CN100462460C - Copper alloy - Google Patents
Copper alloy Download PDFInfo
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- CN100462460C CN100462460C CNB2005800149710A CN200580014971A CN100462460C CN 100462460 C CN100462460 C CN 100462460C CN B2005800149710 A CNB2005800149710 A CN B2005800149710A CN 200580014971 A CN200580014971 A CN 200580014971A CN 100462460 C CN100462460 C CN 100462460C
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
Abstract
The invention relates to a copper alloy for electronic machinery and tools, containing Ni 2.0 to 4.5 mass%, and Si 0.3 to 1.0 mass%, with the balance being Cu and unavoidable impurities, which satisfies the following expression: I{311} x A / (I{311} + I{220} + I{200}) < 1.5 wherein I{311} represents an X-ray diffraction intensity from a {311} plane at a sheet surface; I{220} represents an X-ray diffraction intensity from a {220} plane at the sheet surface; I{200} represents an X-ray diffraction intensity from a {200} plane at the sheet surface; and A ( m) represents a crystalline grain size, and which has good bending property.
Description
Technical field
The present invention relates to a kind of copper alloy that on performance, is improved.
Background technology
New trend along with Electrical and Electronic apparatus and miniaturization of components and manufacturing high-performance Electrical and Electronic apparatus and element has required to have made strict improvement as the material that uses in the junctor parts such as (connector) at various aspect of performances.For example, particularly, the plate thickness that uses at the point of contact of junctor spring has become very thin, to such an extent as to be difficult to guarantee enough contact pressures.That is, at the point of contact of junctor spring, being electrically connected needed contact pressure is to obtain from the reactive force that flexed plate (spring plate) obtains in advance.Therefore, when this plate attenuation, need bigger degree of flexibility to obtain the contact pressure of same degree.Yet when degree of flexibility surpassed the elastic limit of this plate, this plate may stand viscous deformation.Therefore, required further to improve the elastic limit of this plate.
Material for the spring point of contact of junctor also requires other various performances, as proof stress slackness, thermal conductivity, bending property, thermotolerance, plating adhesion property and anti-electric migration performance.In the middle of various performances, physical strength, proof stress slackness, thermal conductivity and electroconductibility and bending property are important.Though phosphor bronze usually has been used to the spring point of contact of junctor, it can not fully satisfy above-mentioned requirements.Therefore, in recent years substituting phosphor bronze with low beryllium content copper alloy (a kind of alloys of Japanese Industrial Standard Committee's 1753 regulations), it has higher physical strength and good proof stress slackness, and good specific conductivity.
Known copper-nickel-silicon-base alloy is the contact member examples of material, and it has the performance that is comparable to low beryllium content copper alloy, and has high relatively intensity as cheap and safe material.Another example of contact member material comprises the copper alloy that improves the proof stress slackness, and it obtains by magnesium being joined in the copper-nickel-silicon base alloy.Another example of contact member material comprises having the copper alloy that is comparable to the low beryllium content copper alloy physical strength, and it obtains by nickel and silicone content in increase copper-nickel-silicon-Ji alloy.
Yet the problem that low beryllium content copper alloy (low beryllium copper) has is that very costliness and metallic beryllium are toxic.Made the intensity that various trials improve copper-nickel-silicon-Ji alloy.Yet the nickel and the silicone content that excessively increase in the copper alloy can reduce bending property, and this bending property is one of desired performance of junctor, have therefore limited the possible application of junctor.Specifically, the grain-boundary brittleness cracking (intergranular embrittlement cracking) of copper alloy in BENDING PROCESS, occurs, cause the copper alloy bending property to reduce.Therefore, find copper-nickel-silicon-Ji alloy as yet with intensity, specific conductivity and bending property of being comparable to low beryllium content copper alloy.And, even magnesium is joined in copper-nickel-silicon-Ji alloy, can not obtain having the proof stress slackness (stress relaxationresistance) that is comparable to the low beryllium content copper alloy performance.
Other and feature and advantage further of the present invention will embody from following explanation more fully.
Summary of the invention
According to the present invention, provide following scheme:
(1) be used for the copper alloy of electronic equipments and element, comprise the nickel of 2.0～4.5 quality % and the silicon of 0.3～1.0 quality %, surplus is copper and unavoidable impurities,
It satisfies following expression formula (1):
I{311}×A/(I{311}+I{220}+I{200})<1.5...(1)
Wherein, in the expression formula (1), the I{311} representative is from { the X-ray diffraction intensity of 311} face (plane) of plate surface (sheet surface); The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size (crysta1 grain size), and
It has good bending property.
(2) be used for the copper alloy of electronic equipments and element, comprise 2.0～4.5 quality % nickel, 0.3～1.0 quality % silicon and greater than 0 and less than the sulphur of 0.005 quality %, surplus is copper and unavoidable impurities,
It satisfies following expression formula (1):
I{311}×A/(I{311}+I{220}I{200})<1.5...(1)
Wherein, in the expression formula (1), the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size, and
It has good bending property.
(3), also comprise the zinc of 0.2～1.5 quality % according to the copper alloy of above-mentioned (1) or (2).
(4) according to above-mentioned (1)～(3) any one copper alloy, also comprise the magnesium of 0.01～0.2 quality %.
(5), also comprise the tin of 0.05～1.5 quality % according to any one copper alloy of above-mentioned (1)～(4).
(6) be used for the copper alloy of electronic equipments and element, comprise magnesium, 0.05～1.5 quality % of silicon, 0.01～0.2 quality % of nickel, 0.3～1.0 quality % of 2.0～4.5 quality % tin, 0.2～1.5 quality % zinc and less than the sulphur of 0.005 quality %, surplus is copper and unavoidable impurities
It satisfies following expression formula (1):
I{311}×A/(I{311}+I{220}+I{200})<1.5...(1)
Wherein, in the expression formula (1), the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size, and
It has good bending property.
(7) according to any one copper alloy of above-mentioned (1)～(6), it also comprises at least a following element that is selected from: the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality % and the boron of 0.001～0.02 quality %, its total content are 0.001～2.0 quality %.
(8) one Albatra metal-s, comprise nickel, 0.3～1.0 quality % of 2.0～4.5 quality % silicon, 0.1～0.5 quality % chromium and less than the sulphur of 0.005 quality %, surplus is copper and unavoidable impurities,
It satisfies following expression formula (2):
I{311}/(I{311}+I{220}+I{200})<0.15...(2)
Wherein, in expression formula (2), the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface.
(9) one Albatra metal-s, comprise nickel, 0.3～1.0 quality % of 2.0～4.5 quality % silicon, 0.1～0.5 quality % chromium and less than the sulphur of 0.005 quality %, surplus is copper and unavoidable impurities,
It satisfies following expression formula (3):
I{311}×A/(I{311}+I{220}+I{200})<1.5...(3)
Wherein, in the expression formula (3), the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size.
