na, K, Sr, Pd, W, Si, Nb, Al, V, Y, Mo, In, Ga, Ge, As, Sb, Bi, Te, B, norium etc., can make identical with above-mentioned first embodiment.

(creating conditions)

Below, preferably the creating conditions of tissue that is used for the copper alloy plate tissue is made the invention described above regulation is described.Copper alloy plate of the present invention is controlled the following preferred final low temperature continuous annealing condition of above-mentioned r value except being used to, and does not need to make common manufacturing process self to become big, uses the operation identical with usual method just can make.

(finally cold rolling)

The final cold rolling usual method of also using.But, as mentioned above, have for content and obtain on the Cu-Fe-P series copper alloy plate of big boundary that tensile strength is more than the 500MPa, hardness is the high strength more than the 150Hv at the solution strengthening element, and according to the relation of present cold rolling working modulus, in the final cold rolling working modulus of strong process side decision.

The minimum draft (cold rolling rate) of each in addition, preferably will be final cold rolling mill train is made as more than 20%.If the minimum draft of final cold rolling each mill train is lower than 20%, the force of compression of width that then results from plate is little, and therefore, thick distortion becomes big and the r value is no longer increased.

(final annealing)

Final final low-temperature annealing condition after cold rolling is that the r value of horizontal direction is influential greatly for the rolling direction with respect to Cu-Fe-P series copper alloy plate.This point in order to be that the r value of horizontal direction is controlled to the rolling direction with respect to Cu-Fe-P series copper alloy plate, and is made as above-mentionedly more than 0.3 in the present invention, and carries out this low-temperature annealing by continuous annealing.At this moment, the plate in connecting is applied 0.1～8kgf/mm ²The suitable tension force of scope.Thus, can give thickness of slab and change little Compression and Expansion distortion.Increase the r value of plate by its viscous deformation.

At the too small not enough 0.1kgf/mm of this tension force ²The time, also make the tension force deficiency that loads on plate because of appointed condition and thickness of slab, can not make rolling direction with respect to Cu-Fe-P series copper alloy plate is that the r value of parallel direction reaches more than 0.3.In addition, surpass 8kgf/mm at overtension ²The time, also because of by appointed condition and thickness of slab, and in the thin finished product thickness range of 0.1 above-mentioned～0.4mm, be easy to make plate fracture in connecting.

This final low temperature continuous annealing condition, except that this r value, also influential greatly to fundamental characteristics such as intensity, elongations.This point in order to obtain characteristics such as elongation, and preferably will be made as in the final annealing condition of this successive heat treated stove at 100～400 ℃ of following cold condition below 300 minutes more than 0.2 minute in the present invention.In the manufacture method of the copper alloy plate that is used for common lead frame, because the reduction of intensity, therefore, except being used for aligned annealing (about 350 ℃ * 20 seconds), do not carry out final annealing after cold rolling final.But, in the present invention, control this strength degradation by the low temperatureization of final annealing.And, improve bendability etc. by carrying out final annealing at low temperatures.

Be lower than 100 ℃ and 0.2 minute time conditions of annealing time less than in the continuous annealing temperature, perhaps do not carry out under this stress relief annealed condition, the tissue characteristics of copper alloy plate is almost indeclinable possibility height in final state after cold rolling.On the contrary, if the temperature and the annealing time that surpass 400 ℃ with annealing temperature were annealed above 300 minutes time,, and excessively produce the permutatation of dislocation and recover phenomenon then owing to the generation recrystallize, also make the precipitate coarse-grainization, thereby the possibility height of stampability and intensity reduction.

In addition, preferably the threading speed in the continuous annealing is made as 10～100m/min scope.If this threading speed is too slow, then can make the recovery recrystallize development of material excessive.Therefore, intensity, elongation reduce.But, because the equipment restriction (capacity limit) in the continuous annealing furnace and the possibility of part are arranged, thereby do not need to make this threading speed near surpassing 100m/min.

Relative therewith, in step final annealing, plate not being applied tension force and can not improve with respect to the rolling direction of Cu-Fe-P series copper alloy plate in annealing process is the r value of parallel direction.In addition, for continuous annealing in the too slow identical reason of threading speed, can not get substrate properties such as intensity, elongation.

＜the three embodiment: the Cu-Fe-P series copper alloy plate that high strength and the stampability when punch process are good 〉

Below, specify as meaning and the embodiment of semiconductor lead frame with each important document of the Cu-Fe-P series copper alloy plate of the present invention that waits the characteristic that is used for satisfied necessity.

(one-tenth of copper alloy plate is grouped into)

In the present invention, use etc. as semiconductor lead frame, preferably having tensile strength is that 500MPa above high strength and hardness are that 150Hv is with first-class fundamental characteristics.And, satisfying on the basis of these fundamental characteristics, be prerequisite perhaps not reduce these fundamental characteristics, realize good stampability.Therefore, as Cu-Fe-P series copper alloy plate, make following essentially consist, promptly in quality %, the content of Fe is made as 0.01～0.50% scope, the content of P is made as 0.01～0.15% scope, surplus is made up of Cu and unavoidable impurities.

In the present invention, with respect to this essentially consist, also can also contain elements such as Zn described later, Sn selectively.In addition, also allow to contain element (impurity element) outside the record in the scope that does not hinder characteristic of the present invention.In addition, the demonstration % of the content of these alloying elements and impurity element all is meanings of quality %.

(Fe)

Fe is intensity and a stable on heating principal element of separating out and improve copper alloy as Fe or Fe base intermetallic compound.If the content of Fe is very few, then make above-mentioned growing amount of separating out crystal grain few because of creating conditions, though satisfy the help deficiency of the raising of electric conductivity, make intensity insufficient to the intensity raising.On the other hand, if crossing, the content of Fe makes electric conductivity and plating Ag decline at most.Therefore, when the above-mentioned amount of separating out of separating out crystal grain being increased, cause the growth coarse-grainization of separating out crystal grain for undue increase electric conductivity.Therefore, do not satisfy intensity and, stampability will be reduced by tensile properties given to this invention.Therefore, the content of Fe is made as 0.01～0.50% scope, preferably is made as 0.15～0.35% scope.

(P)

P still forms Fe and compound and makes the principal element of copper alloy high strength except that having desoxydatoin.When P content is very few, make separating out of compound insufficient because of creating conditions, thereby can not get desired intensity.On the other hand, when P content is too much, electric conductivity is descended, and can not satisfy by tensile properties given to this invention and reduce hot rolling processibility and stampability.Therefore, the content of P is made as 0.01～0.15% scope, preferably is made as 0.05～0.12% scope.

(other element)

About content of Zn, Sn, Mn, Mg, Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au, Pt, S, Pb, Hf, Th, Li, Na, K, Sr, Pd, W, Si, Nb, Al, V, Y, Mo, In, Ga, Ge, As, Sb, Bi, Te, B, norium etc., can be made as identical with above-mentioned first embodiment.

(tensile properties of plate)

Among the present invention, consist of prerequisite with above-mentioned composition, in above-mentioned mode to be that the modulus in tension obtained of the tension test of the test film of length direction and the tensile properties such as ratio of uniform elongation and percentage of total elongation are stipulated the good stampability of assurance Cu-Fe-P series copper alloy plate by adopting with the plate width direction of handing over for hanging down with respect to the rolling direction of Cu-Fe-P series copper alloy plate (right angle orientation).

