CN1327016C - Copper base alloy with improved punchin and impacting performance and its preparing method - Google Patents

Copper base alloy with improved punchin and impacting performance and its preparing method Download PDF

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CN1327016C
CN1327016C CNB021192723A CN02119272A CN1327016C CN 1327016 C CN1327016 C CN 1327016C CN B021192723 A CNB021192723 A CN B021192723A CN 02119272 A CN02119272 A CN 02119272A CN 1327016 C CN1327016 C CN 1327016C
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copper base
alloy
base alloy
ray diffraction
face
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CN1458292A (en
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畠山浩一
菅原章
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Tonghe Holding Group Co ltd
Dowa Metaltech Co Ltd
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Dowa Mining Co Ltd
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Abstract

The present invention relates to alloy based on copper, which comprises elements and the rest of Cu and incidental impurities, wherein the total amount of the elements is 0.01 to 30 weight per cent and at least one of the elements is selected from Sn, Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, Zr and Al. The alloy has an at least 10 of surface X-ray diffraction intensity ratio Snd, wherein the Snd= I{220}/I{200}, I{220} is the X-ray diffraction intensity of a {220} surface, and I{200} is the X-ray diffraction intensity of a {200} surface. Meanwhile, because the alloy can keep balance among electric conductive performance, intensity, rebound performance, hardness and bending performance, the present invention has the improved stamping and punching performance. The present invention also relates to a preparation method of the alloy.

Description

Copper base alloy and preparation method thereof with punching press punching out performance of improvement
Background of invention
The present invention relates to have the copper base alloy and preparation method thereof of the punching press punching out performance of improvement.More specifically, the present invention relates to be suitable for consuming product such as closely spaced information/communications connector, semiconductor lead frame, and the copper base alloy of the punching press punching out performance with improvement of the MST of switchette and rly. (master plate), and the preparation method of described alloy.
Along with the raising of the packaging density of consumption electronic product, information/signal equipment and trolley part, junctor, switch, rly. etc. become more and more littler, and this just requires to use thinner copper base alloy plate and more tiny copper base alloy line in these equipment.
Above-mentioned parts adopt usually on the high velocity ram machine and cooperate punch process to form with metal die.During press process, shearing strain takes place in material under the effect of metal die drift, and then, crackle causes craze and transfiguration from the germinating expansion of blade tip place, thereby this material punching out is become designated shape.Because stamping machine carries out repeatedly punching out, the blade tip of drift can wear and tear gradually, the result, the blade tip of wearing and tearing can cause the inhomogeneous expansion of crackle, the outward appearance of fracture becomes irregular, for example, and shear zone and the interval difference increase of cracking, a large amount of burrs appears, and the surplus material of tail that produces wide variety of materials in the cracking process; These phenomenons all can cause the problem that can't keep the shape of product that requires.
The traditional measures that improves described die life comprises the drift of materials used better quality, uses higher punching press lubricant of oilness and the gap that is suitable for various copper base alloys to set.Yet described these methods of none solve this problem fully.
The inventor has carried out intensive research, to solve the problems referred to above that exist at present.When adopting the high velocity ram machine punching out to match little interval connector of manufacturing and semiconductor lead frame with metal pattern, nearest trend is that lead terminal is thinner thinner narrow, and particularly, thickness is 0.10-0.25mm, and width is 0.10-0.30mm.This design philosophy requires lead terminal to satisfy and is keeping the performance requriements that equilibrated has the punching press punching out performance of improvement again simultaneously between intensity and the bending property.
The invention summary
Therefore, an object of the present invention is to provide wherein the copper base alloy of the punching press punching out performance that the crystalline orientation by control material is improved.
Another object of the present invention provides the preparation method of this alloy.
The intensity that replaces lead terminal for 0.2% yield strength that reaches purpose of the present invention, can adopt the material of making lead terminal.Can adopt the unit elongation that obtains in the tension test to replace the bending property of lead terminal, (t is the thickness of slab of lead terminal, unit: mm because work as W/t≤4; W is its width, unit: in the time of mm), and the distortion of lead terminal generation single shaft.
Be accomplished based on following discovery the present invention, described discovery is: by the diffracted intensity of control copper-based alloy material in the particular crystal direction, can obtain the better copper base alloy of punching press punching out performance, described particular crystal direction is determined by ND face (be the thin plate material surface, abbreviate " ND face " below as) is carried out X-ray diffraction.Particularly, the preparation method of copper base alloy of the present invention comprises the steps: the cold rolling element of specified amount such as the copper base alloy ingot of Sn and Ni of containing, alloy pig after cold rolling is annealed, and, then, carry out cold rollingly with the alloy pig after the comparison annealing depressed that is not less than specified amount, described designated value calculates according to the alloying element content of non-copper.The term of Shi Yonging " X-ray diffraction intensity " refers to the integrated intensity that adopts the copper-based alloy material crystallographic direction that proper method such as X-ray diffraction record herein.