(10), also comprise the zinc of 0.2～1.5 quality % according to the copper alloy of above-mentioned (8) or (9).
(11) according to above-mentioned (8)～(10) any one copper alloy, also comprise the magnesium of 0.01～0.2 quality %.
(12), also comprise the tin of 0.05～1.5 quality % according to any one copper alloy of above-mentioned (8)～(11).
(13) according to any one copper alloy of above-mentioned (8)～(12), also comprise at least a following element that is selected from: the silver of the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality %, the titanium of 0.005～0.3 quality %, 0.005～0.3 quality % and the boron of 0.001～0.02 quality %.
Hereinafter, first embodiment of the invention is meant and comprises above-mentioned described all copper alloys in (1)～(7).
Second embodiment of the invention is meant and comprises above-mentioned described all copper alloys in (8)～(13).
Here, unless otherwise mentioned, the present invention meaning be comprise above-mentioned first and second embodiments both.
Embodiment
Below explain in detail the present invention.
[first embodiment]
According to first embodiment, by the integrated level (integration degree) of strictness control crystalline orientation and the bending property that grain size can improve copper alloy, this copper alloy contains physical strength and the specific conductivity of separating out the nickel-silicon compound in the copper matrix and having appropriateness.
Hereinafter, with the relation of describing between the crystalline orientation of copper alloy (hereinafter, abbreviating first Albatra metal-as) of first embodiment.For the copper alloy that contains nickel and silicon, the present inventor finds: can determine the integrated level of crystalline orientation by the control X-ray diffraction intensity, and can improve the bending property and the physical strength of copper alloy by satisfied expression formula of being drawn by X-ray diffraction intensity.That is, when the following expression formula of copper alloy satisfy (1), can improve the bending property and the physical strength of copper alloy.
I{311}×A/(I{311}+I{220}+I{200})<1.5...(1)
Wherein, the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size.
In above-mentioned expression formula (1), stipulated that the integrated level of crystalline orientation and the relation between the grain size make its value less than 1.5, preferably less than 1.2.The lower limit of this value is not particularly limited, but usually greater than 0.3.Too big value can suppress the common raising of copper alloy bending property and physical strength.Contain the copper alloy recrystallize of nickel and silicon and increase its grain size, thereby increase with respect to the plate surface { integrated ratio of 200} face (integration ratio) and { the integrated ratio of 311} face.This copper alloy is cold rolling with higher processing ratio (reduction rate) process, thereby further increases { the integrated ratio of 220} face with respect to the plate surface.The integrated level of crystalline orientation and the relation between the X-ray diffraction intensity are that high X-ray diffraction intensity provides the high integration of crystalline orientation.Here, the integrated ratio of X-ray diffraction face (integrated level of crystalline orientation) is meant the ratio of the crystal growth rate on the direction of each diffraction surfaces, can measure with the ratio of the X-ray diffraction intensity (I) of each diffraction surfaces.In the present invention, the integrated ratio of representing the X-ray diffraction face with the left side of expression formula (I) (in this case, A=1).For example, by " hot rolling ", " cold rolling ", " solution treatment " and " ageing treatment (aging treatment) " operation, and additional process if necessary " precision work cold rolling (finish cold rolling) " and " distortion eliminate annealing (distortionelimination annealing) " can be produced first Albatra metal-.The integrated level of crystalline orientation and grain size change with the condition of solution treatment and the combination of cold worked processing ratio with the integrated level and the grain size of the processing ratio before the solution treatment, mixed crystal orientation.In the present invention, particularly when nickel and silicone content increase, the grain-boundary brittleness of copper alloy improves the bending property of this copper alloy when suppressing bending, and the inventor provides the proper range with expression formula (1) expression to come relation between regulation crystalline orientation integrated level and the grain size.
Alloying element in first Albatra metal-below will be described.
When joining nickel and silicon in the copper, nickel-silicon series compound (Ni
2The Si phase) separates out in the copper matrix, improved physical strength and specific conductivity.The content of nickel is defined in the scope of 2.0～4.5 quality %.This is because when nickel content during less than 2.0 quality %, can not obtain the physical strength identical with conventional low beryllium content copper alloy or be better than the physical strength of conventional low beryllium content copper alloy.On the other hand, when nickel content surpasses 4.5 quality %, separating out of physical strength appearred being helpless to improve in casting or hot procedure, the corresponding physical strength of nickel content that not only can not obtain Yu add, and cause the problem that hot workability and bending property is had disadvantageous effect.Nickel content is 2.2～4.2 quality % preferably, more preferably 3.0～4.0 quality %.
Because silicon forms Ni with nickel
2The Si phase is determined by the content of nickel so add the content of silicon.When silicone content during less than 0.3 quality %, can not obtain the physical strength identical or be better than the physical strength of low beryllium content copper alloy with low beryllium content copper alloy, be similar to nickel content situation too hour.On the other hand, when the content of silicon surpassed 1.0 quality %, the situation when too big with nickel content is the same identical problem to occur.Silicone content is 0.5～0.95 quality % preferably, more preferably 0.7～0.9 quality %.
Physical strength changes with the content of nickel and silicon, and the proof stress slackness also changes thereupon.Therefore, the content of nickel and silicon should strictly be controlled in the scope of this embodiment regulation, so that obtain the proof stress slackness identical with low beryllium content copper alloy or be better than the proof stress slackness of low beryllium content copper alloy.In addition, also should suitably control subsequently the shape of content, crystal grain diameter and the crystal grain of magnesium, tin and the zinc that will describe.
Magnesium, tin and zinc are the important alloying elements that constitutes copper alloy of the present invention.Be to obtain the various premium propertiess of isostatic, the connection that is relative to each other of these elements in the alloy.
Magnesium mainly improves the proof stress slackness, but it influences bending property unfriendly.The content of magnesium is many more, and it is many more that the proof stress slackness improves, and condition is that Mg content for example is, 0.01 quality % or more than the 0.01 quality %.Yet if Mg content is too big, resulting bending property can not satisfy desired level.Under the occasion that adds magnesium, the preferably strict in the present invention content of controlling magnesium is because compare Ni with the copper-nickel-silicon series alloy of routine
2Separating out of Si phase goes far towards the enhanced degree, so bending property variation often.The content of magnesium is 0.01～0.2 quality % normally, more preferably 0.05～0.15 quality %.
Tin and magnesium are interrelated more to improve the proof stress slackness.Yet this raising effect of tin is so big not as magnesium.When tin content was too low, the enough effects that add tin can not present fully, and when tin content is too big, reduce specific conductivity significantly.The content of tin is 0.05～1.5 quality % normally, more preferably 0.1～0.7 quality %.