(modulus in tension)

At first, the modulus in tension (modulus in tension) that tension test obtains that passes through with Cu-Fe-P series copper alloy plate is made as above 120GPa.Preferred modulus in tension (modulus in tension) is more than the 125GPa.Modulus in tension is big more, and the cumulative deformation with respect to the stress of plate institute load during punching press is more little.Therefore, when punching press, the fracture that produces punching press in early days diminishes the shear surface rate, and improves stampability.

On the other hand, this modulus in tension is low to 120GPa when following, when carrying out punching press, increases for the accumulative total deflection of the stress of load on the plate, can not produce the punching press fracture, and the shear plane rate increases the stampability reduction.

Also consider other reason though this modulus in tension is low to the reason below the 120GPa, but particularly in Cu-Fe-P series copper alloy plate, mainly enumerate, homogenizing when heat treated or heat treated before hot rolling described later, the homogeneous of plate tissue insufficient (plate tissue odds is even) even, and the water cooling starting temperature of hot rolling after finishing low excessively or intermittently carry out final annealing and even carry out final annealing continuously also making threading speed situation etc. too slowly.

(uniform elongation/percentage of total elongation)

Then, with Cu-Fe-P series copper alloy plate pass through uniform elongation that tension test obtains and the ratio of percentage of total elongation is that uniform elongation/percentage of total elongation is made as less than 0.50.Preferably uniform elongation/percentage of total elongation is made as less than 0.45.Uniform elongation/percentage of total elongation is up to more than 0.50, and in other words, if when big with respect to the ratio of the uniform elongation of percentage of total elongation, the ductility distortion takes place plate when punching press (material).Therefore, the deflection until the plate of the fracture of punching press is increased, it is big that the shear surface rate becomes, and then stampability is reduced.Relative therewith, if uniform elongation/percentage of total elongation less than 0.50, produce the punching press fracture and the shear surface rate is diminished then in early days during punching press, thereby stampability improves.

The reason that this uniform elongation/percentage of total elongation increases to more than 0.50 can be enumerated: in Cu-Fe-P series copper alloy plate, thereby make even the water cooling starting temperature particularly after the hot rolling is too high the too high recovery recrystallize development that makes material of precipitate quantity not sufficient, process annealing temperature in the plate tissue excessively, thereby the process annealing time too shortly makes the precipitate quantity not sufficient in the plate tissue carry out final annealing and even anneal continuously threading speed is waited slowly intermittence.

(tension test)

For reproducibility, obtain the tension test condition of the ratio of the modulus in tension of (mensuration) these regulations and uniform elongation and percentage of total elongation, undertaken by following test conditions.Test film is made JIS5 tension test sheet, from the Cu-Fe-P series copper alloy plate that obtains (manufacturing), gather with respect to rolling direction to be the tension test sheet of the direction at right angle as its length direction.After this test film is fixed in test apparatus extensometer is installed, is carried out tension test with draw speed 10.0m/min (until the constant speed of test film fracture).Test apparatus preferably uses 5882 type Instron companies to make universal testing machine.

Tensile strength is obtained according to the numerical value that is obtained by the instrumentation of laboratory apparatus, and percentage of total elongation makes the test film butt joint measure between stoichiometric point length and obtain after the test.In addition, modulus in tension and uniform elongation are obtained according to the numerical value that is obtained by above-mentioned extensometer.

(manufacture method)

Then, do following explanation to being used for that the copper alloy plate tissue is made as preferably creating conditions in the invention described above specialized range.As mentioned above, ratio by modulus in tension given to this invention and uniform elongation and percentage of total elongation, certainly being subjected to the very big influence that the one-tenth of Cu-Fe-P series copper alloy plate is grouped into, but being subjected to the very big influence of manufacture method and condition yet, is not only to depend on to become to be grouped into.Based on this point, for the modulus in tension that obtains in the present invention stipulating in above-mentioned mode and the tensile properties such as ratio of uniform elongation and percentage of total elongation, and manufacture method such as the threading speed during to the heat treated that homogenizes of Cu-Fe-P series copper alloy plate, water cooling temperature, the process annealing temperature after the hot rolling, final continuous annealing and condition are controlled as following record.

That is, at first, become the copper alloy molten metal be grouped into to cast to being adjusted to the invention described above.Melt-casting is undertaken by usual methods such as continuous casting, semicontinuous castings, still, for above-mentioned S, Pb are limited, preferably uses the poor copper melt raw material of S, Pb.Before the homogenize heat treated or the heat treated of ingot casting, use method commonly used to carry out building up by welding.

(heat treated that homogenizes or heat treated)

Ingot casting before hot rolling homogenize during heat treated or during heat treated, if the homogeneous of tissue insufficient (plate tissue odds is even), the Cu-Fe-P series copper alloy plate that then finally obtains is organized also inhomogeneous, not only reduces intensity, but also modulus in tension is dropped to below the 120GPa.Therefore, the homogenize heat treated or the heat treated of preferred ingot casting, according to the thickness of ingot casting and size at least with the temperature more than 900 ℃, carry out more than 2 hours.

(hot rolling)

Hot rolling begins with the temperature more than 900 ℃, and hot rolling is carried out the water cooling of hot-rolled sheet since 700～800 ℃ of temperature ranges after finishing.If the water cooling starting temperature after this hot rolling finishes is higher than 800 ℃, then water cooling starting temperature is too high and can not generate precipitate in the plate tissue, causes the precipitate quantity not sufficient.Therefore, become big, the ratio of uniform elongation and percentage of total elongation can not be made less than 0.50 with respect to the ratio of the uniform elongation of percentage of total elongation.

On the other hand, if the water cooling starting temperature after hot rolling finishes is lower than 700 ℃, then crystal grain grain refining too not only causes modulus in tension to descend, also make ratio become big, still the ratio of uniform elongation and percentage of total elongation can not be made less than 0.50 with respect to the uniform elongation of percentage of total elongation.Owing to generating macrocrystalline precipitate intensity is reduced.

Carry out water-cooled plate after hot rolling finished and further carried out so-called half finish rolling system, annealing, also made with extra care that (finally) is cold rolling, final annealing (low-temperature annealing, refining annealing) after cleaning, made the copper alloy plate of finished product thickness of slab etc.Also can repeat these annealing and cold rolling.For example, be used as under the situation of semi-conductor such as lead frame with the copper alloy plate of material, the finished product thickness of slab is about 0.1～0.4mm.

(process annealing)

In above-mentioned operation, the process annealing condition also has very big influence to uniform elongation/percentage of total elongation.The best process annealing condition that the ratio of uniform elongation and percentage of total elongation is made as less than 0.50 is to carry out more than 5 hours with the temperature below 430 ℃.If this process annealing temperature is too high, the recovery recrystallize development that then makes material excessively, thereby not only reduce intensity but also make ratio become big with respect to the uniform elongation of percentage of total elongation, the ratio of uniform elongation and percentage of total elongation can not be made as less than 0.50.If this process annealing time is too short, the precipitate quantity not sufficient in the plate tissue then, electric conductivity reduction.

(final annealing)

In above-mentioned operation, the final annealing condition is also influential greatly to modulus in tension and uniform elongation/percentage of total elongation.For the modulus in tension that obtains Cu-Fe-P series copper alloy plate surpasses the characteristic of the ratio less than 0.50 of 120GPa, uniform elongation and percentage of total elongation, while and be necessary to carry out making plate (coiled material) in stove, to connect the continuous annealing of handling continuously.

