CN100528550C - Heat resistant film, its manufacturing method, and electrical and electronic parts - Google Patents
Heat resistant film, its manufacturing method, and electrical and electronic parts Download PDFInfo
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- CN100528550C CN100528550C CNB2006101149269A CN200610114926A CN100528550C CN 100528550 C CN100528550 C CN 100528550C CN B2006101149269 A CNB2006101149269 A CN B2006101149269A CN 200610114926 A CN200610114926 A CN 200610114926A CN 100528550 C CN100528550 C CN 100528550C
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Abstract
Provided are a film having excellent heat resistance, formability and solderability, and used for coating the surface of a material, its manufacturing method, and further electrical and electronic parts coated with the film. An Ni or Ni-alloy layer, a Cu layer and an Sn or Sn-alloy layer are applied to the surface of the material composed of copper alloy, etc., in the order named from the surface side. Then reflow treatment is applied at 300-900 deg.C for 1-300s. By this method, the heat resistant film having the following layers can be obtained: an Sn or Sn-alloy layer having a thickness X of 0.05-2 &mu m on the outermost surface side; an alloy layer containing an intermetallic compound composed essentially of Cu-Sn and having a thickness Y of 0.05-2 &mu m on the inner side; and further an Ni or Ni-alloy layer having a thickness Z of 0.01-1mu m on the inner side of the above layer ( where 0.2X<=Y<=5X and 0.05Y<=Z<=3Y are satisfied).
Description
The application be No. 01143394.9, Chinese patent application of the same name divide an application the December 21 calendar year 2001 original bill applying date.
[technical field]
The present invention relates to surface treatment and manufacture method thereof with lower terminal.As surface treatment and its manufacture method of the multipole terminals such as automobile electrical gas distribution of lower wearing and tearing when requiring to have hear resistance concurrently, insert or extract, less coefficient of friction.As require to have good plug number of times performance and surface treatment and its manufacture method of the charging electric motor vehicles plug that big electric current passes through are arranged.Require to have the surface treatment and the manufacture method thereof of brush of the motor of mar proof as contacting in rotary body.As require to have surface treatment and its manufacture method of the accumulator terminal of mar proof corrosion resistance.And the connection of printed circuit board (PCB) etc. must be with surface treatment and its manufacture method of the electric electronic element of soldering welding.
[background technology]
In recent years along with the development of electronics industry, electric wiring is towards complicated, and is highly integrated and make progress, the multipolarization of connector also along with and make progress.And because outside heat and self-heating etc. also become stricter to stable on heating requirement.
General Sn electroplates connector when plug, and frictional force can increase, thereby makes connector be difficult for inserting and have problems.And Sn-plated material is because the influence of heat, Cu from material or lower floor's electrodeposited coating can spread, form Cu-Sn based compound layer, and thereby the oxidation film layer of Cu-Sn based compound makes the contact resistance increase cause its stable on heating deterioration, or under the maintaining requirement of high temperature, high humility, because diffusion and oxidative phenomena produce the low problem of scolding tin welding performance.
As reducing the countermeasure that Sn electroplates the insertion force of multipole connector, implement hard Ni in the lower floor of general Sn electrodeposited coating and electroplate, or form the Cu-Sn diffusion layer, improve the hardness of lower floor, scheme such as diffusion trapping layer is set is proposed.
But, on the Ni electrodeposited coating, implement the occasion that Sn electroplates, the Ni-Sn alloy-layer that after heat run, is produced, or the oxidation film layer of Ni-Sn alloy-layer makes the contact resistance increase, the heat resistance reduction.When terminal inserted, Sn was worn and makes Ni expose, and the oxide of heating back Ni significantly worsens contact resistance.Usually to electroplate lower thickness be 1～2 μ m to Ni, but be easy to generate the shortcoming of cracking when having the connector terminal to carry out bending machining.Even Ni electroplates lower thickness and is thinned to 0.5 μ m, above contact resistance increases phenomenon and can not be satisfactorily resolved.
When utilizing the Cu-Sn diffusion layer, under the situation of long-term heating, produce contact resistance and increase the phenomenon that the soldering welding performance is low as the intermediate layer.With regard to manufacture method, utilize remained on surface Sn layer, its inboard is provided with the method for Cu-Sn diffusion layer and carries out thermal diffusion, but the layer thickness control of diffusion layer is difficulty quite, even carry out layer thickness control, and the influence of temperature environment during use, can not stop the carrying out of diffusion, and make heat resistance reduce.The scheme of carrying out the Sn plating after forming the Cu-Sn diffusion layer also is proposed, but this scheme needs suitable complicated step, and its cost price is improved, and the adherence of surperficial Sn electrodeposited coating, and shaping processability is low to be subtracted, and this scheme is very difficult to be realized thereby make.