Zinc can a little improve bending property.The content of zinc is usually in the scope of 0.2～1.5 quality %.When the zinc that adds is in the specialized range of 0.2～1.5 quality %,, also can obtain the bending property of in fact no problem degree (non-problematic level) even add the magnesium of maximum 0.20 quality %.In addition, zinc can improve the adhesion property of tin plating or soft soldering plating (solder plate), and anti-electric migration performance.When zinc content is too low, can not obtains the effect that zinc adds fully, and when zinc content is too big, reduce specific conductivity.The content of zinc is 0.3～1.0 quality % preferably.
To describe hereinafter to improving effectively time component of physical strength, as cobalt and zirconium.
As nickel, cobalt and silicon form compound, improve physical strength.The content of cobalt is 0.05～2.0 quality % normally.When cobalt contents too hour, can not obtain the effect that cobalt adds fully, and when cobalt contents is too big, tend to reduce bending property.The content of cobalt is 0.05～2.0 quality % normally, is preferably 0.1～1.0 quality %.
Zirconium (finely) is imperceptibly separated out in copper, therefore helps to improve the physical strength of resulting copper alloy, and the effect of the crystalline orientation integrated level that reduces expression formula (1) expression is provided.When zirconium content too hour, can not obtain the effect that zirconium adds fully, and when zirconium content is too big, tend to reduce bending property.From above-mentioned viewpoint, the content of zirconium is 0.005～0.3 quality % normally, is preferably 0.05～0.2 quality %.
During in containing these elements of cobalt, zirconium and boron in the alloy simultaneously at least two kinds, depend on desired performance, determine that its total content usually within 0.001～2.0 quality % scope, is preferably 0.005～2.0 quality %.Boron and nickel form compound, therefore reduce the integrated level of the crystalline orientation of expression formula (1) expression.When boron content too hour, can not obtain the effect that boron adds fully, and when boron content is too big, tend to reduce hot workability.From above-mentioned viewpoint, the content of boron is 0.001～0.02 quality % normally, is preferably 0.005～0.01 quality %.
This copper alloy contains the sulphur of trace usually.When sulphur content was too high, it caused reducing hot workability.Therefore, sulphur content preferably is defined as less than 0.005 quality %, especially preferably less than 0.002 quality %.
In the present invention, in the scope that does not reduce fundamental property such as physical strength and specific conductivity, can add other element of proper content, as iron, phosphorus, manganese, titanium, vanadium, lead, bismuth and aluminium.For example, manganese has the effect that improves hot workability, and the manganese that adds under the degree of unlikely reduction specific conductivity in 0.01～0.5 quality % scope is effective.
Contain the copper alloy recrystallize of nickel and silicon and increase its grain size, thereby increase is with respect to { 200} and { the integrated ratio of 311} face on plate surface.This copper alloy is through rolling, thereby increase is with respect to { the integrated ratio of 220} face on plate surface.
For example, by hot rolling, cold rolling, solution treatment and ageing treatment process, as required, annealing operation is eliminated in the cold rolling and distortion of also additional precision work, can produce first Albatra metal-.For example, in production process, hot rolled condition (temperature and time cycle), ensuing condition (temperature and time cycle) and ensuing cold rolling condition (working modulus) cold rolling and solution treatment strictly are controlled at than in the littler scope of general condition.Therefore, can control the integrated ratio and the grain size of this copper alloy, thereby satisfy expression formula (1).
In producing first Albatra metal-, specifically, by hot-rolled temperature being adjusted in 900～1000 ℃ of scopes, cold rolling working modulus is adjusted to more than 90% or 90% after the hot rolling, solid solution temperature is adjusted to 820～930 ℃ and lasts below 20 seconds or 20 seconds, and below cold rolling subsequently processing rate regulation to 30% or 30%, can satisfy expression formula (1).
When rolling was the plastic working of carrying out at last, here the direction of the final plastic working of Shi Yonging was meant rolling direction, and maybe when stretch (linear stretch) was the plastic working of carrying out at last, the direction of final plastic working was meant draw direction.Plastic working refers to rolling and stretching, and still, for example the processing for smooth (leveling) (vertically smooth) purpose is not included in this plastic working, for example uses tension level(l)er.
[second embodiment]
According to second embodiment, to satisfy recent needs, the bending property and the physical strength that contain the copper alloy of coprecipitated nickel hydroxide-silicon compound in the copper matrix can be improved by the integrated level of control chromium content and crystalline orientation by following method improvement copper-nickel-silicon-Ji alloy.
Hereinafter, will each component of the copper alloy (hereinafter, abbreviating second Albatra metal-as) of second embodiment be described.
As everyone knows, by nickel and silicon being joined in the copper coprecipitated nickel hydroxide in the copper matrix-silicon series compound (Ni
2The Si phase), improve physical strength and specific conductivity.In the present invention, the content of nickel is usually in the scope of 2.0～4.5 quality %, preferably in the scope of 2.2～4.2 quality %, and more preferably in the scope of 3.0～4.0 quality %.
The content of nickel as defined above.This is because when nickel content is too low, can not obtain the physical strength identical with conventional beryllium-copper alloy or be better than the physical strength of conventional beryllium-copper alloy.On the other hand, when the nickel too high levels, in casting or hot procedure, separated out the precipitate that is helpless to improve physical strength, the corresponding physical strength of nickel content that not only can not obtain Yu add, and cause the problem that hot workability and bending property is had disadvantageous effect.
Because silicon forms Ni with nickel
2The Si phase is to determine by the content of determining nickel so add the optimum content of silicon.Silicone content is 0.3～1.0 quality % normally, preferably 0.5～0.95 quality %, more preferably 0.7～0.9 quality %.When silicone content too hour, can not obtain the physical strength identical or be better than the physical strength of beryllium-copper alloy with beryllium-copper alloy, be similar to nickel content situation too hour.On the other hand, when the content of silicon was too big, the situation when too big with nickel content is the same identical problem to occur.
Control the chromium content and the X-ray diffraction intensity of formed copper alloy, thereby improve the bending property and the physical strength of sheet alloy.
That is, be 0.1～0.5 quality % and satisfy expression formula as described below (2) or (3), improve the bending property and the physical strength of this sheet alloy by regulating chromium content.
And chromium is present in this alloy with chromium cpd such as chromium-silicon series or chromium-nickel-silicon series, and it has the effect that suppresses the effect that grain size increases and reduce the integrated level of the crystalline orientation that this expression formula represents during solution treatment.Yet too low chromium content can not provide effect of sufficient, and too high chromium content reduces the bending property of alloy.From these viewpoints, the content of chromium is 0.1～0.5 quality % normally, is preferably 0.15～0.4 quality %.