And, in order to obtain this characteristic, the threading speed in the continuous annealing need be controlled at 10～100m/min scope.If this threading speed is too slow, then make the recovery recrystallize development of material excessive.Therefore, not only intensity reduces, and makes the ratio with respect to the uniform elongation of percentage of total elongation become big, the ratio of uniform elongation and percentage of total elongation can not be made as less than 0.50.In addition, can not make modulus in tension surpass 120GPa.But, because the equipment restriction (capacity limit) in the continuous annealing and the possibility of part are arranged, so will this threading speed not add near surpassing 100m/min.

Relative therewith, in intermittent type final annealing temperature, for with continuous annealing in the too slow identical reason of threading speed, and can not get in the present invention ratio with the modulus in tension in the tension test of above-mentioned mode defined and uniform elongation and percentage of total elongation.

＜the four embodiment: the Cu-Fe-P series copper alloy plate that high strength and plating are good 〉

(one-tenth of copper alloy plate is grouped into)

In the present invention, use etc. as semiconductor lead frame, preferably having tensile strength is that 500MPa above high strength and hardness are that 150Hv is with first-class fundamental characteristics.And, satisfying on the basis of these fundamental characteristics, be prerequisite perhaps not reduce these fundamental characteristics, have the good plating that prevents that plating from separating out unusually.Therefore, as Cu-Fe-P series copper alloy plate, make following essentially consist, that is, in quality %, the content of Fe is made as 0.01～0.50% scope, the content of P is made as 0.01～0.15% scope, surplus is made up of Cu and unavoidable impurities.

One-tenth among the present invention is grouped into, and it is characterized in that, with respect to this essentially consist, also contains C:3～15ppm, and is controlled to be respectively below the O:40ppm, below the H:0.7ppm.

Be grouped into respect to such one-tenth, also can also contain elements such as Zn described later, Sn selectively.In addition, also allow in the scope that does not hinder characteristic of the present invention and contain element (impurity element) outside the record.In addition, the demonstration % of the content of these alloying elements and impurity element all is meanings of quality %.

(Fe)

Fe is intensity and a stable on heating principal element of separating out and improve copper alloy as Fe or Fe base intermetallic compound.If the content of Fe is very few, then make above-mentioned growing amount of separating out crystal grain few because of creating conditions, though satisfy the help deficiency of the raising of electric conductivity to the intensity raising, and make intensity insufficient.On the other hand, if the content of Fe is crossed electric conductivity is descended.Therefore, if undue increase electric conductivity and the above-mentioned amount of separating out of separating out crystal grain is increased, then cause the growth coarse-grainization of separating out crystal grain and reduce plating Ag.Moreover, intensity and thermotolerance are all reduced.Therefore, the content of Fe is made as 0.01～0.50% scope, preferably is made as 0.15～0.35% scope.

(P)

P still forms Fe and compound and makes the principal element of copper alloy high strength except that having desoxydatoin.If P content is very few, then makes separating out of compound insufficient, thereby can not get desired intensity because of creating conditions.On the other hand, if P content is too much, electric conductivity is descended, and reduce the hot rolling processibility.Therefore, the content of P is made as 0.01～0.15% scope, preferably is made as 0.05～0.12% scope.

(C)

The inevitable starting point that becomes inclusion and through hole with O, H in a certain amount of Cu-Fe-P of the being present in series copper alloy plate.These O, H are easy to aggegation, are forming under the agglutinative situation, make the inclusion of generation and through hole become coarse-grain, become the starting point of separating out unusually (reason) of above-mentioned plating Ag etc.On Cu-Fe-P series copper alloy plate surface, also have inclusion and through hole usually, but they are only otherwise special coarse-grainization, in the size of common size and even miniaturization, can not become the starting point of separating out unusually of above-mentioned plating Ag etc.

C suppresses with the O in a certain amount of Cu-Fe-P of the being present in series copper alloy plate, the aggegation of H inevitable, and the starting point of inclusion and through hole is increased, and the inclusion of generation and the size of through hole are made the common size and even the size of miniaturization.Prevent the inclusion that generates and through hole thickization especially thus, prevent that these inclusiones and through hole from becoming the starting point of separating out unusually of above-mentioned plating Ag etc.

In order to bring into play the above-mentioned effect of C, be more than the 3ppm and contain C.If C contains quantity not sufficient 3ppm, then become and the C content of sneaking into naturally does not have marked difference, bring into play the above-mentioned effect of separating out unusually that prevents to plate Ag etc. less than C.

On the other hand, surpassing 15ppm at the content of C, is to surpass under the situation of 10ppm strictly speaking, owing to generate macrocrystalline carbide, becomes the starting point of separating out unusually (reason) of above-mentioned plating Ag etc. on the contrary.In addition, as mentioned above, because C is easy to dissipation, as patent documentation 11, even add the Fe-C mother alloy in the molten metal fluid, it is also very difficult to make C content surpass 15ppm.

Therefore, the content of C is made as 3～15ppm scope, preferably is made as 3～10ppm scope.In addition, according to JIS Z 2615 standards, the content of C is to heat in oxygen atmosphere gas and extract carbon in the sample out, analyzes by the burning infrared absorption.

(O、H)

In the present invention, in order to guarantee the action effect of above-mentioned C, and the O of the starting point that becomes inclusion and through hole, the content of H are limited.Particularly, be restricted to respectively below the O:40ppm, be preferably below the 20ppm, below the H:1.0ppm, be preferably below the 0.5ppm.Under and/or the situation that H is too much too much at O, even contain C in above-mentioned scope, also can make the inclusion of generation and through hole become coarse-grain, become the starting point of separating out unusually (reason) of above-mentioned plating Ag etc. because of the amount that makes the inoperative O of C, H too much make these O, H cohesion.

But, in the higher limit of the content of this O given to this invention, H compared with prior art, neither the numerical value of low especially (lacking) is not again the numerical value of high especially (many).In a sense, by Cu-Fe-P series copper alloy plate, be common concentration level.That is, the higher limit of this O, H content is in the casting melting process stage of the present invention, even contain to a certain degree hydrogen and oxygen etc., also can make the corresponding to regulation of the purpose of separating out unusually that prevents (can prevent) above-mentioned plating.

In addition, O, analyzes by infrared absorption by the oxygen in the rare gas element method of fusion extraction sample according to the JISZ2613 standard.In addition, H is according to the JISZ2614 standard, extracts hydrogen in the sample out by the rare gas element method of fusion, by the conscientious analysis of thermal conductivity method.

(other element)

(manufacture method)

Then, do following explanation to being used for that copper alloy plate is made as preferably creating conditions in the invention described above specialized range.Copper alloy plate of the present invention except being used to control the preferred condition of above-mentioned C, H, O content, does not need common manufacturing process self is become big, just can make by the operation identical with method commonly used.

At first, become the copper alloy molten metal be grouped into to cast to being adjusted to the invention described above.Melt-casting is undertaken by usual methods such as continuous casting, semicontinuous castings.At this moment, because above-mentioned S, Pb sneak into from the copper melt raw material, thereby in order to limit these S, Pb, and preferably use the poor copper melt raw material of S, Pb.