Present electric automobile must carry out once above charging in one day, guaranteed that charging just seems very important with the abrasion performance of male component.And the electric current that passes through is very big more than 10A, so caloric value is very big, and problems such as peeling off of electrodeposited coating will appear in general methods such as Sn plating.
Printed circuit board (PCB) based on pollution regulations, will have high temperature scolding tin such as the Pb-free solder of use from now on when connecting, and will shift or the tendency of the solvent (scolder) that activity degree is smaller to scolding tin, therefore require to electroplate than general Sn to have better soldering weldability.Particularly, the not moisture that can produce because of when keeping, or hot environment, and make the soldering weldability low, be to keep its good soldering weldability.
At above-mentioned problem, clearly general surface treatment method can not meet the demands.Though Sn or Sn alloy-layer, Cu-Sn alloy-layer, and the film forming and the film build method of Cu layer, Ni layer, Ni alloy-layer all be suggested,, its optimal combination, and optimal bed thickness also all is not studied.
[summary of the invention]
The invention solves above-mentioned problem, and propose following scheme: the most surperficial formation Sn or Sn alloy-layer, its inboard is Cu-Sn alloy-layer (Cu
3Sn, Cu
4Sn, Cu
6Sn
5Deng the Cu-Sn intermetallic compounds layer, or the alloy-layer of the Cu-Sn-Ni that generates because of thermal diffusion of the Ni of lower floor etc. etc.).Or because of the residual Cu layer of reaction, and Ni layer, the Ni alloy-layer of the bed thickness that requires of side formation within it, thereby make its connector, charging electric vehicle with desired good hear resistances such as plug, less coefficient of friction and good mar proof with multi-pole plug for example.And have surface-treated layer and its manufacture method on good soldering weldability surface, and the electric electronic element that utilizes above material manufacturing.
Particularly, the invention provides the following invention.The 1st of the present invention is the heat-resistance protection film, it is characterized in that, by superficial layer is Sn layer or the Sn alloy-layer of bed thickness X 0.05～2 μ m, its la m is the layer based on the intermetallic compound of Cu-Sn of containing of bed thickness Y 0.05～2 μ m, and innermost layer is that Ni or the Ni alloy-layer of bed thickness Z 0.01～1 μ m constitutes; The 2nd is the heat-resistance protection film of the 1st record, wherein 0.2X≤Y≤5X, and 0.05Y≤Z≤3Y; The 3rd is the heat-resistance protection film of the 1st or 2 record, and between above-mentioned intermetallic compounds layer and above-mentioned Ni or the Ni alloy-layer, having thickness is the following Cu layer of 0.7 μ m; The 4th is the heat-resistance protection film of wantonly 1 record in the 1st～3, and above-mentioned material or the material of being protected by the heat-resistance protection film is Cu or Cu alloy in the surface at least; The 5th is the manufacture method of the heat-resistance protection film of wantonly 1 record in the 1st～4, it is characterized in that forming Ni or Ni alloy-layer successively from material surface, behind Cu layer, Sn or the Sn alloy-layer, it is heat-treated; The 6th is the manufacture method of the heat-resistance protection film of wantonly 1 record in the 1st～4, after it is characterized in that forming Ni or Ni alloy-layer, Cu layer, Sn or Sn alloy-layer successively from material surface, it is carried out remelting handle; The 7th is the manufacture method of the heat-resistance protection film of wantonly 1 record in the 1st～4, it is characterized in that 10 average light slipperies in surface flatness are below 1.5 μ m, and its center line average light slippery is on the material surface below the 0.15 μ m, after forming Ni or Ni alloy-layer, Cu layer, Sn or Sn alloy-layer successively from material surface, it is heat-treated; The 8th is the manufacture method of the heat-resistance protection film of wantonly 1 record in the 1st～4, it is characterized in that 10 average light slipperies in surface flatness are below 1.5 μ m, and its center line average light slippery is on the material surface below the 0.15 μ m, after forming Ni or Ni alloy-layer, Cu layer, Sn or Sn alloy-layer successively from material surface, it is carried out remelting handle; The 9th is the manufacture method of the heat-resistance protection film of wantonly 1 record in the 5th～8, it is characterized in that before with above-mentioned Ni or Ni alloy-layer film forming, forms Cu or Cu alloy-layer earlier; The 10th is electric electronic element, it is characterized in that forming at material surface the heat-resistance protection film of wantonly 1 record in the 1st～4.
[description of drawings]
Fig. 1 is the method for testing schematic diagram of coefficient of friction in the embodiment of the invention.