First purpose of the present invention can realize that described alloy contains at least a Sn of being selected from that total amount is 0.01-30 weight %, Ni by a kind of copper base alloy with punching press punching out performance of improvement, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the element of Zr and Al the rest is Cu and incidental impurity, and the surperficial X-ray diffraction intensity of described alloy compares S NDBe at least 10[S ND=I { 220}/ I { 200}I { 220}Be { X-ray diffraction intensity of 220} face, I { 200}Be the X-ray diffraction intensity of 200} face].
First purpose of the present invention also can realize that described alloy contains at least a Sn of being selected from that total amount is 0.01-30 weight %, Ni by a kind of copper base alloy with punching press punching out performance of improvement, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the element of Zr and Al the rest is Cu and incidental impurity, and the surperficial X-ray diffraction intensity of described alloy compares S NDBe at least 10[S ND(I { 220}+ I { 311})/I { 200}I { 220}Be { X-ray diffraction intensity of 220} face, I { 311}Be { X-ray diffraction intensity of 311} face, I { 200}Be the X-ray diffraction intensity of 200} face].
First purpose of the present invention can also realize that described alloy contains at least a Sn of being selected from that total amount is 0.01-30 weight %, Ni by a kind of copper base alloy with punching press punching out performance of improvement, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the element of Zr and Al the rest is Cu and incidental impurity, and the surperficial X-ray diffraction intensity of described alloy compares S NDBe at least 10[S ND=(I { 220}+ I { 111})/I { 200}I { 220}It is { the X-ray diffraction intensity of 220} face; I { 111}Be { X-ray diffraction intensity of 111} face, I { 200}Be the X-ray diffraction intensity of 200} face].
First purpose of the present invention can realize that described alloy contains at least a Sn of being selected from that total amount is 0.01-30 weight %, Ni by a kind of copper base alloy with punching press punching out performance of improvement again, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the element of Zr and Al the rest is Cu and incidental impurity, and the surperficial X-ray diffraction intensity of described alloy compares S NDBe at least 10[S ND=(I { 220}+ I { 111}+ I { 311})/I { 200}I { 220}Be { X-ray diffraction intensity of 220} face, I { 111}Be { X-ray diffraction intensity of 111} face, I { 311}Be { X-ray diffraction intensity of 311} face, I { 200}Be the X-ray diffraction intensity of 200} face].
In a preferred embodiment, the copper base alloy of every kind of above-mentioned definition can contain the Sn of 0.3-3.0 weight %.
Second purpose of the present invention can be realized by a kind of method for preparing any above-mentioned copper base alloy, described method comprises the steps: the copper base alloy ingot is implemented the annealing cold rolling and that carry out subsequently of at least one round-robin, described copper base alloy contains at least a Sn of being selected from that total amount is 0.01-30 weight %, Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the element of Zr and Al the rest is Cu and incidental impurity, afterwards, carry out cold rollingly with the alloy after the comparison annealing depressed that is not less than designated value, described designated value is determined according to the content of described at least a element.
Second purpose of the present invention also can be realized by a kind of method for preparing any above-mentioned copper base alloy, described method comprises the steps: the copper base alloy ingot is implemented cold rolling and subsequently the anneal of at least one round-robin, described copper base alloy contains at least a Sn of being selected from that total amount is 0.01-30 weight %, Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the element of Zr and Al, the rest is Cu and incidental impurity, and, afterwards, carry out cold rolling than Z to the alloy after annealing to depress, wherein, Z satisfies following equation:
Z≥100-10X-Y (1)
[wherein, Z is a per-cent under the cold rolling; X is the content (weight %) of Sn; Y is the total content (weight %) of other element except that Sn].
Second purpose of the present invention can also realize that described method comprises the steps by a kind of method for preparing any above-mentioned copper base alloy; The copper base alloy ingot is implemented cold rolling and subsequently the anneal of at least one round-robin, and described copper base alloy contains at least a Sn of being selected from that total amount is 0.01-30 weight %, Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the element of Zr and Al, the rest is Cu and incidental impurity, afterwards, carry out cold rollingly to depress than the alloy of Z after to annealing, described Z satisfies following equation:
Z≥100-10X-Y (1)
[wherein, Z is a per-cent under the cold rolling; X is the content (weight %) of Sn; Y is the total content (weight %) of the element except that Sn], and, described alloy after rolling is carried out cold anneal being lower than under the temperature of recrystallization temperature subsequently.
In a preferred embodiment, before described one or more circulations that constitute by annealing cold rolling and subsequently, ingot casting is carried out homogenizing annealing or hot rolling or the two have concurrently.
The accompanying drawing summary
Fig. 1 shows per-cent under the cold rolling, direction density and S NDBetween relation; And
Fig. 2 shows the relation between per-cent under the cold rolling, tensile strength, 0.2% yield strength and the unit elongation.
Detailed Description Of The Invention
We introduce the present invention in detail now. The present invention is based on following discovery, described discovery refers to: by the diffracted intensity of control copper-based alloy material on the particular crystal direction, can obtain to have the acid bronze alloy of the punching press punching out performance of improvement, described diffracted intensity is determined by described alloy material surface is carried out X-ray diffraction.