(control of C content)

C is in the melt-casting operation with common air melting stove to solid solution (fusing) source of molten metal, from furnace wall refractory and cut off the carbon material etc. of usefulness from the atmosphere of mounting on the molten metal of air melting stove.In addition, in the vacuum melting stove also from furnace wall refractory.In the present invention, even do not use intentional C addition means such as Fe-C mother alloy interpolation, as long as control copper alloy molten metal temperature (temperature of fusion), just can control the solid solution capacity to molten metal from the C in these C solid solution sources.As this copper alloy molten metal temperature control, in the present invention, with respect to the copper alloy molten metal temperature at common melting process is 1200 ℃ below the degree, will be arranged to higher high temperature more than 1300 ℃ at the copper alloy molten metal temperature (temperature of fusion) of air melting stove and vacuum melting stove.In addition, intention is to use carbon system crucible and adds the addition means of Fe-C mother alloy, with the control combination of above-mentioned copper alloy molten metal temperature together, much less also can make in the above-mentioned C content range of the present invention.

By the copper alloy molten metal temperature is made as such high temperature, increase from above-mentioned C solid solution source to the C of molten metal fusing amount (C content), be made as in the above-mentioned C content range of the present invention.If the copper alloy molten metal temperature is the low temperature of 1300 ℃ of less thaies, just can be not different with method commonly used, make the fusing quantity not sufficient of C, have only the C quantity not sufficient 3ppm in the final Cu-Fe-P series copper alloy plate.In addition, under the situation of air melting stove and vacuum melting stove, if it is too slow to 600 ℃ average cooling rate (setting rate) from the casting beginning, then since halfway the C in the molten metal loss takes place, might make the fusing quantity not sufficient of C, therefore, preferably this average cooling rate is made as and surpasses 5.0 ℃/second high speed.

(the content control of O and H)

For the content that suppresses O and H increases, the appearance molten metal that as far as possible suppresses copper in the melt-casting process with atmospheric contact very important.For example, under the situation of vacuum oven (the solid solution source of C is a furnace wall refractory), atmospheric furnace, the average cooling rate (setting rate) from the casting beginning to 600 ℃ is made as above 5.0 ℃/second.As mentioned above, this average cooling rate control is good effective to the control of C content.In addition, operation below, it is also effective to the reduction of O and H amount that the atmosphere surrounding of annealing furnace is controlled.

The ingot casting that obtain carried out building up by welding after, again carried out heating or homogenize heat treated after carry out hot rolling, plate hot rolling after carried out water cooling thereafter.Moreover, carry out so-called half refining rolling, annealing, clean after, make with extra care again that (finally) is cold rolling, low-temperature annealing (final annealing, refining annealing), make the copper alloy plate of finished product thickness of slab.Also can make these annealing and cold rolling repeating.For example, under as the situation of semi-conductors such as lead frame with the copper alloy plate of material, the finished product thickness of slab is 0.1～0.4mm.

In addition, also can before once cold rolling, carry out the solution treatment of copper alloy plate and the quenching of being undertaken by water cooling.At this moment, solid solution temperature for example can be selected in 750～1000 ℃ of scopes.

After finally cold rolling, also can direct cold rolling make final finished, but also can be used for aligned annealing at low temperatures.

Embodiment

(embodiment 1)

Below, embodiments of the invention are described.Cu-Fe-P series copper alloy thin plate as shown in table 2, that each chemical ingredients as shown in table 1 is formed only carries out various changes to the clean condition of following the chemical milling behind the final annealing and makes.And, the adaptation (exfoliation temperature of maintenance epithelium) of the oxide scale film of these each copper alloy thin plate is estimated.These results are as shown in table 2.

Particularly, after the copper alloy that each chemical ingredients shown in the table 1 is formed dissolves with induction furnace respectively, cast ingot casting, obtain the ingot casting of thick 70mm * wide 200mm * long 500mm by the semicontinuous casting method.The surface is carried out building up by welding and to after each ingot casting heating, carried out the plate that thick 16mm is made in hot rolling under 950 ℃ temperature, water, quench from the temperature more than 750 ℃.Then, remove after the descaling, carry out once cold rolling (half is refining rolling).After this plate carried out building up by welding, carry out while anneal and carry out the finally cold rolling of four cold rolling mill traines, follow, under 350 ℃, 20 seconds cold condition, carry out final continuous annealing, obtain being adapted to the copper alloy plate of thick 0.15mm of the slimming of lead frame.

At this moment, above-mentioned final cold rolling all be common in each example, the minimum draft of each mill train is made as 30%, uses and make roller surface below the center line average roughness Ra:0.2 μ m and the superfine high-gloss finish roll (surface grinding roll) that gets below the maximum height Rmax:1.5 μ m.

In addition, after above-mentioned final continuous annealing, press the condition shown in the table 2, carry out Cu-Fe-P series copper alloy plate be impregnated in the clean processing of following acid etching to follow of aqueous sulfuric acid (room temperature), the Rku on control Cu-Fe-P series copper alloy plate surface.

In addition, for the copper alloy shown in the table 1, forming except that the surplus after the record amount of element all is Cu, as other impurity, the content of Hf, Th, Li, Na, K, Sr, Pd, W, S, Si, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B, norium is counted below the 0.1 quality % by the total of these elements.

In addition, under the one or more kinds of situations in containing Mn, Mg, Ca, the total amount is made as the scope of 0.0001～1.0 quality %, under the one or more kinds of situations in containing Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au, Pt, the total amount is made as 0.001～1.0 mass range, in addition, also that these elements are whole total amounts are made as below the 1.0 quality %.

For each copper alloy plate that obtains in the above described manner, in each example all is to cut out sample from copper alloy plate, has measured characteristics such as tensile strength, hardness, electric conductivity, and center line average roughness Ra, maximum height Rmax in the surface roughness measurement that with the JISB06010 method is benchmark, standout (kurtosis value) Rku of roughness curve of these each copper alloy plates.These results are as shown in table 2 respectively.

(measurement of surfaceness)

Use the surfagauge (name of product: サ one Off コ system 1400D) of Tokyo Seimitsu Co., Ltd's system, measured center line average roughness Ra (μ m), the maximum height Rmax (μ m) on the above-mentioned copper alloy plate test film surface that obtains, standout (kurtosis value) Rku of roughness curve according to JIS B0601 method.Measurement is that any 3 points (3 positions) to test film carry out every 4.0mm length, and this result has been carried out on average.

(hardness measurement)

Cut out the test film of 10 * 10mm from the above-mentioned copper alloy plate that obtains, (trade name: microhardness tester) load that applies 0.5kg has carried out hardness measurement 4 positions, and hardness is got their mean value to use the micro-DPH meter of loose damp precision instrument Co., Ltd. system.

(conductivity measurement)

The electric conductivity of copper alloy plate sample is to use milling machine that the flaky test film of the weak point of wide 10mm * long 30mm is processed, and uses double bridge formula electric resistance measuring apparatus measuring resistance, calculates by the average cross-section method.

(oxide film adaptation)

In addition, each oxide film fitness test for the sample of having a try passes through the band spalling test, in the ultimate temperature of peeling off oxide film it is estimated.The band spalling test is the test film that cuts out 10 * 30mm from the copper alloy plate that obtains in the above described manner, after the temperature of usefulness regulation heated 5 minutes in atmosphere, the band (trade name: Sumitomo 3M corporate system is gluedd joint band) of market sale is pasted on the test film surface that oxide film generates, peels off.At this moment,, obtain oxide film and produce the minimum afore mentioned rules temperature of peeling off in that Heating temperature is risen when changing by 10 ℃ of pitches, with this as the oxide film exfoliation temperature.