[explanation of symbol]
1. the upper strata test film that has the depression structure
2. lower floor's test film
3. heavily cut or polish jade with an emery wheel
4. horizontal stand
5. pulley
6. load gauge measuring device
[concrete form of implementation]
Carry out specific description with regard to content of the present invention below.The reason of data area that the present invention limits at first is described.
At first, with the Sn bed thickness of superficial layer, the occasion of bed thickness below 0.05 μ m, the stability of contact resistance, the soldering welding performance will reduce.Particularly the contact resistance when underload will easily produce wild effect, and the moisture, the high temperature that produce during because of keeping make it that reduction of soldering weldability take place.And, because of H
2S, SO
2The corrosion of gas is having under the situation of moisture NH
3Gas makes problems such as its corrosion resistance reduction.When the bed thickness of Sn layer surpasses the occasion of 2 μ m, cause when connector inserts and the turn up friction that produces inserts it into the resistance increase, fatigue properties are low, the problem such as unfavorable of economic face.And, if the bed thickness of the Cu-Sn diffusion layer that its inboard forms by heat treatment is blocked up, be easy to generate cracking man-hour adding, make the shaping processability of material low.Therefore, the bed thickness scope of Sn layer is between 0.05～2 μ m.Preferably in 0.1～1 mu m range.
The formation method of Sn layer has plating, melt impregnation, shot-peening processing, coating method etc., takes all factors into consideration from the control of bed thickness and the aspect of production cost, to electroplate to well.Here the Sn bed thickness of indication is meant the bed thickness of the most surperficial Sn layer after DIFFUSION TREATMENT such as heat treatment are over, the skin of Cu-Sn intermetallic compound (face side) part.Because of heat treated influence, can contain the Sn element in addition below 20%.Element amount beyond the Sn surpasses 20%, the soldering weldability will take place, problems such as contact resistance after long-term heating.The most surperficial Sn protective film before the DIFFUSION TREATMENT also can be alloy plating such as Sn-Cu, Sn-Ag, Sn-Bi, Sn-Zn, Sn-Pb and Sn-In melt impregnation etc.Certainly, its inboard must be provided with the Cu-Sn intermetallic compounds layer, makes it carry out DIFFUSION TREATMENT, Cu, Ag, Bi, Zn, Pb, In etc. during long-term the heating among the Sn are diffused into the most surperficial, also do not influence its soldering weldability after the oxidation, and cause that contact resistance hangs down inferior phenomenon, this point is quite important.
The lower floor of Sn layer must be provided with the intermetallic compounds layer of 0.05～2 μ m.This formation that contains the intermetallic compounds layer of Cu-Sn alloy forms preferably through the Sn layer formation alloying of diffusion with the surface with the Cu in the Cu layer (for example Cu electrodeposited coating) that makes lower floor by heat treatment.Therefore, the lower floor of Sn layer comprises the residual Cu layer in reaction back.But the thickness of residual Cu layer should be below 0.7 μ m, preferred should be below 0.3 μ m.Residual Cu layer because of long-term heating produces diffusion, grows up the Cu-Sn diffusion layer, causes the thickness minimizing of the Sn layer of superficial layer, causes contact resistance, the soldering weldability lowly.
Above-mentioned gained Cu-Sn intermetallic compound has suppressed effectively from the next Ni of diffused inside, thereby has suppressed surperficial Ni-Sn alloy-layer, and the formation of oxide.Because above effect, successfully suppressed the increase of the contact resistance after the long-term heating.And, because of the formation of the Cu-Sn series intermetallic compound of hard makes it have the effect that reduces insertion force.In order to embody this effect better, the thickness of Cu-Sn intermetallic compounds layer should be more than 0.05 μ m, preferably more than 0.1 μ m.
But, contain the too thick occasion of layer thickness of Cu-Sn intermetallic compound, can make processability obviously low.Because the increase by the Cu-Sn diffusion layer that forms of diffusion surface roughness, even the most surperficial Sn layer of adjusting also exerts an adverse impact to outward appearance and insertion force easily.Therefore, the thickness of preferred Cu-Sn layer should be below 2 μ m, more preferably below 1 μ m.
And, must form Ni or Ni alloy-layer in the inboard of the layer that contains the Cu-Sn intermetallic compound.This Ni or Ni alloy-layer not only have the diffusion effect of inhibition from the Cu of copper, copper alloy mother metal, have more inhibition from the interpolation elemental diffusion effect in the copper alloy, prevent contact resistance, soldering weldability, the effect that heat-resisting adherence is low.The for example Zn in the brass, the P in the phosphor bronze etc.