At first, in order to implement gratifying punch process, i.e. work in-process, after the material generation detrusion, crackle is evenly expanded from the blade tip place of drift, thereby obtains effective craze and transfiguration, and importantly the crystallographic direction of material is by certain orientations. The brilliant material in Cu Quito with face-centered cubic (FCC) crystal structure have altogether 12 by 111} face and<110〉slip system of direction formation, this depend on slide surface 111} and glide direction<110〉and combination (what described bracket provided is the set symbol that is equal to crystal face, described angle bracket is the set symbol that is equal to the crystal orientation), and at least one described slip system is in effective status in distortion. In the shearing distortion, become the most low-angle slip system effective with the punching out direction.
Here, consider four oikocryst faces of light sheet material, { the 110} face, { the 111} face, { the 311} face is with { 100} face, condition are that the appointment material surface is the ND face. If described material is carried out shearing distortion, then have two slip systems consistent with the punching out direction { the 110} face is the most effective crystal face that improves its punching press punching out performance. Inferior effective crystal face is { 111} and { the 311} face that has with punching out direction slip system at a slight angle. By contrast, 8 in 12 slip systems all become miter angle { 100} are maximum in the face of the adverse effect of punching press punching out performance with the punching out direction. Especially, the stress that acts on the drift blade tip is very large, and blade tip wearing and tearing are accelerated, and the metal fragment that is produced by craze and transfiguration is more and stick to (between drift and the die) in the mould, thereby accelerated the blade tip wearing and tearing, final material behind cracking produces higher burr.
When metal with FCC crystal structure such as acid bronze alloy are carried out X-ray diffraction, { 110}, { 111}, { 311} and { diffracted intensity of 100} face is respectively I{220},I {111},I {311}And I{200}
Consider these facts, the inventor has carried out intensive research, to solve the above-mentioned problems in the prior art. They have measured acid bronze alloy { 220}, { 111}, { 311} and { the diffracted intensity I of 200} face{220},I {111},I {311}And I{200}, introduced a new parameter SND(=I {220}/I {200}), and, by adopting SNDControl as index alloy structure, successfully improved the punching press punching out performance of this alloy. What particularly point out is to work as SNDBe at least at 10 o'clock, the terminal that can punching out goes out to have excellent in shape. On the other hand, work as SNDLess than 10 o'clock, along with the increase of press punching out number of times, blade tip ground off gradually, can only punching out goes out the terminal of shape difference.
According to the type of acid bronze alloy, I{311}May be greater than I{220}1/10th, perhaps I{111}May be greater than I{220}1/10th, perhaps, I{111}With I{311}Sum may be I{220}1/10th. In this case, preferably use respectively SND=(I {220}+I {311})/I {200},S ND=(I {220}+I {111})/I {200}, and SND=(I {220}+I {111}+I {311})/I {200}Substitute respectively SND=I {220}/I {200}
Chemical composition to acid bronze alloy of the present invention is stipulated, so that it contains at least a Sn of being selected from that total amount is the 0.01-30 % by weight, and Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the element of Zr and Al the rest is Cu and subsidiary impurity. This requires and must satisfy, so that in the punching press punching out performance of improving described alloy material, keeps the balance of its electric conductivity, tensile strength, 0.2% yield strength, percentage elongation and bending property.
If at least a Sn that is selected from, Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the total content of the element of Zr and Al is lower than 0.01 % by weight, although then can obtain higher electric conductivity, is difficult to obtain other performance, for example tensile strength, 0.2% yield strength and punching press punching out performance. If rolling drafts is increased to 98%, then tensile strength and 0.2% yield strength can improve, but punching press punching out performance without obvious improvement, and bending property descends. If at least a Sn that is selected from, Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the total content of the element of Zr and Al are greater than 30 % by weight, and then tensile strength and 0.2% yield strength can be improved, and electric conductivity and bending property descend.
For this reason, determine to contain at least a Sn of being selected from that total amount is the 0.01-30 % by weight in the chemical composition of acid bronze alloy of the present invention, Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, the element of Zr and Al the rest is Cu and subsidiary impurity. Except above-mentioned each element, can add at least a Ag of being selected from that total amount is no more than 2 % by weight, Au, Bi under the condition of further improvement of punching press punching out performance not disturbing above-mentioned main interpolation element and help, In, Mn, La, Pb, Pd, Sb, Se, the element of Te and Y.
Now, we introduce the limit range of above-mentioned essential element, and the interpolation total amount of at least a element wherein must be in above-mentioned specified scope.
(1)Sn
Tin (Sn) is a kind of guarantee good punching press punching out performance and intensity and flexible requisite element. If be dissolved in the Cu matrix, Sn can significantly reduce be unfavorable for punching press punching out performance gathering of 200} face, and, when when thermal-mechanical treatment is combined, Sn also can significantly improve { 220} face, { 111} face and { gathering of 311} face finally promotes the improvement of punching press punching out performance. Simultaneously, also can obtain the improvement of intensity and plasticity. Yet, if Sn content is lower than 0.01 % by weight, can not obtain desired effect. If Sn content surpasses 10 % by weight, then electric conductivity and forging property can significantly descend, and hot-workability also can affect adversely. Because Sn is a kind of expensive metal, therefore, also can produce disadvantage economically. So, Sn content should be remained the 0.01-10 % by weight, preferred 0.3-3.0 % by weight.