Magnesium, tin and zinc are the important alloying elements that constitutes copper alloy of the present invention.These elements in alloy connection that is relative to each other obtains various isostatic premium propertiess.
Magnesium improves the proof stress slackness, but it has disadvantageous effect to bending property.The content of magnesium is many more, and it is many more that the proof stress slackness improves, and condition is that Mg content is 0.01 quality % or more than the 0.01 quality % for example.Yet if Mg content is too big, resulting bending property can not satisfy desired level.Under the occasion that adds magnesium, preferably strictly control the content of magnesium in the present invention, because compare Ni with the copper-nickel-silicon series alloy of routine
2Separating out of Si phase helps the enhanced degree far away, for this reason bending property variation often.The content of magnesium is 0.01～0.2 quality % normally, more preferably 0.05～0.15 quality %.
Tin and magnesium are interrelated more to improve the proof stress slackness.When tin content too hour, the enough effects that add tin can not present fully, and when tin content is too big, reduce specific conductivity significantly.The content of tin is 0.05～1.5 quality % normally, more preferably 0.1～0.7 quality %.
Zinc can improve bending property.Zinc content is generally 0.2～1.5 quality %, is the magnesium of 0.20 quality % even add maximum, by adding zinc, also can obtain bending property no problem on practical level.In addition, zinc improves tin to be electroplated or the galvanized adhesion property of soft soldering, and anti-electric migration performance.When zinc content too hour, can not obtain the effect that zinc adds fully, and when zinc content is too big, the reduction specific conductivity.The content of zinc is 0.3～1.0 quality % preferably.
Each all has the effect of the integrated level of the crystalline orientation that reduces any one expression of expression formula as described below zirconium, cobalt, titanium, silver and boron.
Zirconium has the effect of the integrated level that reduces the crystalline orientation that this expression formula represents, and helps to improve the intensity of alloy simultaneously.Yet too low zirconium content can not provide enough effects, and too high zirconium content reduces the bending property of alloy.From these viewpoints, the content of zirconium is 0.005～0.3 quality % normally, is preferably 0.05～0.2 quality %.
Similar to nickel, cobalt and silicon form compound improving the intensity of alloy, and have the effect of the integrated level that reduces the crystalline orientation that this expression formula represents.The content of cobalt is 0.05～2.0 quality % normally.When cobalt contents too hour, can not obtain the effect that cobalt adds fully, and when cobalt contents is too big, the reduction bending property.The content of cobalt is 0.1～1.0 quality % preferably.
Similar to chromium, zirconium, titanium, silver and other elements, cobalt has and suppresses the effect that grain size increases and reduce the integrated level of the crystalline orientation that this expression formula represents.
Boron has the effect of the integrated level that reduces the crystalline orientation that this expression formula represents.Too low boron content can not provide enough effects, and too high boron content then reduces hot workability.From these viewpoints, the content of boron is 0.001～0.02 quality % normally, is preferably 0.005～0.01 quality %.
Titanium improves the thermotolerance and the physical strength of alloy, and has and suppress the effect that grain size increases and reduce the integrated level of the crystalline orientation that this expression formula represents.Too low titanium content can not provide enough effects; The then remaining undissolved titanium of too high titanium content can't provide effect, and plating performance is had adverse influence etc.From these viewpoints, the content of titanium is 0.005～0.3 quality % normally, is preferably 0.05～0.2 quality %.
Silver improves the thermotolerance and the physical strength of alloy, and has and suppress the effect that grain size increases and reduce the integrated level of the crystalline orientation that this expression formula represents.If the content of silver is too little, then it can't enough produce the effect that adds silver; And if the content of silver is too big, even observe a large amount of silver of adding resulting performance there is not adverse influence, it also causes alloy cost height.From above-mentioned viewpoint, the content of silver is 0.005～0.3 quality % normally, is preferably 0.05～0.2 quality %.
More preferably when at least two kinds of elements are included in the alloy simultaneously in cobalt, zirconium, titanium, silver and the boron, depend on desired performance, its total content is defined within the scope of 0.005～2.0 quality %.
This copper alloy contains the sulphur of trace usually.When sulphur content was too high, it caused reducing hot workability.Therefore, sulphur content preferably is defined as less than 0.005 quality %, especially preferably less than 0.002 quality %.
In the present invention, in the scope that does not reduce fundamental property such as physical strength and specific conductivity, can add other element of proper content, as iron, phosphorus, manganese, vanadium, lead, bismuth and aluminium.For example, manganese has the effect that improves hot workability, and the manganese that adds in 0.01～0.5 quality % scope is effectively, can not reduce specific conductivity.
Below, will the crystalline orientation of second Albatra metal-be described.
In the copper alloy that contains nickel and silicon, resulting crystal recrystallize also increases its grain size, thereby increases { 200} and { the integrated ratio on 311} face and plate surface.This copper alloy is through rolling, thus increase { the integrated ratio on 220} face and plate surface.
For example, by hot rolling, cold rolling and ageing treatment process, as required, the cold rolling and distortion elimination annealing operation of also additional precision work can be produced second Albatra metal-.For example, in production process, hot rolled condition (temperature and time cycle), ensuing condition (temperature and time cycle) and ensuing cold rolling condition (processing ratio) cold rolling and solution treatment strictly are controlled at than in the littler scope of general condition, thereby control sets is proportional and grain size.
The copper alloy that the present inventor's discovery has the integrated level of the crystalline orientation in the specialized range is having improvement aspect bending property and the physical strength, and this integrated level is to be determined by the X-ray diffraction intensity of the integrated ratio of expression.Here, the integrated ratio of X-ray diffraction face (integrated level of crystalline orientation) refers to the crystal growth degree ratio on the direction of each diffraction surfaces, and X-ray diffraction intensity (I) ratio that can each diffraction surfaces is measured.Specifically, satisfy following expression formula (2) and have the copper alloy of chromium content in above-mentioned specified range and can on bending property and physical strength, improve:
I{311}/(I{311}+I{220}+I{200})<0.15...(2)
Wherein, the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; And the I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface.
In above-mentioned expression formula (2), the integrated level value of crystalline orientation is less than 0.15, preferably less than 0.12.The lower limit of this value is not particularly limited, but usually greater than 0.03.If this value is too big, bending property and physical strength that it can cause suppressing copper alloy improve.
And the copper alloy that satisfies following expression formula (3) can arriving on bending property and tensile strength improve:
I{311}×A/(I{311}+I{220}+I{200})<1.5...(3)
Wherein, to above-mentioned similar, the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size.