And this Ni or Ni alloy-layer have the effect that performances such as the insertion force impedance that makes its outer field Cu-Sn intermetallic compounds layer, hear resistance, corrosion resistance make progress.The formation method of this Ni or Ni alloy-layer is the most common with electro-plating method, and aforesaid Sn formation method is the same, and the whole bag of tricks can be used.And be not limited to the Ni layer, the Ni alloy-layer also can.As Ni-Co, the Ni alloy-layer of electric electro-plating method such as Ni-P also can.Also can be to heat-treat the alloy-layers such as Ni-Cu that form from mother metal or the diffusion of Cu electrodeposited coating that produced when forming the Cu-Sn diffusion layer.
Above technology also can be used in the material beyond copper such as ferrous materials, stainless steel, Al alloy, the copper alloy.In this case, in order to improve the adherence of Ni layer, Ni alloy-layer, can implement Cu lower floor electroplates, existence because of Ni layer, Ni alloy-layer, can suppress diffusion effectively from the Cu of Cu electrodeposited coating, make it have contact resistance under the long-term heating environment of inhibition, the effect of soldering welding performance deterioration.
Generally speaking, consider that material serves as preferred with copper, copper alloy, but also is not limited to this from the property the treated face of necessity such as the electrical conductivity of electric element, elasticity, magnetic.Mother metal is the occasion of copper, copper alloy, must have following structure, and is outside from mother metal, is followed successively by Ni or Ni alloy, (Cu), the alloy that contains the Cu-Sn intermetallic compound, Sn or Sn alloy.Perhaps be followed successively by Cu or Cu alloy, Ni or Ni alloy, (Cu), Cu-Sn intermetallic compound, Sn or Sn alloy.
When mother metal is copper alloy, intensity with regard to material, elasticity, the electrical conductivity degree, processability, faces such as corrosion resistance consider that the scope of desirable interpolation element is Zn:0.01～50wt%, Sn:0.1～12wt%, Fe:0.01～5wt%, Ni:0.01～30wt%, Co:0.01～5wt%, Ti:0.01～5wt%, Mg:0.01～3wt%, Zr:0.01～3wt%, Ca:0.01～1wt%, Si:0.01～5wt%, Mn:0.01～20wt%, Cd:0.01～5wt%, Al:0.01～10wt%, Pb:0.01～5wt%, Bi:0.01～5wt%, Be:0.01～3wt%, Te:0.01～1wt%, Y:0.01～5wt%, La:0.01～5wt%, Cr:0.01～5wt%, Ce:0.01～5wt%, Au:0.01～5wt%, Ag:0.01～5wt%, P:0.005～0.5wt%.Above element is minimum to be contained more than a kind, contains total amount in 0.01～50wt%.
From raw material utilize angle again, it is desirable to contain the copper alloy of Ni, Sn.
Below the thickness of each layer of explanation limits reason.
The thickness (X) of the most surperficial Sn layer or Sn alloy-layer, the thickness (Y) that its inboard Cu-Sn layer is the intermetallic compounds layer of main body, its inboard Ni layer or Ni alloy-layer (Z), the ideal thickness of each layer is narrated in the above.But,, therefore be necessary to limit the thickness ratio of each layer because of each interlayer has interaction.
Particularly, each elemental diffusion that produces for fear of long-term heating, thereby the deterioration of the electric property that oxidation causes, are being coagulated insertion force are increased at the impedance that causes because of turn up when inserting because of connector, problems such as abrasion, corrosion must have the best bed thickness ratio.Desirable bed thickness ratio is because of satisfying with following formula
0.2X≤Y≤5X 1 formula
0.05Y≤Z≤3Y 2 formulas
The bed thickness ratio surpasses the upper limit or is lower than the occasion of lower limit, the contact resistance after the heating, and the soldering welding performance after the humidity test, the insertion force opposing of connector, abrasion loss, corrosion resisting property will be low, and can not satisfy various requirement.Therefore, Ceng thickness must satisfy 1 formula and the 2 formulas particular importance that just seems.
About the surface roughness of mother metal, assay method is according to the regulation of JIS B 0601, and its 10 mean roughness are preferably below 1.5 μ m, and center line average roughness is preferably below 0.15 μ m.By limiting the surface roughness of mother metal, make each laminar surface that forms on the mother metal surface have stable smoothness, and make its adherence, appearance property is improved.Carrying out the occasion of electroplating,, film thickness distribution also there is good effect to heat-resisting adherence.
Regulation, particularly lower floor to the surface roughness of mother metal are Cu layer or Cu alloy-layer, and the middle level is Ni or Ni alloy, the Cu layer, and the surface is Sn or Sn alloy-layer, carries out thereafter making it have stable outward appearance and surface roughness after the heat treatments such as remelting.Surface roughness after the remelting heat treatment, preferably its 10 mean roughness are below 1.0 μ m, and center line average roughness is preferably below 0.1 μ m.