(2)Ni
Nickel (Ni) is dissolved in the Cu matrix and can improves its intensity, elasticity and solderability. It also with P, sometimes with Si, chemical combination forms the compound of disperse educt, thereby improves electric conductivity and intensity and elasticity. Nickel also helps to improve heat resistance and removes stress characteristics. If Ni content is lower than 0.01 % by weight, then can not fully obtain the above-mentioned effect of Ni. If Ni content surpasses 4.0 % by weight, then can in addition have P (occasionally, the obvious decline of electric conductivity appears in the situation about Si) existing, and, also can produce disadvantage economically. Therefore, Ni content should be remained the 0.01-4.0 % by weight, be preferably the 0.40-3.0 % by weight.
(3)P
Phosphorus (P) plays the deoxidier of motlten metal between melting and casting cycle, its also with Ni, sometimes with Fe, Mg or Co chemical combination form the compound of disperse educt, thereby improve electric conductivity, and intensity and elasticity. If P content is lower than 0.01 % by weight, then can not fully obtain the above-mentioned effect of P. If P content surpasses 0.20 % by weight, what for to existing under the Ni condition of (by accident, Fe, Mg or Co), the remarkable decline of electric conductivity and solder weatherability also can occur. Hot-workability also can affect adversely. Therefore, P content should be remained the 0.01-0.20 % by weight, preferred 0.02-0.10 % by weight.
(4)Zn
Zinc (Zn) is dissolved in the Cu matrix and can improves its intensity and elasticity; It also can promote the deoxidation of melt, thereby reduces the meltage of oxygen in the Cu matrix.In addition, Zn helps to improve the weathering resistance and the anti-migration performance of solder.Yet,, can not obtain the above-mentioned effect of Zn if its content is lower than 0.01 weight %.If Zn content surpasses 30 weight %, then electroconductibility and weldability all can descend.Even excessive Zn combines with other element, but the susceptibility of the stress corrosion crack of alloy is higher undesirably.Therefore, Zn content should be remained 0.01-30 weight %, be preferably 0.01-10 weight %, more preferably 0.03-3.0 weight %.
(5)Si
Silicon (Si), if with Ni coexistence, then can in the Cu matrix, separate out to form and a kind ofly help to improve intensity and elasticity but can not cause the compound that electroconductibility obviously descends.If its content is lower than 0.01 weight %, then can not obtain these effects of silicon.If Si content surpasses 1.0 weight %, the remarkable decline of hot workability then can appear.Therefore, Si content should be remained 0.01-1.0 weight %.
(6) Fe, Co, Mg, Ti, Cr, Zr and Al
This this element dissolves in the Cu matrix or separates out to be formed with and helps improve intensity, elasticity and thermotolerance, and the compound of punching press punching out performance.If a kind of addition of described these elements is lower than 0.01 weight %, then above-mentioned effect can not obtain.If a kind of content of these elements is higher than 3.0 weight %, the obvious decline of electroconductibility then can appear, and, also be disadvantageous economically, for example, need during making, alloy heat-treat under the excessive temperature that need not expect.Therefore, at least a Fe that is selected from, Co, Mg, Ti, Cr, the total amount of the element of Zr and Al should remain 0.01-3.0 weight %.
(7) oxygen
The a word that must say about oxygen is: if its too high levels, Fe then, Mg, P and other element can form oxide compound, and this may damage plating reliability and other performance of copper base alloy of the present invention.Therefore, preferred oxygen content is not higher than 20ppm.
Now, we introduce the thermal treatment of preparation copper base alloy of the present invention and the standard of other procedure of processing.The preparation of copper base alloy of the present invention can comprise the steps: to reach the appointment thickness of slab by the copper base alloy ingot of the chemical constitution that repeats and anneal cycles, make to have aforementioned regulation cold rolling; Then, carry out cold rollingly with the described thin plate of comparison of depressing that is not less than prescribed value, described prescribed value determined by the content that adds element, described depressing than being defined as per-cent Z under the cold rolling of satisfying equation (1) by special; If necessary, the thin plate after cold rolling is carried out the thickness of cold annealing to obtain to require being lower than under the temperature of recrystallize point.
If before cold rolling, ingot casting is carried out homogenizing annealing or hot rolling, then can effectively remove the microcosmic or the macrosegregation of the dissolving element that occurs between casting cycle, thereby obtain the uniform distribution of this dissolving element.Especially, preliminary hot rolling helps the grain orientation stochastic distribution of ingot casting and produces tiny and uniform crystal grain; Because the rolling thickness that makes obviously reduces, and therefore, also is favourable economically.Therefore, be recommended in and implement homogenizing annealing or hot rolling or both before the cold rolling ingot casting and have concurrently.Homogenizing annealing and hot rolling were preferably carried out under 700-900 ℃ 0.5-2 hour.
Per-cent Z should satisfy following equation under the cold rolling:
Z(%)≥100-10X-Y (1)
Wherein, X is the content (weight %) of Sn; Y is the total content (weight %) of any element except that Sn and Cu.