Because this oxide film exfoliation temperature is in more than 350 ℃, thereby can be described as essential (fully) oxide film adaptation under the high temperatureization of Heating temperature in the heating process of the making that is used for copper alloy plate and lead frame.

In addition, 5 minutes heating in above-mentioned atmosphere of the present invention, heat-up time is long, we can say that the evaluation test condition of oxide film adaptation of the heating of 200～500 ℃ under carrying out 3 minute short period more such than patent documentation 2,3 is more strict.In other words, heat-up time of the present invention long oxide film fitness test with the oxide film adaptation under the high temperatureization of Heating temperature corresponding (being correlated with) of the heating process of the making that is used for copper alloy plate and lead frame.

Relative therewith, carrying out in the evaluation test condition of the oxide film adaptation of the heating of above-mentioned 3 minute short period of patent documentation 2,3, we can say insufficient with corresponding (relevant) of the oxide film adaptation under the high temperatureization of Heating temperature of the heating process of the making that is used for copper alloy plate and lead frame.That is, under the evaluation test condition of the oxide film adaptation of patent documentation 2,3, even the result is good, also may not be good in the oxide film adaptation under the high temperatureization of Heating temperature of the heating process of the making that is used for copper alloy plate and lead frame.

As indicated in table 1,2, the copper alloy in the present invention forms is an example 1～13rd, and tensile strength is that 500MPa is above, hardness is the above high strength of 150Hv.In addition, this copper alloy plate be that center line average roughness Ra in the surface finish measurement of benchmark is below the 0.2 μ m with the JISB0601 method, maximum height Rmax is below the 1.5 μ m.

And example 1～13 is owing to the clean processing of using aqueous sulfuric acid after final continuous annealing by preferred condition, thereby the standout of roughness curve (kurtosis value) Rku is below 5.0.It is good oxide film adaptation more than 350 ℃ that its result has the oxide film exfoliation temperature.Therefore, example 1～13 is as the semi-conductor mother metal, the resin when the assembling of semiconductor packages and the adaptation height of pad, the reliability height of encapsulation.

Relative therewith, comparative example 14,15 is not used the clean processing of aqueous sulfuric acid according to preferred condition after final continuous annealing.The sulfuric acid concentration of the clean processing of comparative example 16 these aqueous sulfuric acids of usefulness is low excessively.The sulfuric acid concentration of the clean processing of comparative example 17 these aqueous sulfuric acids of usefulness is too high.The dipping time of the clean processing of comparative example 18 these aqueous sulfuric acids of usefulness is long.These results are that the standout of the roughness curve of comparative example 14～18 (kurtosis value) Rku surpasses 5.0.

On the other hand, comparative example 14～18th, the copper alloy in the present invention forms, be that tensile strength is that 500MPa is above, hardness is the above high strength of 150Hv, the center line average roughness Ra in the surface roughness measurement is below the 0.2 μ m, and maximum height Rku is below the 1.5 μ m.But, because standout (kurtosis value) Rku of the roughness curve of comparative example 14～18 surpasses 5.0, thereby 350 ℃ of oxide film exfoliation temperature less thaies, the oxide film adaptation is poor.Therefore, comparative example 14～18 is as the semi-conductor mother metal, and the resin when the assembling of semiconductor packages and the adaptation of pad are low, and the reliability of encapsulation is also low.

Comparative example 19～22 is owing to use the clean processing of aqueous sulfuric acid according to preferred condition after final continuous annealing, thereby the standout of roughness curve (kurtosis value) Rku is below 5.0, has good oxide film adaptation.

But the content of the Fe of comparative example 19 is lower than lower limit 0.01%, and strength level is low, can not use as the semi-conductor mother metal.

The content of the Fe of comparative example 20 is higher than the upper limit 5.0%, and electric conductivity obviously reduces, and can not use as the semi-conductor mother metal.

The content of the P of comparative example 21 is lower than lower limit 0.01%, and strength level is low, can not use as the semi-conductor mother metal.

The content of the P of comparative example 22 is higher than the upper limit 0.15%, cracks in hot rolling, therefore, carves at this moment and interrupts trial-production.

Confirmed according to The above results, except that high strength, the one-tenth that is used to have the copper alloy plate of the present invention of good oxide film adaptation is grouped into, the critical meaning of surfaceness regulation, and is used to obtain the meaning of preferably creating conditions of this surfaceness.

Table 1

* in the expression of each constituent content ,-expression detects below the boundary.

Table 2

Embodiment 2

The following describes embodiments of the invention.As shown in table 4, the tension force condition during only to final low-temperature annealing is carried out various changes, has made the Cu-Fe-P series copper alloy thin plate that each chemical ingredients shown in the table 3 is formed.And, r value and bendability that these rolling directions with respect to each copper alloy thin plate are horizontal direction are estimated.These results are as shown in table 4.

Particularly, after the copper alloy that each chemical ingredients shown in the table 3 is formed dissolves with induction furnace respectively, cast ingot casting, obtain the ingot casting of thick 70mm * wide 200mm * long 500mm by the semicontinuous casting method.To the surface of each ingot casting carry out building up by welding and the heating after, carry out the plate that thick 16mm is made in hot rolling, quench water from the temperature more than 650 ℃.Then, remove after the descaling, carry out once cold rolling (half is refining rolling).After this plate carried out building up by welding, carry out the limit and carry out the process annealing limit and carry out cold rollingly, then carry out final annealing, obtain being adapted to the copper alloy plate of thick 0.15mm of the slimming of lead frame at 400 ℃.

When the minimum draft of final cold rolling each mill train and final low-temperature annealing to the plate load tension force as shown in table 4.So just the tension force condition of the plate when the minimum draft of final cold rolling each mill train and the final low-temperature annealing being carried out various changes, is the r value of parallel direction with control with respect to the rolling direction of each copper alloy plate.

In addition, copper alloy as shown in table 3 all is to consist of Cu except the surplus after the record amount of element, as other impurity, the content of Hf, Th, Li, Na, K, Sr, Pd, W, S, Si, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B, norium is counted below the 0.1 quality % by the total of these elements.

In addition, each example all is to cut out sample from the copper alloy plate that obtains, and carries out mensuration, pliability tests such as tension test, electric conductivity.These results are as shown in table 4.

(tension test)

Tension test is the condition according to above-mentioned r pH-value determination pH, uses the universal testing machine of 5882 type Instron society systems, is under the condition of 10.0mm/min, GL=50mm in room temperature, trial speed, has measured tensile strength, 0.2% yielding stress, r value.

(conductivity measurement)

The electric conductivity of copper alloy plate sample is to use milling machine that the flaky test film of the weak point of wide 10mm * long 300mm is processed, and uses double bridge formula electric resistance measuring apparatus measuring resistance, calculates by the average cross-section method.

(evaluation test of bendability)

The pliability test of copper alloy plate is carried out according to Japanese copper association technological standard.Sheet material is cut into wide 10mm * long 30mm, and the bending of Good Way (bending axis is the right angle in rolling direction) is carried out on the limit, and the limit has or not the crackle of bend with 50 times observation by light microscope.And, obtained the ratio R/t of the thickness t (0.15mm) of the minimum profile curvature radius R that do not crack and copper alloy plate.The has excellent bending properties that this R/t is little.But, because the high more bendability that must make of intensity is low more, thereby under the situation as the copper alloy plate of semiconductor materials such as lead frame, if hardness is then obtained R/t less than 1.5 in 150～200Hv, if then obtain R/t less than 2.0 more than the 200Hv.Because not enough 150Hv is the outer soft (low strength) of object of the present invention, if not enough 150Hv then obtains R/t less than 0.5.