The oxidated layer thickness of mother metal self has suitable importance to the formation of each layer later on.Special relevant with preliminary treatment, with the occasion that electro-plating method comes film forming (layer), influence its adherence, outward appearance, the hole generation during diffusion etc., the oxidated layer thickness of mother metal should be below 20nm, below the preferred 12nm.
Form the hear resistance film (layer) of following structure effectively according to above method, surface thickness is Sn layer or the Sn alloy-layer of 0.05～2 μ m, its inboard is that thickness is that 0.05～2 μ m and the Cu-Sn that satisfies formula 1 are the intermetallic compounds layer or the Cu layer of main body, and side is that thickness is the hear resistance film (layer) of 0.01～1 μ m and Ni layer that satisfies formula 2 or Ni alloy-layer within it.
Below manufacture method is described.
Hereinafter explain the method that obtains the present invention's structure effectively.
At first, prepare to pass through surface roughness, the mother metal that oxidated layer thickness is adjusted will carry out Cu layer film forming earlier in some cases in advance.When being copper, copper alloy as mother metal, the Cu layer of lower floor can omit.Below just preferred film build method galvanoplastic be that example is introduced.
Mother metal or carry out carrying out Ni or Ni alloy plating on the mother metal after Cu electroplates.Certainly, consider its adherence, must carry out sufficient degreasing, washing procedures such as pickling.Carrying out Cu then electroplates.Should illustrate that in order to improve the outward appearance of Cu electrodeposited coating, adherence is preferably carried out pickling between the operation that Ni electroplates and Cu electroplates.
Carry out top layer Sn or Sn alloy plating thereafter.As mentioned above, form from bottom begin for the essential structure this point of Ni layer, Cu layer, Sn layer considerably important.
Secondly, middle diffusion of electroplating Cu layer and the most surperficial Sn layer obtains the Cu-Sn diffusion layer.This processing method it would be desirable with the most surperficial Sn fusion remelting processing and carries out simultaneously.Mode of heating when particularly, suitably adjusting the remelting processing obtains the thickness of desired Sn, Cu-Sn diffusion layer.Should illustrate that the thickness that middle Cu electroplates does not need residual Cu electrodeposited coating down can form the Cu-Sn diffusion layer for suitable after the reaction.Concrete speech, residual Cu layer thickness are preferably below 0.7 μ m, more preferably below 0.3 μ m.Remaining Cu layer can spread after through long-term heating, makes the Cu-Sn diffusion layer grow up, thereby the Sn layer thickness on top layer is reduced, causing the contact resistance performance, the soldering welding performance lowly.
The condition that remelting is handled, temperature: 300～900 ℃, the time: 1～300 second condition is an ideal conditions.Be lower than 300 ℃ or be higher than 900 ℃ as temperature, control remelting and the diffusion difficulty that just seems simultaneously.From obtaining surface of good state, inhibition oxidation aspect, the control of thickness of diffusion layer suppresses the sharp play of diffusion layer subregion and grows up and the Anomalous Diffusion aspect of formation, and temperature is an important key element.According to different remelting modes, atmosphere can appropriate change.Main remelting mode has, and combustion system, hot air circulation mode, infrared mode, Joule heat mode etc. can be selected above any way.But the heat time heating time of variety of way is different, under 1 second the situation of less than, can not obtain sufficient diffusion layer, surpasses under 300 seconds the situation, and effect is in saturation state, and is unfavorable to reducing cost.
And wish that the oxide skin layer thickness after the remelting of Sn layer handled is thin as much as possible, its thickness is wished below 30nm.After the oxidated layer thickness on surface surpassed 30nm, its contact resistance will increase, and extremely unstable, made the electric property deterioration.And the adherence performance of soldering welding performance, oxide layer is low, produces in manufacturing procedure thereafter and peels off phenomenon.Preferred oxidated layer thickness is wished below 20nm.The oxide layer here is based on tin oxide, comprises diffusion in interpolation element, the Cu in the Cu-Sn diffusion layer, the Ni of lower floor layer or the Ni alloy-layer in the Sn layer and diffusion and the composite oxides that contain element and Sn formation that come in the Cu base alloy of the element that comes, mother metal.
The oxide on surface that the surface forms and the Cu-Sn diffusion layer of lower floor, Ni layer or Ni alloy-layer interact and have the abrasion performance of making, the effect that slickness makes progress.But oxide on surface is to contact resistance, and the soldering welding performance has bad influence, therefore wishes its thickness of control, more Bao Yuehao.
More than the protective film of Gou Chenging (layer) is applied to the hero of electrical equipment connector, and female terminal is fit to be applied to hero, either party of female terminal, or two sides.Also can be applied to part necessary in the connector.
Below record and narrate embodiments of the invention.