When with satisfy relational expression (1) depress than cold rolling latten the time, be unfavorable for punching press punching out performance { 200} face gathering on the ND face declined to a great extent, and simultaneously, can improve { the 220} face of its punching press punching out performance, { 111} face and { gathering of 311} face, particularly the 220} face gather obvious increase, thereby the punching press punching out performance that is improved.In this case, parameter S NDBe not less than 10 (S ND〉=10).And tensile strength and 0.2% yield strength all are improved, thereby have improved unit elongation, and unit elongation descends along with the increase of rolling draught.When with depress than Z cold rolling after, when under being lower than the temperature of recrystallize point, carrying out cold annealing, { 200} face, { 220} face, { the 111} face is with { it is almost constant that 311} face relative gathered degree, and tensile strength and 0.2% yield strength are still kept, as a result, the thin plate after the annealing has with the equally good punching press punching out performance of the thin plate of rolling attitude.And cold annealing helps to improve unit elongation or bending property.
Therefore, in optimal pattern, with satisfy relational expression (1) depress than Z (%) carry out cold rolling with combine being lower than the cold annealing of carrying out under the temperature of recrystallize point.Preferably, cold annealing was carried out 0.5-2 hour under the recrystallization temperature 50-250 that is lower than copper base alloy ℃ temperature, typically, carried out under 250-350 ℃ 0.5-1 hour.As long as can provide described alloy material a considerable amount of heat, adopt other temperature and time combination, also can obtain desired characteristic certainly.
When not satisfy the depressing when cold rolling of relational expression (1), { gathering almost of 200} face do not reduce, and { gathering of 220} face is not increased to the degree that is enough to improve punching press system performance yet.In this case, S NDLess than 10.When depressing when not satisfying relational expression (1), along with depress than increase, tensile strength and 0.2% yield strength are improved, still, on the other hand, unit elongation and bending property all descend.When not satisfy the depressing than after cold rolling of relational expression (1), when carrying out cold annealing again under the temperature that is lower than recrystallize point, { the 200} face, { the 220} face, { the 111} face is not with { the relative degree of gathering of 311} face almost changes, and can not improve punching press punching out performance.The trial that improves bending property has caused the decline of tensile strength and 0.2% yield strength, and the result can not keep the balance between these three performance parameters.
Provided exemplary illustration among Fig. 1 and Fig. 2 to these phenomenons.Fig. 1 shows Cu-1.0 weight %Ni-0.90 weight %Sn-0.05 weight %P alloy, and rolling per-cent and the various crystallographic direction depressed gathered relation between the degree, Fig. 2 shows rolling per-cent and its three performances depressed of same copper base alloy, tensile strength, the relation between 0.2% yield strength and the unit elongation.Form to timing when alloy, if the Z value is 89.95% or higher, then per-cent Z satisfies relational expression (1) under the cold rolling.As seen from Figure 1, when Z equals 89.95% at least, to punching press punching out performance deleterious the 200} face gather remarkable decline, and to punching press punching out performance useful the 220} face gather obvious increase.With regard to S ND, it is 12 when Z=90%, it increases to 22 when Z=92.5.Interesting is, can see tensile strength, 0.2% yield strength in this experiment, and even unit elongation can both improve (referring to Fig. 2).
Putting the purpose of stating embodiment is for the present invention is further specified and limits it by no means.
Embodiment 1
In argon atmospher,, carry out melting and vertically be cast into the ingot casting that is of a size of 20mm * 80mm * 1000mm in the continuous caster for 6-9 number and 11-16 number copper base alloy sample with the chemical composition analysis result (weight %) shown in the table 1 1-4 number.Under 900 ℃ obtaining ingot casting is carried out homogenizing thermal treatment, the time is 1 hour.Afterwards, (numbering 1-4,6-9 and 11-16) carries out hot rolling to described ingot casting, makes its thickness reduce to 6.0mm by 20mm, adopts water quick cooling and carries out pickling.The cold rolled thin plate that 6.0mm is thick is to all thickness: being numbered 1,7 and 8 sample thickness is 2.5mm; Being numbered 2,3 and 16 thickness of sample is 2.0mm; Being numbered 4,6 and 15 thickness of sample is 1.0mm; Being numbered 9 thickness of sample is 3.5mm; The thickness of sample of numbering 11 is 0.6mm; The thickness of sample of numbering 12 is 0.5mm; The thickness of sample of numbering 13 is 0.3mm; The thickness of sample of numbering 14 is 0.23mm.
5,10,17 and 18 the copper base alloy sample of being numbered that will have the chemical analysis results shown in the table 1 (weight %) carries out melting in argon atmospher, and pours into the ingot casting that is of a size of 10mm * 80mm * 1000mm in horizontal caster.Under 800 ℃ obtaining ingot casting is carried out homogenizing thermal treatment, the time is 1 hour, then, carries out cold rolling, annealing, cold rolling recirculation, so that ingot casting thickness is reduced to following each value: No. 5 samples are 0.6mm; No. 10 samples are 0.3mm; No. 17 samples are 0.25mm; No. 18 samples are 0.24mm.