In above-mentioned expression formula (3), the integrated level of regulation crystalline orientation and the relation between the grain size preferably should be worth less than 1.2 to obtain the value less than 1.5.The lower limit of this value is not particularly limited, but usually greater than 0.3.Similar to the above, this is worth too conference and suppresses the bending property of copper alloy and the raising of physical strength.Therefore, this grain size is preferably as far as possible little, and specifically, grain size is preferably less than 10 μ m, more preferably 5～8 μ m.
In producing second Albatra metal-, for example, by hot-rolled temperature being adjusted in 900～1000 ℃ of scopes, after the hot rolling more than the cold rolling processing rate regulation to 90% or 90%, solid solution temperature is adjusted to 820～930 ℃ and lasts below 20 seconds or 20 seconds, and below ensuing cold rolling processing rate regulation to 30% or 30%, can satisfy expression formula (2) or (3).
According to the present invention, a kind of copper alloy as materials such as terminal (terminal), junctor, switches can be provided, it has for example good physical strength, specific conductivity and bending property, except that these performances, also has good proof stress slackness and electroplates sticking power sometimes.
Copper alloy of the present invention for example has, good physical strength, specific conductivity and bending property (above-mentioned first embodiment), and except that above-mentioned performance, also have good proof stress slackness (above-mentioned second embodiment).The minitype high-performance parts that can be used to produce Electrical and Electronic apparatus and element by the Cu alloy material of worked copper alloy acquisition.For example, copper alloy of the present invention can be preferably applied to terminal, junctor or switch, and the general conductive material of lead frame, rly. etc.
Embodiment
To describe the present invention in more detail based on following embodiment, but the present invention is not limited to these embodiment.Below among the embodiment, embodiment 1 and 2 examples, and embodiment 3 and 4 examples corresponding to second embodiment corresponding to first embodiment.
(embodiment 1)
Each has composition as shown in table 1 (ingot bar (ingot) number A to V, WA to WH, X and Z) copper alloy, and every kind of alloy is melted in the high-frequency melting stove by the direct current method respectively, casts the ingot bar of 150 millimeters of 30 millimeters of thickness, 100 millimeters of width and length.Then, these ingot bars are heated to 1000 ℃.With ingot bar after keeping 1 hour under this temperature, resulting ingot bar is rolled into the plate of 12 millimeters of thickness, then cooling fast separately.
Then, to both ends of the surface cutting (the cutting sth. askew) 1.5 millimeters of each hot-rolled sheet, remove the oxide film of each face.Resulting plate is processed into the plate of 0.15～0.25 millimeter of thickness by cold rolling (a).Then, this cold-reduced sheet changes solid solution temperature simultaneously through Overheating Treatment 15 seconds in 825～925 ℃ scope, afterwards, cool off with the cooling rate more than 15 ℃/second or 15 ℃/second immediately.Then, carried out ageing treatment 2 hours in inert gas atmosphere under 475 ℃, then, depend on sample, if necessary, carry out cold rolling (c) as last plastic working, adjusting last plate thickness is 0.15 millimeter.After ageing treatment or last plastic working, this sample is through 375 ℃ of following low-temperature annealings 2 hours, thus manufactured copper alloy sheets (sample 1 and 5 to 41) respectively.
(embodiment 2)
Under the condition, by processing the copper alloy (ingot bar J) with composition as shown in table 1 respectively, production thickness is 0.15 millimeter copper alloy plate below.That is, begin to remove oxide film after hot rolling from fusing, working condition is identical with the production stage of embodiment 1.Then, by cold rolling (a) resulting plate being worked into thickness is 0.15～0.5 millimeter, then thermal treatment 15 seconds under the solid solution temperature in 825～925 ℃ of scopes.After this, cool off this plate with the cooling rate more than 15 ℃/second or 15 ℃/second immediately.
Then, depend on sample, if necessary, resulting plate with the processing ratio below 50% or 50% through cold rolling (b), then, under the condition identical with embodiment 1, ageing treatment in inert gas atmosphere respectively, final plastic working (cold rolling (c) becomes final plate thickness is 0.15 millimeter), low-temperature annealing then, thereby production of copper alloy sheets (sample 2 to 4).
Table 1
| Ingot bar No. | Ni quality % | Si quality % | Mg quality % | Sn quality % | Zn quality % | S quality % | Other element quality % |
| A | 3.8 | 0.89 | - | - | - | 0.002 | - |
| B | 3.4 | 0.83 | - | - | - | 0.002 | - |
| C | 3.2 | 0.77 | - | - | - | 0.002 | - |
| D | 3.8 | 0.9 | 0.1 | - | - | 0.002 | - |
| E | 3.8 | 0.9 | - | 0.15 | - | 0.002 | - |
| F | 3.8 | 0.9 | - | - | 0.5 | 0.002 | - |
| G | 3.8 | 0.9 | 0.1 | 0.15 | - | 0.002 | - |
| H | 3.8 | 0.9 | 0.1 | - | 0.5 | 0.002 | - |
| I | 3.8 | 0.9 | - | 0.15 | 0.5 | 0.002 | - |
| J | 3.8 | 0.9 | 0.1 | 0.15 | 0.5 | 0.002 | - |
| K | 3.5 | 0.84 | 0.1 | 0.16 | 0.47 | 0.002 | - |
| L | 3.3 | 0.78 | 0.1 | 0.16 | 0.48 | 0.002 | - |
| N | 3.8 | 0.89 | 0.1 | 0.15 | 0.5 | 0.002 | Zr：0.1 |
| O | 3.8 | 0.89 | 0.1 | 0.15 | 0.5 | 0.002 | Co：0.25 |
| D | 3.8 | 0.89 | 0.1 | 0.15 | 0.49 | 0.002 | B：0.01 |
| Q | 5 | 1.17 | 0.1 | 0.21 | 0.49 | 0.002 | - |
| R | 3.8 | 0.9 | 0.1 | 0.15 | 1.7 | 0.002 | - |
| S | 3.8 | 0.9 | 0.38 | 0.2 | 0.5 | 0.002 | - |
| T | 3.8 | 0.89 | 0.08 | 2.01 | 0.5 | 0.002 | - |
| V | 4.1 | 0.9 | 0.1 | 0.15 | 0.48 | 0.002 | B：0.03 |
| WA | 2.3 | 0.56 | - | - | - | 0.002 | - |
| WB | 2.3 | 0.56 | 0.1 | - | - | 0.002 | - |
| WC | 2.2 | 0.54 | - | 0.15 | - | 0.002 | - |
| WD | 2.3 | 0.56 | - | - | 0.5 | 0.002 | - |
| WE | 2.4 | 0.55 | 0.1 | 0.15 | - | 0.002 | - |
| WF | 2.3 | 0.56 | 0.1 | - | 0.5 | 0.002 | - |
| WG | 2.4 | 0.55 | - | 0.15 | 0.5 | 0.002 | - |
| WH | 2.3 | 0.56 | 0.1 | 0.15 | 0.5 | 0.002 | - |
| X | 3.8 | 0.9 | 0.1 | 0.15 | 0.5 | 0.011 | - |
| Z | 1.7 | 0.27 | 0.1 | 0.15 | 0.5 | 0.002 | - |
Annotate: the surplus of every kind of alloy is copper and unavoidable impurities;
"-", add.