Embodiment 1
Table 1. has been charged to formation and the thickness of 16 kinds of surface treatment materials that No.1 to No.16 prepares in advance.The formation method of each layer all is galvanoplastic.Particularly, the Ni layer is to bathe with dithiocarbamic acid Ni, and the Cu layer is to bathe with copper sulphate, and the Sn layer is to be used as electroplate liquid with sulfate baths, carrying out Ni electroplating work procedure front and back, carries out pickling.
No.9, No.10, No.15 do not carry out Ni and electroplate, and No.11 does not carry out Ni, Cu and electroplates, and No.12 does not carry out Cu and electroplates, and No.16 does not carry out Sn and electroplates (table 1 is labeled as one).
Mother metal is that amount is the copper alloy plate of 1%Ni, 0.9%Sn, 0.05%P, and thickness of slab is the calendering material of 0.25mm, and surface roughness is, 10 mean roughness 0.9 μ m, center line average roughness 0.08 μ m, the about 7nm of surface oxidation layer thickness of mother metal is little more a lot of than the 20nm thickness that requires.
Change the condition of remelting in the test, carry out temperature range from 450 to 700 degree, the processing time scope is handled from 4 seconds to 20 seconds continuous remelting, when carrying out the remelting processing, forms diffusion layer.The thickness of the surface oxide layer after remelting is handled use AES, and the measurement result of ESCA method is, the thickness of No.1 to No.14 is 3～8nm, No.15,16 the about 15nm of thickness, more than 16 kinds of materials surface oxide layer thickness all below 30nm a lot.Its surface roughness is 10 mean roughness 0.2～0.7 μ m, center line average roughness 0.05～0.10 μ m.
More than the thickness of each layer, from superficial layer, in layer after the dissolving, measure its thickness with electrolysis by thick mensuration meter of radiopaque layer and electrolysis.The bed thickness that thickness is relatively thinner, with 0J electronics light-dividing device (AES), photoelectron light-dividing device (ESCA) etc., the cross section is measured with transmission electron microscope (TEM), observes.And the conformability of separating out electric weight and each layer thickness by calculating further improves the mensuration precision.Represent with ND in table for the layer (Sn＜0.05 μ m, Cu-Sn＜0.05 μ m, Cu＜0.05 μ m) that can not measure its thickness.
Projects such as the coefficient of friction of the above test of mensuration investigation material, shaping processability, soldering welding performance, heat-resisting adherence, contact resistance, variable color.
The Determination of Friction Coefficient method, as shown in Figure 1, surface treatment plate with 3 of inner radius R=1mm depression structures is as upside, place the load of 15N thereon, the speed of dividing with 100mm/ moves on the downside sheet material of handling through similar face, measure frictional force by the load gauge measuring device, calculate coefficient of friction.
90 ° of W bend tests (is standard with JIS H 3110, R=0.2mm, rolling direction is with the perpendicular direction of rolling direction) are carried out in the be shaped evaluation of processing, observe the protrusion surface of test portion central portion with 24 times of stereomicroscopes, estimate.And observe the surface of measuring the depression structure that coefficient of friction uses with 24 times of stereomicroscopes simultaneously, confirm to have or not cracking.What cracking phenomena was not all observed in above binomial trials is zero seal, and what either party observed cracking phenomena is * seal.
The evaluation of soldering welding performance is a standard with MIL-STD-202F-208, and exposure adopted nonactive scolder to carry out test evaluation after 1 hour in the steam of boiling.Result of the test is zero seal with the wetted more than 95% of the test portion of test film, is lower than the 95% * seal of being.
The evaluation of heat-resisting adherence, 160 ℃, after the heating in 1000 hours, (with JIS H 3110 is standard, R=0.2mm, rolling direction to carry out 90 ° of W bend tests, with the perpendicular direction of rolling direction) after, implement disbonded test with adhesive plaster, what do not have peeling off phenomenon after the disbonded test is zero seal, peeling off phenomenon be * print.Carry out visual surface discolouration inspection simultaneously, with the heating before compare, take place obvious metachromatism for * seal.
The test of contact resistance, test material, with low current low-voltage determinator, are carried out 4 utmost point leads method and are measured after the heating in 1000 hours through 160 ℃.When the maximum of Au contact increases the weight of to 0.5N, measure its resistance value.
Above evaluation of measuring result is shown in the table 2.
[table 1]
[table 2]
According to table 1, the evaluation of measuring result of table 2, No.1 of the present invention～No. 8 material, its coefficient of friction is very little, and has good shaping processability, soldering welding performance, the adherence of heating back protective film (layer), contact resistance, discoloration-resistant performance.Therefore above many good characteristics make it widely be used for the multipole connector of using, charging terminal, printed circuit board (PCB) etc. the element that continues.