Thin plate sample to preparation like this is heat-treated under 550 ℃ for 1-18 number, and the time is 1 hour.Grain-size in the thin plate after the processing is 5-20 μ m; X-ray diffraction is carried out on surface (ND face) to each thin plate, and measures its S NDValue is found S NDBe at least 0.5 but less than 2.0.
The condition of measuring X-ray diffraction intensity is as follows: spot, Cu; Pipe is pressed, 40kV; Tube current, 30mA; The sampling width, 0.020 ℃; Monochromator uses; Specimen holder, Al.
These are not the unique conditionals that carries out X-ray diffraction analysis, can carry out various corrections according to sample type.
Then, the 1-18 sample is cold-rolled to the final thickness of 0.20mm.In this final step, described sample is carried out 30 minutes thermal treatment being lower than under 300 ℃ of recrystallization temperature.The sample of preparation like this is carried out the evaluation of various performances.
At first, measure and estimate S NDAfterwards, estimate electroconductibility, 0.2% yield strength, 180 ° of bending properties and punching press punching out performance.Electroconductibility and 0.2% yield strength are measured and are estimated according to JIS H 0505 and JIS Z 2241 respectively.In order to estimate bending property, carry out 180 ° of pliability tests (JIS H 3110) in the following manner: go out the pin shape test specimens that width is 0.50mm by each sample along the direction punching out parallel, and carry out pliability test until crackle occurring with rolling direction; Adopt the R/t minimum value when flawless occurs in the pliability test to estimate bending property, wherein, R is aduncate radius, and t is a sheet gauge.In order to estimate punching press punching out performance, adopt continuous punching to make the terminal of the wide 0.50mm of pin, through 5 * 10 4After the inferior punching out, adopt SEM that the maximum height of burr on the pin is measured.
Table 1
Sample No. Form (weight %) Per-cent Z (%)=100-10X-Y under the ideal cold rolling Per-cent (%) under the actual cold rolling S ND (≥10) Burr height (micron) Electroconductibility (%IACS) 0.2% yield strength (N/mm 2) 180 ° of bending property R/t *(in 0 ° of direction)
× Y
Sn Ni P Other element Cu
This invention sample No.1 0.91 1.02 0.05 - Rem 89.8 92.5 22 3 40.2 590 0
No.2 1.50 0.47 0.02 Zn:1.48 Rem 83.0 90.0 25 4 33.8 605 0.5
No.3 2.00 1.21 0.07 Zn:0.20,Fe:0.05 Rem 78.4 90.0 35 2 30.9 645 0.5
No.4 2.00 - 0.03 Fe:0.10 Rem 79.8 80.0 20 3 35.4 620 0
No.5 4.00 - 0.03 Fe:0.10 Rem 59.8 67.0 25 3 22.4 660 0
No.6 1.75 - - Zn:10.6,Fe:1.70,Co:0.20 Rem 70.0 80.0 18 4 33.8 605 0.5
No.7 0.52 2.00 - Si:0.50,Zn:1.00 Rem 91.3 92.5 20 6 47.3 630 0.5
No.8 0.50 3.20 - Si:0.70,Zn:1.00 Rem 90.1 92.5 15 5 43.9 640 0.5
No.9 0.30 2.30 - Si:0.55,Zn:0.50,Mg:0.10 Rem 93.5 94.3 12 8 42.3 630 0.5
No.10 8.00 0.40 0.20 Fe:0.10,Zn:0.10 Rem 19.2 33.0 13 5 12.5 660 0.5
Control sample No.11 0.91 1.02 0.05 - Rem 89.8 67.0 5.0 5 40.2 530 0
No.12 1.50 0.47 0.02 Zn:1.48 Rem 83.0 58.0 7.0 15 33.8 530 0
No.13 2.00 1.21 0.07 Ti:0.01,Cr:0.02,Zr:0.01 Rem 78.7 33.0 8.5 12 30.9 540 0
No.14 0.52 2.00 - Si:0.50,Zn:1.00 Rem 91.3 13.0 2.9 18 42.3 580 0.5
No.15 0.50 3.20 - Si:0.70,Zn:1.00 Rem 90.1 80.0 9.0 12 43.9 680 2.0
No.16 0.30 2.30 - Si:0.55,Zn:0.50,Mg:0.10 Rem 93.5 90.0 7.5 12 40.2 670 2.0
No.17 6.00 - 0.20 - Rem 39.8 20.0 9.0 12 14.5 530 0
No.18 8.00 - 0.20 - Rem 19.8 16.0 8.0 12 12.8 570 0.5
*: when with thick t millimeter, the test specimens of wide W millimeter (W/t=2.5) curves inwardly with the radius of R millimeter and the R/t minimum value of flawless when occurring.