Test and measure (1) crystal grain diameter of every kind of copper alloy plate of producing thus, (2) crystalline orientation, (3) tensile strength, (4) specific conductivity and (5) bending property.
Measure crystal grain diameter (1) according to JIS H 0501 (cutting method).
Determine crystalline orientation (2) by following method: with the surface (thickness is 0.15 millimeter) of the copper alloy plate of x-ray bombardment the finished product state; With the intensity of measuring from diffraction surfaces.Wherein, relatively demonstrate with the bending property strong correlation 200}, 220} and 311} face diffracted intensity separately, thus obtain crystalline orientation strength ratio (I{311} * A/ (I{311}+I{220}+I{200})).The condition of x-ray bombardment is: x-ray source CuK α 1; 40 kilovolts of tube voltages; With 20 milliamperes of tube currents.
Use the #5 testpieces of describing among the JIS Z 2201, it is formed by each sample panel, determines tensile strength (3) according to JIS Z2241.
Determine specific conductivity (4) according to JIS H 0505.
Method with description among the JIS H 3110 is fundamental measurement bending property (5).It with the flecxure width of 1000 kilogram forces 10 millimeters test specimen.Go up cutting sample in GW direction (with the vertical bending axis of rolling direction) or BW direction (bending axis parallel) with rolling direction.Measure bending property with ratio R/t, wherein the R representative forms the minimum bending radius under the limit (a limit of crack formation) in the crack, and t represents the thickness of test specimen.
From the result shown in the table 2, be apparent that sample 1,5 to 19 (embodiment 1) and sample 2 to 4 (embodiment 2) have good performance separately, satisfy bending property (R/t) less than 2, tensile strength is that the above and specific conductivity of 800MPa or 800MPa is 35%IACS or more than the 35%IACS.And sample 34 to 41 has low a little tensile strength, but have good performance separately, satisfy bending property (R/t) less than 2 and specific conductivity be 35%IACS or more than the 35%IACS.
On the contrary, the value of sample 20 to 25 (comparative example) expression formula (1) separately and has the bending property of significance difference not in the scope of the present invention regulation, and the chances are causes because solid solution temperature is too high for it.
Because the content of nickel and silicon is too big, the crack appears, so can not ordinary production go out sample 26 (comparative example) in hot procedure.
Sample 27 (requiring the comparative example of the present invention of (3) about aforesaid right) satisfies the value of expression formula (1), and has good bending property.Yet, because zinc content is too high, so the electric conductivity difference of this sample.
Because Mg content is too high, the bending property of sample 28 (requiring the comparative example of the present invention of (4) about aforesaid right) is poor.
Because tin content is too high, edge crack appears, so can not produce sample 29 (requiring the comparative example of the present invention of (5) about aforesaid right) in cold-rolled process.
Because boron content is too high, the crack appears, so can not ordinary production go out sample 31 (requiring the comparative example of the present invention of (7) about aforesaid right) in hot procedure.
Because sulphur content is too high, the crack appears, so stop production sample 32 (requiring the comparative example of the present invention of (2) about aforesaid right) in hot procedure.
The value that No. 33 samples provide is outside the specialized range of expression formula of the present invention (1).The nickel and the silicone content of this sample are too little, bad mechanical strength, and do not reach the performance of beryllium copper far away.
Table 2
(embodiment 3)
Every Albatra metal-has composition as shown in table 3 (ingot bar 2-A to 2-O, 2-PA to 2-PH, 2-Q to 2-S, 2-Z and 2-A-1), by the direct current method every kind of alloy is melted in the high-frequency melting stove respectively, cast thickness and be 30 millimeters, width and be 100 millimeters and length and be 150 millimeters ingot bar.Then, these ingot bars are heated to 1000 ℃.With ingot bar after keeping 1 hour under this temperature, each resulting ingot bar is rolled into the plate of 12 millimeters of thickness, then cooling fast.
Then, to both ends of the surface cutting (the cutting sth. askew) 1.5 millimeters of each hot-rolled sheet, remove oxide film.Resulting plate is processed into the plate of 0.15～0.25 millimeter of thickness by cold rolling (2-a).Then, in 825～925 ℃ temperature range, change solid solution temperature,, afterwards, then cool off with the cooling rate more than 15 ℃/second or 15 ℃/second immediately cold-reduced sheet thermal treatment 15 seconds.Then, carried out ageing treatment 2 hours in inert gas atmosphere under 475 ℃, then, if necessary, depend on sample, carry out cold rolling (2-c) as final plastic working, adjusting final plate thickness is 0.15 millimeter.After ageing treatment or final plastic working, this sample descended the process low-temperature annealings 2 hours at 375 ℃, thereby produced copper alloy plate (sample number 2-0 to 2-2,2-1-1 and 2-5 to 2-30) respectively.
(embodiment 4)
Under the condition, by processing the copper alloy (ingot bar 2-B) with composition as shown in table 3 respectively, production thickness is 0.15 millimeter copper alloy plate below.That is, begin to remove oxide film after hot rolling from fusing, working condition is identical with the production process of embodiment 3.Then, by cold rolling (2-a) resulting plate being worked into thickness is 0.15～0.5 millimeter, then thermal treatment 15 seconds under the solid solution temperature in 825～925 ℃ of scopes.After this, cool off this plate with the cooling rate more than 15 ℃/second or 15 ℃/second immediately.Then, depend on sample, if necessary, resulting plate with the processing ratio below 50% or 50% through cold rolling (2-b), then, under the condition identical with embodiment 3, ageing treatment in inert gas atmosphere, final plastic working (cold rolling (2-c) becomes final thickness is 0.35 millimeter plate), low-temperature annealing then, thereby production of copper alloy sheets (sample 2-3 and 2-4) respectively.