Compare with above result, do not have the coefficient of friction of the No.9 of Ni floor, No. 10 materials just bigger, and the heating back produces contact resistance, problems such as variable color.The No.11 material does not carry out the operation of the Ni of lower floor layer and middle Cu electrodeposited coating, therefore mother metal Cu and surperficial Sn layer takes place form diffusion layer, though coefficient of friction is very little, the soldering welding performance takes place, heating back contact resistance, problems such as variable color.
Do not carry out centre Cu and electroplate, do not have the No.12 material of Cu-Sn diffusion layer, the soldering welding performance takes place, heating back contact resistance, problems such as variable color.
Protective film thickness of the present invention; the No.13 material that the Ni layer thickness is thicker; its shaping processability is just relatively poor; the No.14 material that the Sn layer thickness is thicker, its coefficient of friction is just relatively poor, does not have the thicker No.15 material of thickness of Ni floor and Cu-Sn diffusion layer; shaping processability takes place; the soldering welding performance takes place, heating back contact resistance, problems such as variable color.The soldering welding performance takes place in the No.13 material that does not have the Sn layer, heating back contact resistance, problems such as variable color.
Having each electric electrodeposited coating identical with embodiment 1 forms.But No.17, the mother metal of 18, No. 21 materials are that brass is a kind of, thickness of slab 0.8mm, and No.19, the mother metal of 20, No. 22 materials is phosphor bronzes, thickness of slab 0.2mm.Above mother metal is that brass material and mother metal are that the surface roughness of phosphor bronze material is that 10 mean roughness are respectively 1.0,0.9 μ m, center line average roughness is respectively 0.13,0.08 μ m, the surface oxidation layer thickness of mother metal all is about 8nm, and is thin more many than the 20nm that requires.
Second carries out 350～800 ℃, and 5～20 seconds continuous remelting is handled, and when carrying out the remelting processing, forms the Cu-Sn diffusion layer, is ready to above material as stated above.With the coefficient of friction of test material more than the method researching determining identical, processing and forming, soldering welding performance, heat-resisting adherence, contact resistance, characteristics such as variable color with embodiment 1..
[table 3]
[table 4]
Table 3, table 4 show that very significantly the coefficient of friction of No.17 of the present invention～No. 20 material is very little, and, have good processing and forming, soldering welding performance, heat-resisting adherence, contact resistance, characteristics such as anti-variable color.According to above result of the test, no matter mother metal is brass or phosphor bronze, and the present invention has identical effect.
The No.21 that does not have the Ni layer, the coefficient of friction of No. 22 materials is just bigger, and the heating back produces contact resistance, problems such as variable color.No.22 material particularly, the adherence of heating back protective film is deterioration significantly, and with NO.19, No. 20 material compared just can find that effect of the present invention is considerably big.
On embodiment 1 identical materials, carry out the identical plating of embodiment 1, form various electrodeposited coatings.The surface electrical coating of No.23,24, No. 27 materials changes to the Sn alloy-layer.Lower floor's electrodeposited coating of No.23, No. 27 materials changes to the Ni floor.Lower floor's electrodeposited coating of No.24 material changes to the Ni alloy-layer.The surface electrical coating of No.25,26, No. 28 materials is the Sn floor, and lower floor's electrodeposited coating changes to the Ni alloy-layer.
The Sn alloy plated layer uses organic complex salt solution, carries out Sn-10%Zn and electroplates.The Ni alloy plated layer uses the watt that adds phosphorous acid to bathe, and carries out Ni-5%P and electroplates.
Select the remelting condition identical with embodiment 1. to carry out remelting and handle, Zn can be diffused into the surface in the Sn-Zn alloy plating process, and formation is the oxide at center with oxidation Zn, but does not influence the variation of contact resistance.And thickness of oxide layer is approximately 5～11nm, and is more a lot of than the 30nm thin thickness of regulation.
No.23～No. 26 material generates the Cu-Sn diffusion layer because of the heat affecting of remelting, and No.27, No. 28 materials do not generate the Ni-Sn diffusion layer because of there not being the Cu floor so do not generate the Cu-Sn diffusion layer.
[table 5]
[table 6]
At table 5, shown in the table 6 that No.23 of the present invention～No. 26 material has good very little coefficient of friction, and had characteristics such as good shaping processability, soldering welding performance, the protective film adherence after the heat run, contact resistance, anti-variable color.Therefore, the Sn layer on surface changes to the Sn alloy-layer, and the Ni layer changes to the Ni alloy-layer, can not change effect of the present invention for the present invention.