Rem: all the other
Can know by table 1 and to find out: satisfy S NDDuring 〉=10 and Z (%) 〉=100-10X-Y, can not produce the burr that highly surpasses 10 μ m to the punching out of 1-10 copper base alloy sample according to the present invention; Except the punching press punching out performance of improving, these samples of the present invention have good balance between electroconductibility, 0.2% yield strength and bending property; On the other hand, to be lower than the S of depressing of ideal value than cold rolling 11-18 control sample NDValue is less than 10, and the burr height that produces during the punching press punching out is not less than 10 μ m.The burr height that occurs in the 15-18 sample is 12 μ m, with 10 μ m difference be not very big; 15 and No. 16 sample has good balance between electroconductibility and 0.2% yield strength, but flexural strength is lower; 17 and No. 18 sample has good balance between 0.2% yield strength and bending property, but their electroconductibility is lower than 15%IACS.
Embodiment 2
To No. 1 sample alloy according to the present invention (referring to above-mentioned table 1; Thickness of slab 0.20mm), industrial phosphor bronze alloy (C5191; State, H; Thickness of slab, 0.20mm; 6.5 weight %Sn, 0.2 weight %P the rest is Cu) and industrial copper base alloy (C7025; State, H; Thickness of slab, 0.20mm; 3.2 weight %Ni, 0.70 weight %Si, 0.15 weight %Mg the rest is Cu) electroconductibility, 0.2% yield strength, the spring deflection limit, Vickers' hardness, press processability and bending property are estimated.
Electroconductibility, 0.2% yield strength, the measurement of the spring deflection limit and Vickers' hardness is respectively according to JIS H 0505, JIS Z 2241, JIS H 3130 and JIS Z 2244 carry out.In order to estimate press processability, adopt the drawing method continuous punching out similar to go out the terminal that pin widths is 0.50mm with embodiment 1, until the burr that forms highly above 25 μ m, and, will be designated as maximum punching out number of times until number of times that at this moment can punching out.Drift is made by ultrahigh-strength steel, and die is made by die steel; Gap between drift and die is 8 μ m; The speed of rotation of punch press is 250rpm.In order to estimate bending property, adopt following manner to carry out 180 ° of pliability tests (JIS H 3110): to go out the pin shape test sample that width is 0.50mm by each sample punching out, and carry out pliability test until crackle occurring; The minimum value of the R/t of employing when flawless occurs in pliability test is estimated bending property, and wherein, R is aduncate radius, and t is a thickness of slab.The results are shown in the table 2.
Table 2
Electroconductibility (%IACS) 0.2% yield strength (N/mm 2) 0 ° of 90 ° of direction of direction The Elastic deflection limit (N/mm 2) 0 ° of 90 ° of direction of direction Vickers' hardness (HV) Maximum punching out number of times (* 10 4) R/t *90 ° of directions of 0 ° of direction of minimum value
No. 1 sample of alloy of the present invention 40 590、615 470、600 195 320 0、0
C5191 H 13 600、610 390、540 200 300 0、0
C7025 H 50 640、600 560、540 220 150 1.0、0.5
*: the R/t minimum value when the curved surface flawless occurs.
Table 2 shows: be used for junctor at present, the typical copper base alloy C5191 of switch and rly. compares with C7025, and the balance of copper base alloy of the present invention between electroconductibility, 0.2% yield strength, the spring deflection limit, Vickers' hardness, press processability and bending property is better.In order to be applied to little interval connector, 0.2% yield strength on 90 ° of directions, the spring deflection limit and flexural strength should be higher, and alloy of the present invention can successfully satisfy this requirement.
As introducing at aforementioned each page, the invention provides the copper base alloy that is used for junctor, switch, rly. etc., this alloy has the punching press punching out performance that is greatly improved, can reduce the wearing and tearing of drift blade tip, and described alloy also has good balance between electroconductibility, 0.2% yield strength, rebound performance, hardness and bending property.Described alloy can be processed into thinner sheet material or thinner wire rod, to satisfy the requirement of modern consumption electronic product, information/communication equipment and trolley part to higher packing density, and described alloy also helps to prolong the life-span of compacting tool set, thereby manufacturing cost is obviously descended.

Claims (24)

1. have the copper base alloy of the punching press punching out performance of improvement, the Sn that it contains 0.01-10 weight % is selected from Ni, P, Zn, Si, Fe, CO, Mg, Ti, Cr, one or more optional elements of Zr and Al, the total amount of Sn and described optional element is 0.01-30wt%, the rest is Cu and incidental impurity, and the surperficial X-ray diffraction intensity of described copper base alloy compares S NDBe at least 10, wherein S ND=I { 220}/ I { 200}I { 220}Be { X-ray diffraction intensity of 220} face, I { 201}It is { the X-ray diffraction intensity of 200} face.
2. according to the copper base alloy of claim 1, this alloy comprises at least a among the P of the Ni of 0.01-4.0wt% and 0.01-0.20wt%.
3. according to the copper base alloy of claim 1, this alloy comprises at least a among the Si of the Zn of 0.01-10wt% and 0.01-1.0wt%.
4. according to the copper base alloy of claim 2, this alloy comprises at least a among the Si of the Zn of 0.01-10wt% and 0.01-1.0wt%.
5. according to each copper base alloy among the claim 1-4, this alloy comprises the Fe that is selected from of 0.01-3.0wt%, Co, Mg, Ti, Cr, at least a element of Zr and Al.