Table 3
| Ingot bar No. | Ni quality % | Si quality % | Mg quality % | Sn quality % | Zn quality % | Cr quality % | S quality % | Other element quality % |
| 2-Z | 3.74 | 0.89 | - | - | - | 0.23 | 0.002 | - |
| 2-A | 3.76 | 0.89 | - | - | 0.49 | 0.25 | 0.002 | - |
| 2-A-1 | 3.75 | 0.89 | 0.10 | 0.15 | - | 0.24 | 0.002 | - |
| 2-B | 3.78 | 0.9 | 0.09 | 0.15 | 0.49 | 0.21 | 0.002 | - |
| 2-C | 3.52 | 0.83 | 0.11 | 0.16 | 0.51 | 0.22 | 0.002 | - |
| 2-D | 4.1 | 0.95 | 0.10 | 0.15 | 0.52 | 0.2 | 0.002 | - |
| 2-E | 3.21 | 0.72 | 0.09 | 0.14 | 0.5 | 0.19 | 0.002 | - |
| 2-F | 3.79 | 0.9 | 0.12 | 0.15 | 0.48 | 0.24 | 0.002 | Ag：0.1 |
| 2-G | 3.8 | 0.91 | 0.10 | 0.15 | 0.47 | 0.21 | 0.002 | Co：0.31 |
| 2-H | 3.81 | 0.92 | 0.08 | 0.17 | 0.51 | 0.2 | 0.002 | Zr：0.17 |
| 2-I | 3.76 | 0.89 | 0.10 | 0.15 | 0.5 | 0.25 | 0.002 | Ti：0.16 |
| 2-J | 3.76 | 0.91 | 0.09 | 0.14 | 0.5 | 0.6 | 0.002 | - |
| 2-K | 5 | 1.17 | 0.11 | 0.21 | 0.49 | 0.23 | 0.002 | - |
| 2-L | 3.78 | 0.88 | 0.08 | 0.16 | 1.7 | 0.21 | 0.002 | - |
| 2-M | 3.81 | 0.92 | 0.38 | 0.20 | 0.5 | 0.2 | 0.002 | - |
| 2-N | 3.74 | 0.87 | 0.08 | 2.01 | 0.48 | 0.19 | 0.002 | - |
| 2-O | 3.76 | 0.9 | 0.12 | 0.17 | 0.52 | 0.1 | 0.002 | - |
| 2-PA | 2.3 | 0.56 | - | - | - | 0.27 | 0.002 | - |
| 2-PB | 2.3 | 0.56 | 0.10 | - | - | 0.27 | 0.002 | - |
| 2-PC | 2.3 | 0.56 | - | 0.14 | - | 0.27 | 0.002 | - |
| 2-PD | 2.3 | 0.56 | - | - | 0.51 | 0.27 | 0.002 | - |
| 2-PE | 2.3 | 0.56 | 0.10 | 0.14 | - | 0.27 | 0.002 | - |
| 2-PF | 2.3 | 0.56 | 0.10 | - | 0.51 | 0.27 | 0.002 | - |
| 2-PG | 2.3 | 0.56 | - | 0.14 | 0.51 | 0.27 | 0.002 | - |
| 2-PH | 2.3 | 0.56 | 0.10 | 0.14 | 0.51 | 0.27 | 0.002 | - |
| 2-Q | 3.8 | 0.89 | 0.11 | 0.15 | 0.46 | 0.22 | 0.011 | - |
| 2-R | 3.78 | 0.91 | 0.10 | 0.16 | 0.5 | - | 0.002 | - |
| 2-S | 1.7 | 0.27 | 0.10 | 0.14 | 0.51 | 0.27 | 0.002 | - |
Annotate: the surplus of every kind of alloy is copper and unavoidable impurities;
＂-＂ does not add.
(1) crystal grain diameter, (2) crystalline orientation, (3) bending property, (4) tensile strength, (5) specific conductivity and (6) proof stress slackness of the copper alloy plate of producing separately among test and the mensuration embodiment 3 and 4.
(1) measures crystal grain diameter (size) according to JIS H 0501 (section method).
(2) determine crystalline orientation by following method: with the surface (thickness is 0.15 millimeter) of the copper alloy plate of x-ray bombardment the finished product state; With the intensity of measuring from diffraction surfaces.Wherein, the diffracted intensity of I{220}, I{200}, I{311} face relatively obtains integrated level (I{311}/(I{311}+I{220}+I{200})) and (I{311} * A/ (I{311}+I{220}+I{200})) of crystalline orientation thus.The condition of x-ray bombardment is: x-ray source CuK α 1; 40 kilovolts of tube voltages; With 20 milliamperes of tube currents.
(3) measure bending property based on the method for describing among the JIS H 3110.It with the flecxure width of 1000 kilogram forces 10 millimeters test specimen.Go up the cut-out test specimen in GW direction (with the vertical bending axis of rolling direction) or BW direction (bending axis parallel) with rolling direction.Measure bending property with ratio R/t, wherein the R representative forms the minimum bending radius under the limit in the crack, and t represents the thickness of test specimen.
(4) use the #5 test specimen of describing among the JIS Z 2201, determine tensile strength according to JIS Z 2241.
(5) determine specific conductivity according to JIS H 0505.
(6) as the index of proof stress slackness, by using the monolateral fixedly clustering method (one-side holding block method) of Nippon Standard electronics material association of manufacturer (EMAS-3003), determine stress relaxation ratio (S.R.R), wherein regulate stress-loaded, so that maximum surface stress is 80%YS (80% a yield strength, or 0.2% proof stress (proof stress)), and with resulting test specimen in 150 ℃ thermostatic chamber, kept 1000 hours.
The results are shown in the table 4.
Obviously find out from the result shown in the table 4, sample 2-0 to 2-2,2-1-1 and 2-5 to 2-11 (embodiment 3) and sample 2-3 and 2-4 (embodiment 4) have good performance separately, satisfy bending property (R/t) less than 2, tensile strength is 810MPa or more than the 810MPa, and specific conductivity is that the above and stress relaxation rate of 35%IACS or 35%IACS is all properties below 10% or 10%.And sample 2-23 to 2-30 has low a little tensile strength, and have have a low a little stress relaxation ratio, but all have good performance separately, satisfy bending property (R/t) less than 2 and specific conductivity be 35%IACS or more than the 35%IACS both.
With above-mentioned opposite, sample 2-12 and 2-13 (comparative example) separately expression formula (2) or the value of (3) not in the scope of the present invention's regulation, and have the bending property of significance difference, the chances are causes because solid solution temperature is too high for it.
Sample 2-14 (comparative example) is because chromium content is too big, and its bending property is poor.
Because the content of nickel and silicon is too big, the crack appears, so can not ordinary production go out sample 2-15 (comparative example) in hot procedure.
Because zinc content is too high, the electric conductivity difference of sample 2-16 (requiring the comparative example of the present invention of (10) relevant for aforesaid right).
The proof stress slackness of sample 2-17 (requiring the comparative example of the present invention of (11) relevant for aforesaid right) is fabulous, but because Mg content is too high, its bending property is poor significantly.
Because tin content is too high, in the cold working process crack appears, so can not ordinary production go out sample 2-18 (requiring the comparative example of the present invention of (12) relevant for aforesaid right).
Because the value of the expression formula (2) of sample 2-19 (comparative example) or (3) is not in the scope of the present invention's regulation, so its bending property is poor significantly.