As indicated in table 3,4, the copper alloy in the present invention forms is an example 31～43rd, and tensile strength is that 500MPa is above, hardness is the above high strength of 150Hv.And, because example 31～43 makes the preferred tension force of plate load when final annealing, thereby be that the r value of parallel direction is more than 0.3 with respect to the rolling direction of copper alloy thin plate.Therefore, example 31～43 is as the has excellent bending properties of semi-conductor mother metal.

Relative therewith, comparative example 44,45 does not apply tension force to plate when final annealing.Consequently, comparative example 44,45 is the copper alloy of the present invention in forming, though be that tensile strength is that 500MPa is above, hardness is the above high strength of 150Hv, is the r value less than 0.3 of parallel direction with respect to the rolling direction of copper alloy plate.Therefore, comparative example 44,45 is poor as the bendability of semi-conductor mother metal.

The content of the Fe of comparative example 46 is lower than lower limit 0.01%, and strength level is low, in this point, although be that the r value of mean direction is more than 0.3 with respect to the rolling direction of copper alloy thin plate, can not use as the semi-conductor mother metal.

The content of the Fe of comparative example 47 departs from the upper limit 5.0% a little, and for the distribution of intensity, bendability is poor.In addition, even compare with example equality strength level example, also the distribution electric conductivity for intensity obviously reduces, and can not use as the semi-conductor mother metal.

The content of the P of comparative example 48 is lower than lower limit 0.01%, and strength level is low, in this point, although be that the r value of mean direction is more than 0.3 with respect to the rolling direction of copper alloy thin plate, can not use as the semi-conductor mother metal.

The content of the P of comparative example 49 is higher than the upper limit 0.15%, owing in hot rolling, crack, thereby interrupt trial-production at this moment.

The minimum draft less than 20% of each final cold rolling mill train of comparative example 50.Therefore, although be the copper alloy of the present invention in forming, be the r value less than 0.3 of parallel direction with respect to the rolling direction of copper alloy plate, bendability is poor.

Confirmed that according to The above results except that high strength, the one-tenth that is used for the also good copper alloy plate of the present invention of bendability is grouped into, the critical meaning of r value regulation and be used to obtain this r value and high-intensity meaning of preferably creating conditions.

Table 3

Table 4

Embodiment 3

Below, embodiments of the invention are described.Threading speed when changing water cooling starting temperature after homogenize heat treated, the hot rolling, process annealing temperature, final continuous annealing etc. is created conditions, and has made Cu-Fe-P series copper alloy thin plate.And to the modulus in tension of these each copper alloy plates and the tensile properties such as ratio of uniform elongation and percentage of total elongation, perhaps characteristics such as tensile strength, hardness, electric conductivity, shear surface rate are estimated.These results are as shown in table 5.

Particularly, using the air melting stove is that induction furnace has melted the copper alloy molten metal that each chemical ingredients shown in the table 5 is formed, and has obtained the ingot casting of thick 70mm * wide 200mm * long 500mm with the semicontinuous casting method.

Building up by welding is carried out on surface to these each ingot castings, carried out the heating soaking by the condition shown in the table 6 (temperature * time) after, under 950 ℃ temperature, carry out the plate that thick 16mm is made in hot rolling, quench water from the starting temperature shown in the table 6.Then, remove descaling, carried out once cold rolling (half is refining rolling) afterwards.This plate is carried out after the building up by welding, and the cold rolling finally cold rolling of 4 mill traines carried out on the process annealing limit of being undertaken handling in 10 hours by the temperature limit shown in the table 6, obtains being suitable for the copper alloy plate of thick 0.15mm of the thin plateization of lead frame.This copper alloy plate at 350 ℃ of final annealings that carry out carrying out by the threading speed shown in the table 6 continuous annealing, is made the finished product copper alloy plate.

In addition, copper alloy shown in the table 5 all is that the surplus of having removed after the record amount of element consists of Cu, as other impurity, the content of Hf, Th, Li, Na, K, Sr, Pd, W, Si, Nb, Al, V, Y, Mo, In, Ga, Ge, As, Sb, Bi, Te, B, norium is counted below the 0.1 quality % by the total of these elements.

For the copper alloy plate that obtains like this, each example all is will cut out test film (sample) as length direction with respect to the vertical plate width direction of rolling direction from copper alloy plate, to the modulus in tension of each sample and the ratio of uniform elongation and percentage of total elongation, perhaps characteristics such as tensile strength, hardness, electric conductivity, shear surface rate are estimated.These evaluation results are as shown in table 6 respectively.

(shear surface rate mensuration)

The shear surface rate (shear surface ratio) of the lead-in wire section that the punching press of the lead-in wire stamping-out by using the analogue copper alloy sheets designs is estimated stampability.If this shear surface rate is below 75%, it is good then can be evaluated as stampability.According to the evaluation that this shear surface rate is carried out, compared with the lead-in wire of stamping-out on copper alloy plate, measure the evaluation test of the stampability of overlap height at this moment, can estimate desired stampability exactly.

Punching test is to use stamping machine (gap: 5%), as shown in Figure 2, the G-6316 lubricating oil that uses Japan's work oil to make on the lead-in wire of wide 1mm * long 10mm, stamping-out is made with respect to the rolling direction shown in the arrow to be the punching 2 of vertical plate width direction as length direction successively on copper alloy plate (test film) 1.

Thus, cut off the center of (with dashed lines 3 expression place of incisions) punching 2 along its length, observe the cut surface of punching 2, obtain by image analysis according to the surface picture of having used the microscopical cut surface of optical profile type from the direction of arrow 4.The shear surface rate is the area ratio (area of the area/cut surface of shear surface) of the shear surface in cut surface, the area of cut surface is made the thickness of slab 0.15mm * mensuration width 0.5mm of copper alloy face, the area of shear surface is made the area of the shear surface in the scope of measuring width 0.5mm.(adding up to 9 positions) measured in 3 holes of each sample stamping-out, each hole 3 positions, obtain its mean value.

(measurement of hardness)

The load-carrying that the measurement of hardness of copper alloy plate sample is to use micro-DPH meter to apply 0.5kg is carried out in any 3 positions of sample, and hardness is to go out as their mean value calculation.

(electric conductivity measuring)

As indicated in table 5,6, copper alloy in the present invention forms is an example 51～61, its composition consists of in the scope of the invention, and the threading speed when the water cooling starting temperature after the heat treated that homogenizes, hot rolling, final continuous annealing etc. is made in creating conditions to preferred range.Therefore, example 51～61 has modulus in tension and surpasses 120GPa, simultaneously, and the tensile properties of uniform elongation/percentage of total elongation less than 0.50.

Consequently, example 51～61 for tensile strength be more than the 500MPa, hardness is the high-intensity distribution more than the 150Hv, is relative high conductivity, in addition, the shear surface rate is below 75%, stampability is also good.

But the content of Fe is near the example 55 of the content crystallization lower limit of the example 53 of lower limit and P, compares with other example 51,52 etc., and strength ratio is lower.In addition, the content of Fe is compared with other example 51,52 near the content of the example 54 of the upper limit and the P example 56 near the upper limit, and the shear surface rate is than higher, and electric conductivity is also lower.