6. the copper base alloy that has the punching press punching out performance of improvement contains the Sn of 0.01-10 weight %, is selected from Ni, P, Zn, S i, Fe, Co, Mg, Ti, Cr, one or more optional elements of Zr and Al, the total amount of Sn and described optional element is 0.01-30wt%, the rest is Cu and incidental impurity, and the surperficial X-ray diffraction intensity of described copper base alloy compares S NDBe at least 10, wherein S ND=(I { 220}+ I { 331})/I { 200}I { 220}Be { X-ray diffraction intensity of 220} face, I { 311}It is { the X-ray diffraction intensity of 311} face; I { 200}It is { the X-ray diffraction intensity of 200} face.
7. according to the copper base alloy of claim 6, this alloy comprises at least a among the P of the Ni of 0.01-4.0wt% and 0.01-0.20wt%.
8. according to the copper base alloy of claim 6, this alloy comprises at least a among the Si of the Zn of 0.01-10wt% and 0.01-1.0wt%.
9. according to the copper base alloy of claim 7, this alloy comprises at least a among the Si of the Zn of 0.01-10wt% and 0.01-1.0wt%.
10. according to each copper base alloy among the claim 6-9, this alloy comprises the Fe that is selected from of 0.01-3.0wt%, Co, Mg, Ti, Cr, at least a element of Zr and Al.
11. have the copper base alloy of the punching press punching out performance of improvement, contain the Sn of 0.01-10 weight %, be selected from Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, one or more optional elements of Zr and Al, the total amount of Sn and described optional element is 0.01-30wt%, the rest is Cu and incidental impurity, and the surperficial X-ray diffraction intensity of described copper base alloy compares S NDBe at least 10, wherein S ND=(I { 220}+ I { 111}}/I 200)I { 220}Be { X-ray diffraction intensity of 220} face, I { 111}Be { X-ray diffraction intensity of 111} face, I { 200}It is { the X-ray diffraction intensity of 200} face.
12. according to the copper base alloy of claim 11, this alloy comprises at least a among the P of the Ni of 0.01-4.0wt% and 0.01-0.20wt%.
13. according to the copper base alloy of claim 11, this alloy comprises at least a among the Si of the Zn of 0.01-10wt% and 0.01-1.0wt%.
14. according to the copper base alloy of claim 12, this alloy comprises at least a among the Si of the Zn of 0.01-10wt% and 0.01-1.0wt%.
15. according to each copper base alloy among the claim 11-14, this alloy comprises the Fe that is selected from of 0.01-3.0wt%, Co, Mg, Ti, Cr, at least a element of Zr and Al.
16. have the copper base alloy of the punching press punching out performance of improvement, contain the Sn of 0.01-10 weight %, be selected from Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, one or more optional elements of Zr and Al, the total amount of Sn and described optional element is 0.01-30wt%, the rest is Cu and incidental impurity, and the surperficial X-ray diffraction intensity of described copper base alloy compares S NDBe at least 10, wherein S ND=(I { 220}+ I { 111}+ I { 311})/I { 200}I { 220}Be { X-ray diffraction intensity of 220} face, I { 111}Be { X-ray diffraction intensity of 111} face, I { 311}Be { X-ray diffraction intensity of 311} face, I { 200}It is { the X-ray diffraction intensity of 200} face.
17. according to the copper base alloy of claim 16, this alloy comprises at least a among the P of the Ni of 0.01-4.0wt% and 0.01-0.20wt%.
18. according to the copper base alloy of claim 16, this alloy comprises at least a among the Si of the Zn of 0.01-10wt% and 0.01-1.0wt%.
19. according to the copper base alloy of claim 17, this alloy comprises at least a among the Si of the Zn of 0.01-10wt% and 0.01-1.0wt%.
20. according to each copper base alloy among the claim 16-19, this alloy comprises the Fe that is selected from of 0.01-3.0wt%, Co, Mg, Ti, Cr, at least a element of Zr and Al.
21. preparation method according to one of among the claim 1-20 copper base alloy, it comprises following step: the ingot casting of copper base alloy is carried out cold rolling and subsequently the anneal of at least one round-robin, this copper base alloy has each the identical composition of copper base alloy with claim 1-20, afterwards, to depress than the alloy after the cold rolling described annealing of Z, described Z satisfies following relational expression:
Z≥100-10X-Y (1)
Wherein, Z is a per-cent under the cold rolling; X is the content in the Sn of weight %; Y is the total content in all elements except that Sn and Cu of weight %.
22. according to the method for claim 21, this method further comprises depressing after the described step than the cold rolled annealed alloy of Z, this rolled alloy carried out cold annealing being lower than under the temperature of recrystallization temperature.
23., wherein, before described one or more circulations that constitute by cold rolling and annealing subsequently, ingot casting is implemented homogenizing annealing or hot rolling or both has concurrently according to the method for claim 21.
24., wherein, before described one or more circulations that constitute by cold rolling and annealing subsequently, ingot casting is implemented homogenizing annealing or hot rolling or both has concurrently according to the method for claim 22.
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