Because the content of sulphur is too big, the crack appears, so can not ordinary production go out sample 2-20 (comparative example) in hot procedure.
Because the value of the expression formula (2) of sample 2-21 (comparative example) or (3) is not in the scope of the present invention's regulation, so its bending property is poor significantly.
Because nickel and silicone content are too little, so the physical strength of sample 2-22 (comparative example) and proof stress slackness are poor significantly.
Industrial applicibility
Copper alloy of the present invention is preferably as the material that is used for terminal, junctor and lead frame, and it for example is used for switch and rly. also preferably as general conductive material.
Though described and the relevant invention of our present embodiments, yet our intention is that the present invention is not limited to any details of specification sheets, unless otherwise mentioned, but is interpreted as widely in the spirit and scope of appended claims statement.
Claims (11)
1. a copper alloy that is used for electronic equipments and element comprises the nickel of 2.0～4.5 quality % and the silicon of 0.3～1.0 quality %, and surplus is copper and unavoidable impurities,
It satisfies following expression formula (1):
I{311}×A/(I{311}+I{220}+I{200})<1.5...(1)
Wherein, in expression formula (1), the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size, and
It has good bending property.
2. according to the copper alloy of claim 1, it also comprises at least a element in the tin of the magnesium of the zinc that is selected from 0.2～1.5 quality %, 0.01～0.2 quality % and 0.05～1.5 quality %.
3. require 1 copper alloy according to aforesaid right, it also comprises at least a following element that is selected from: the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality % and the boron of 0.001～0.02 quality %, its total content are 0.001～2.0 quality %.
4. according to the copper alloy of claim 1, it also comprises greater than 0 and less than the sulphur of 0.005 quality %.
5. according to the copper alloy of claim 4, it also comprises at least a element in the tin of the magnesium of the zinc that is selected from 0.2～1.5 quality %, 0.01～0.2 quality % and 0.05～1.5 quality %.
6. require 4 copper alloy according to aforesaid right, it also comprises at least a following element that is selected from: the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality % and the boron of 0.001～0.02 quality %, its total content are 0.001～2.0 quality %.
7. according to the copper alloy of claim 1, its also comprise magnesium, 0.05～1.5 quality % of 0.01～0.2 quality % tin, 0.2～1.5 quality % zinc and greater than 0 and less than the sulphur of 0.005 quality %.
8. according to the copper alloy of claim 7, it also comprises at least a following element that is selected from: the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality % and the boron of 0.001～0.02 quality %, its total content are 0.001～2.0 quality %.
9. according to the copper alloy of claim 1, it also comprises the chromium of 0.1～0.5 quality % and less than the sulphur of 0.005 quality %.
10. according to the copper alloy of claim 9, it also comprises at least a element in the tin of the magnesium of the zinc that is selected from 0.2～1.5 quality %, 0.01～0.2 quality % and 0.05～1.5 quality %.
11. according to the copper alloy of claim 9, it also comprises at least a following element that is selected from: the silver of the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality %, the titanium of 0.005～0.3 quality %, 0.005～0.3 quality % and the boron of 0.001～0.02 quality %.
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| JPH1143731A (en) * | 1997-07-23 | 1999-02-16 | Kobe Steel Ltd | High strength copper alloy excellent in stamping property and suitable for silver plating |
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| US4016010A (en) * | 1976-02-06 | 1977-04-05 | Olin Corporation | Preparation of high strength copper base alloy |
| US4110132A (en) * | 1976-09-29 | 1978-08-29 | Olin Corporation | Improved copper base alloys |
| JPS57206540A (en) * | 1981-06-12 | 1982-12-17 | Nippon Gakki Seizo Kk | Manufacture of parts for spectacle frame |
| US4594221A (en) * | 1985-04-26 | 1986-06-10 | Olin Corporation | Multipurpose copper alloys with moderate conductivity and high strength |
| DE4115998C2 (en) * | 1991-05-16 | 1999-02-25 | Diehl Stiftung & Co | Process for the production of copper alloys |
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| JP3797786B2 (en) * | 1998-03-06 | 2006-07-19 | 株式会社神戸製鋼所 | Copper alloy for electrical and electronic parts |
| JP3739214B2 (en) * | 1998-03-26 | 2006-01-25 | 株式会社神戸製鋼所 | Copper alloy sheet for electronic parts |
| JP3800279B2 (en) * | 1998-08-31 | 2006-07-26 | 株式会社神戸製鋼所 | Copper alloy sheet with excellent press punchability |
| JP2000080428A (en) * | 1998-08-31 | 2000-03-21 | Kobe Steel Ltd | Copper alloy sheet excellent in bendability |
| JP3520046B2 (en) * | 2000-12-15 | 2004-04-19 | 古河電気工業株式会社 | High strength copper alloy |
| JP4729680B2 (en) * | 2000-12-18 | 2011-07-20 | Ｄｏｗａメタルテック株式会社 | Copper-based alloy with excellent press punchability |
| KR100513943B1 (en) * | 2001-03-27 | 2005-09-09 | 닛꼬 긴조꾸 가꼬 가부시키가이샤 | Copper and copper alloy, and method for production of the same |
-
2004
- 2004-11-11 JP JP2004328177A patent/JP4809602B2/en active Active
-
2005
- 2005-05-24 US US11/135,289 patent/US20050263218A1/en not_active Abandoned
- 2005-05-26 DE DE112005001197.6T patent/DE112005001197B4/en not_active Expired - Fee Related
- 2005-05-26 WO PCT/JP2005/010096 patent/WO2005116282A1/en active Application Filing
- 2005-05-26 CN CNB2005800149710A patent/CN100462460C/en not_active Expired - Fee Related
- 2005-05-26 TW TW094117169A patent/TWI371499B/en active
- 2005-05-26 MY MYPI20052404A patent/MY142123A/en unknown
- 2005-05-26 KR KR1020067024910A patent/KR100929276B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1143731A (en) * | 1997-07-23 | 1999-02-16 | Kobe Steel Ltd | High strength copper alloy excellent in stamping property and suitable for silver plating |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200604354A (en) | 2006-02-01 |
| KR20070018092A (en) | 2007-02-13 |
| KR100929276B1 (en) | 2009-11-27 |
| MY142123A (en) | 2010-09-15 |
| JP4809602B2 (en) | 2011-11-09 |
| TWI371499B (en) | 2012-09-01 |
| CN1950525A (en) | 2007-04-18 |
| DE112005001197B4 (en) | 2016-11-03 |
| DE112005001197T5 (en) | 2007-04-19 |
| WO2005116282A1 (en) | 2005-12-08 |
| US20050263218A1 (en) | 2005-12-01 |
| JP2006009137A (en) | 2006-01-12 |
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