Relative therewith, in the comparative example 62～67, although be to form interior copper alloy with example 1 identical the present invention of being, the threading speed when the water cooling starting temperature after the heat treated that homogenizes, the hot rolling, final continuous annealing etc. is created conditions and is departed from preferred range.Therefore, in the comparative example 62～67, modulus in tension cross low for 120GPa following or uniform elongation/percentage of total elongation too high be more than 0.5.Consequently, comparative example 62～67 shear surface rates surpass 75%, and stampability is obviously relatively poor.

The time that homogenizes during heat treated of comparative example 62 is too short.The temperature that homogenizes during heat treated of comparative example 63 is low excessively.Water cooling starting temperature after the hot rolling of comparative example 64 is too high.Water cooling starting temperature after the hot rolling of comparative example 65 is low excessively.The process annealing temperature of comparative example 66 is too high.Threading speed during the final continuous annealing of comparative example 67 is too slow.

Although the copper alloy of comparative example 68～71 is made in manufacture method is preferred condition, its composition departs from the scope of the invention.Therefore, in the comparative example 68～71, modulus in tension cross low for 120GPa following or uniform elongation/percentage of total elongation too high be more than 0.50.Consequently, comparative example 68～71 shear surface rates surpass 75%, and stampability is obviously relatively poor.

The content of the Fe of comparative example 68 is lower than lower limit 0.01%.Therefore, shear surface rate height, stampability is poor, can not realize high strength.

The content of the Fe of comparative example 69 is higher than the upper limit 5.0%.Therefore, shear surface rate height, stampability is poor, can not realize high strength.

The content of the copper alloy plate P of comparative example 70 is lower than lower limit 0.01%, therefore, shear surface rate height, stampability is poor, can not realize high strength.

The content of the copper alloy plate P of comparative example 71 is higher than the upper limit 0.15%.Therefore crack at course of hot rolling.

Confirmed according to The above results, except that high strength, the critical meaning of tensile properties such as the one-tenth that is used for the also good copper alloy plate of the present invention of punch process is grouped into, modulus in tension, uniform elongation/percentage of total elongation, and the meaning of preferably creating conditions that is used to obtain such tensile properties.

Table 5

Table 6

(embodiment 4)

Below, embodiments of the invention are described.Particularly change temperature of fusion and average cooling temperature (setting rate: ℃/second) in the air melting stove, made and have the copper alloy thin plate that contains various C, O, H from casting beginning to 600 ℃.And, characteristics such as the tensile strength of these each copper alloy thin plate, hardness, electric conductivity, plating are estimated.These results are as shown in table 8.

Particularly, the copper alloy that each chemical ingredients shown in the his-and-hers watches 7 is formed as shown in table 8ly changes temperature of fusion separately and has cast ingot casting from casting beginning to 600 ℃ average cooling rate like that.It is induction furnace that the air melting stove is used in fusing, has obtained the ingot casting of thick 70mm * wide 200mm * long 500mm by the semicontinuous casting method.

The surface is carried out building up by welding and with after these a few ingot casting heating, carried out the plate that thick 16mm is made in hot rolling under 950 ℃ temperature, water, quench from the temperature more than 750 ℃.Then, remove descaling, afterwards, carried out cold rolling successively (half is refining rolling).After this plate carried out building up by welding, carry out the limit and adopt the process annealing limit to carry out cold rolling finally cold rolling of four round-robin, then, carry out final annealing, obtained meeting the copper alloy plate of thick 0.15mm of the thin plateization of lead frame at 350 ℃ of cold condition with 20 seconds.

In addition, copper alloy shown in the table 7 all is that the surplus of having removed after the record amount of element consists of Cu, as other impurity, the content of Hf, Th, Li, Na, K, Sr, Pd, W, Si, C, Nb, Al, V, Y, Mo, In, Ga, Ge, As, Sb, Bi, Te, B, norium is counted below the 0.1 quality % by the total of these elements.

The content of oxygen (O) is to use the made EMGA-650A type device of Japanese hole factory's making, according to JIS Z 2613, with the oxygen in the rare gas element method of fusion extraction sample, analyzes with infrared absorption.The RH-402 type device that the content of hydrogen (H) is to use LECO company to make according to JIS Z 2614, with the hydrogen in the rare gas element method of fusion extraction sample, is analyzed with radiant heat method.The content of carbon (C) is to use the made EMIA610 type device of Japanese hole factory's making, according to JIS Z 2615, heats the oxygen of extracting out in the sample in oxygen atmosphere, analyzes with the burning infrared absorption.

To the copper alloy plate that obtains like this, each example all is to cut out sample from copper alloy plate, and characteristics such as the tensile strength of each sample, hardness, electric conductivity, plating are estimated.These results are as shown in table 8 respectively.

(evaluation of plating)

For the copper alloy plate sample, after the above-mentioned copper alloy plate that obtains cuts out the sample of 25mm * 60mm, implement the plating Ag of the plating operation in the actual lead frame of simulation, stereomicroscope (* 40) is 10cm near any sample central part ²Scope observed the table the inside of plating face.And, measured work and separated out (projection) generation number unusually as the observed plating of projection of the plating layer as shown in Figure 3 at this mensuration position.If 2/cm of number less than takes place ²Then be evaluated as zero, if 2/cm ²More than, then because of causing rack of fusion etc., can not be evaluated as the semiconductor lead frame use *.Above-mentioned plating Ag is in the table the inside of having implemented the sample that electrolytic degreasing, pickling, washing etc. handle in earlier stage, implements to implement pure Ag plating with the plating Ag salt bath of market sale after the Cu substrate plating with the plating Cu salt bath of market sale.Cu substrate plating is at 60～65 ℃ of temperature, current density 5A/dm ², 10 seconds of treatment time condition under carry out, pure Ag plating is at 60～65 ℃ of temperature, current density 7A/dm ², 60 seconds of treatment time condition under carry out.

(measurement of hardness)

The measurement of hardness of copper alloy plate sample applies the load-carrying of 0.5kg to carry out at 3 positions with micro-DPH meter, and hardness is got their mean value.

(electric conductivity measuring)

The electric conductivity of copper alloy plate sample is to use milling machine that the flaky test film of the weak point of wide 10mm * long 300mm is processed, and uses double bridge formula electric resistance measuring apparatus measuring resistance, calculates by average transverse section method.

As indicated in table 7,8, the copper alloy of the present invention in forming is example 81～95, be make at the temperature of fusion of the molten metal of air melting stove and average cooling rate from the casting beginning to 600 ℃ suitable and make.Therefore, the Fe of example 81～95, P and C content are within the scope of the present invention.

Consequently, even example 81～95 exists to a certain degree O, H, according to tensile strength more than the 500MPa, the high-intensity ratio of hardness more than 150Hv, also be relative high conductivity, in addition, plating is also good.

Relative therewith, in the comparative example 96,97, the temperature of fusion in the air melting stove is low excessively or the casting beginning is too small to 600 ℃ average cooling rate, C content is very few certainly.Consequently, although O, H content exist, compare with example, plating is poor.

The O of comparative example 98,99, H too high levels.Consequently, though C content is many equally because of O, H content height, compare the obvious variation of intensity and plating with the example 84,85 of upper limit level.

The content of the Fe of comparative example 100 is very few.Therefore, although C content within the scope of the present invention, plating is good, intensity and hardness are low.

The copper alloy of comparative example 101, Fe content is too much.Therefore, although C content within the scope of the present invention, intensity and hardness, electric conductivity are all low.

The copper alloy of comparative example 102, P content is very few.Therefore, although C content within the scope of the present invention and plating good, intensity and hardness, electric conductivity are all low.

The copper alloy of comparative example 103, P content is too much.Therefore produced crackle in course of hot rolling plate end.

The temperature of fusion height of comparative example 104 in the air melting stove, C content is too much.Consequently, although O, H content within the scope of the present invention, compare with example, plating is poor.

Confirmed according to above result, except that high strength, the critical meaning of the C content that the good plating of separating out unusually that is used to make high strength and prevent plating all can be realized etc. and the meaning of preferably creating conditions that is used to obtain such tensile properties.

Table 7

Table 8

Though understand the present invention in detail with reference to specific embodiment,, understand as industry professional, do not breaking away from the spirit and scope of the present invention in addition various changes and correction.Present patent application is based on the Japanese patent application (the special 2006-311899 of hope) of the Japanese patent application (the special 2006-274309 of hope) of the Japanese patent application (the special 2006-270918 of hope) of on October 2nd, 2006 application, application on October 5th, 2006, application on November 17th, 2006 and the Japanese patent application of application on November 17th, 2006 (special be willing to 2006-311900), its content at this as reference.

Application feasibility on the industry

As described above,, can provide not only high strength, and the oxide film adaptation is also good, and makes these characteristics and deposit the Cu-Fe-P series copper alloy plate of (having both) according to the present invention.The adaptation height of resin in the time of consequently, can providing the semiconductor packages assembling and pad and the high semi-conductor mother metal of reliability of encapsulation.Therefore, use as miniaturization and light-weighted electrical and electronic parts, except that semiconductor device is used lead frame, can also be applied to the purposes that lead frame, junctor, terminal, switch, rly. etc. require the reliability of high strength and oxide film adaptation=encapsulation.

In addition, according to the present invention, can provide not only high strength but also bendability also good, and make these characteristics and deposit the Cu-Fe-P series copper alloy plate of (having both).Consequently, can provide reliability high semi-conductor mother metal.Therefore, as miniaturization and light-weighted electrical and electronic parts usefulness, except that semiconductor device is used lead frame, can also be applied to the purposes that lead frame, junctor, terminal, switch, rly. etc. require high strength and bendability.

In addition, according to the present invention, can provide not only high strength but also stampability also good, and make these characteristics and deposit the Cu-Fe-P series copper alloy plate of (having both).Consequently, as miniaturization and light-weighted electrical and electronic parts usefulness, except that semiconductor device is used lead frame, can also be applied to the purposes that lead frame, junctor, terminal, switch, rly. etc. require the bendability of high strength and strictness.

Moreover, according to the present invention, can provide not only high strength, and plating is also good, and makes these characteristics and deposit the Cu-Fe-P series copper alloy plate of (having both).Consequently, as miniaturization and light-weighted electrical and electronic parts usefulness, except that semiconductor device is used lead frame, can also be applied to the purposes that lead frame, junctor, terminal, switch, rly. etc. require the bendability of high strength and strictness.

Claims

1. a copper alloy plate for electric and electronic parts is characterized in that, contains Fe:0.01～0.50%, P:0.01～0.15% in quality %, and surplus is Cu and unavoidable impurities, wherein,

The center line average roughness Ra of this copper alloy plate of measuring according to the surface roughness measurement method stipulated among the JIS B0601 is below the 0.050 μ m, and maximum height Rmax is below the 1.5 μ m,

And the standout of roughness curve is that kurtosis value Rku is below 3.1.

2. copper alloy plate for electric and electronic parts as claimed in claim 1 is characterized in that, the r value on the direction parallel with rolling direction of described copper alloy plate is more than 0.3.

3. electric and electronic copper alloy plate as claimed in claim 1, it is characterized in that, described copper alloy plate adopts the modulus in tension of the described copper alloy plate that will obtain to carry out tension test with the orthogonal plate width direction of rolling direction as the test film of length direction to surpass 120GPa, and the ratio of uniform elongation and percentage of total elongation is that uniform elongation/percentage of total elongation is lower than 0.50.

4. copper alloy plate for electric and electronic parts as claimed in claim 1 is characterized in that described copper alloy plate also contains C:3～15ppm, and, O is defined as below the 40ppm, H is defined as below the 1.0ppm.

5. as each described copper alloy plate for electric and electronic parts in the claim 1～4, it is characterized in that described copper alloy plate also contains Sn:0.005～5.0% in quality %.

6. copper alloy plate for electric and electronic parts as claimed in claim 1 is characterized in that described copper alloy plate also contains Zn:0.005～3.0% in quality %.

7. copper alloy plate for electric and electronic parts as claimed in claim 1 is characterized in that, in described copper alloy plate, S is defined as below the 20ppm, and Pb is defined as below the 20ppm.

8. copper alloy plate for electric and electronic parts as claimed in claim 1 is characterized in that, the tensile strength of described copper alloy plate is more than the 500MPa, and hardness is more than the 150Hv.

9. copper alloy plate for electric and electronic parts as claimed in claim 1 is characterized in that, described copper alloy plate also contains in quality % and adds up to a kind of or two or more among 0.0001～1.0% Mn, Mg, the Ca.

10. copper alloy plate for electric and electronic parts as claimed in claim 1, it is characterized in that described copper alloy plate also contains in quality % and adds up to a kind of or two or more among 0.001～1.0% Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au, the Pt.

11. copper alloy plate for electric and electronic parts as claimed in claim 1, it is characterized in that, described copper alloy plate also contains in quality % and adds up to a kind of or two or more among 0.0001～1.0% Mn, Mg, the Ca, with add up to a kind of or two or more among 0.001～1.0% Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au, the Pt, and the total content of these elements that contained is below 1.0%.

12. copper alloy plate for electric and electronic parts as claimed in claim 1, it is characterized in that, in described copper alloy plate, the total content of Hf, Th, Li, Na, K, Sr, Pd, W, S, Si, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B, these elements of norium is below the 0.1 quality %.

13. a copper alloy plate for electric and electronic parts is characterized in that, contains Fe:0.01～0.50%, P:0.01～0.15% in quality %, surplus is Cu and unavoidable impurities, wherein,

Tensile strength is more than the 500MPa, and hardness is more than the 150Hv,

R value on the direction parallel with rolling direction of copper alloy plate is more than 0.3.

14. a copper alloy plate for electric and electronic parts is characterized in that, contains Fe:0.01～0.50%, P:0.01～0.15% in quality %, surplus is Cu and unavoidable impurities, wherein,

The modulus in tension that employing will be obtained to carry out tension test with the orthogonal plate width direction of rolling direction as the test film of length direction surpasses 120GPa,

And the ratio of uniform elongation and percentage of total elongation is that uniform elongation/percentage of total elongation is lower than 0.50.

15. copper alloy plate for electric and electronic parts, it is characterized in that, contain Fe:0.01～0.50%, P:0.01～0.15%, C:3～15ppm in quality %, surplus is Cu and unavoidable impurities, in this unavoidable impurities, O is defined as below the 40ppm, H is defined as below the 1.0ppm, S is defined as below the 20ppm, Pb is defined as below the 20ppm.

16., it is characterized in that described copper alloy plate is used for semiconductor lead frame as each described electrical and electronic parts alloy sheets in the claim 1,13,14,15.