Above relatively result; having or not of interlayer Cu-Sn but has very big influence; the soldering welding performance that does not have the No.27 material in Cu-Sn intermediate layer; the contact resistance performance can be low; the soldering welding performance that does not have the No.28 material in Cu-Sn intermediate layer; protective film adherence after the heat run, the contact resistance performance can be low.Therefore, can illustrate that effect of the present invention is very big.
[effect of invention]
Above embodiment has shown clearly, uses surface treatment of the present invention and manufacturing side thereof Method is so that the electric electronic element that uses the present invention to process has good friction opposing, moulding Processing, the characteristics such as Welding, and after for a long time overheated, have good adherence, the contact electricity Resistance, the characteristics such as anti-variable color, the usefulness such as Hyundai Motor Denso product that can apply to densification connect Device also can apply to require to have abrasion performance, and the printed circuit board (PCB) of Welding performance connects Continue and use connector, so that use material of the present invention to become good electric electronic element material.
Claims (12)
1. heat-resistance protection film; it is characterized in that; by superficial layer is Sn or the Sn alloy-layer of bed thickness X 0.05～2 μ m; its la m is the alloy-layer based on the intermetallic compound of Cu-Sn of containing of bed thickness Y 0.05～2 μ m; innermost layer is that Ni or the Ni alloy-layer of bed thickness Z 0.01～1 μ m forms; 10 average light slipperies of its surface flatness are at 0.2～0.7 μ m, and its center line average light slippery is at 0.05～0.10 μ m.
2. the heat-resistance protection film of claim 1 is characterized in that, described film has passed through the remelting processing.
3. the heat-resistance protection film of claim 2 record, wherein remelting is handled and was carried out 1～300 second under 300～900 ℃ of temperature.
4. the heat-resistance protection film of each record of claim 1～3, wherein 0.2X≤Y≤5X, and 0.05Y≤Z≤3Y.
5. the heat-resistance protection film of each record of claim 1～3, between the alloy-layer of compound and above-mentioned Ni or the N i alloy-layer, having thickness is the following Cu layer of 0.7 μ m between above-mentioned containing metal.
6. the heat-resistance protection film of each record of claim 1～3 is Cu or Cu alloy by the superficial layer at least of the material of above-mentioned heat-resistance protection film protection.
7. the heat-resistance protection film of each record of claim 1～3, the oxide skin layer thickness of above-mentioned Sn or Sn alloy-layer is below 30nm.
8. the manufacture method of the described heat-resistance protection film of claim 1; it is characterized in that forming Ni or Ni alloy-layer successively from material surface; the Cu layer; behind Sn or the Sn alloy-layer; its remelting of carrying out under 300～900 ℃ of temperature 1～300 second is handled, at the most surperficial above-mentioned Sn or the inboard alloy-layer that contains based on the intermetallic compound of Cu-Sn that forms of Sn alloy-layer.
9. the manufacture method of the described heat-resistance protection film of claim 8 is characterized in that it is to carry out 4～20 seconds that remelting is handled under 450～700 ℃ of temperature.
10. the manufacture method of heat-resistance protection films of claim 8 or 9 records it is characterized in that 10 average light slipperies at described material surface smoothness below 1.5 μ m, and its center line average light slippery is below 0.15 μ m.
11. the manufacture method of heat-resistance protection films of claim 8 or 9 records is characterized in that before with above-mentioned Ni or Ni alloy-layer film forming, formation Cu or Cu alloy-layer earlier on the above-mentioned material surface.
12. electric electronic element is characterized in that the heat-resistance protection film in each record of material surface formation claim 1～7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP024031/2001 | 2001-01-31 | ||
| JP2001024031A JP2002226982A (en) | 2001-01-31 | 2001-01-31 | Heat resistant film, its manufacturing method, and electrical and electronic parts |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB011433949A Division CN1325696C (en) | 2001-01-31 | 2001-12-21 | Heat-resistance protection film, its manufacture method and electric electronic element |
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| CN1940137A CN1940137A (en) | 2007-04-04 |
| CN100528550C true CN100528550C (en) | 2009-08-19 |
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| CNB2006101149269A Expired - Lifetime CN100528550C (en) | 2001-01-31 | 2001-12-21 | Heat resistant film, its manufacturing method, and electrical and electronic parts |
| CNB011433949A Expired - Lifetime CN1325696C (en) | 2001-01-31 | 2001-12-21 | Heat-resistance protection film, its manufacture method and electric electronic element |
| CN 200710108823 Pending CN101081554A (en) | 2001-01-31 | 2001-12-21 | Heat resistant film, its manufacturing method, and electrical and electronic parts |
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| CNB011433949A Expired - Lifetime CN1325696C (en) | 2001-01-31 | 2001-12-21 | Heat-resistance protection film, its manufacture method and electric electronic element |
| CN 200710108823 Pending CN101081554A (en) | 2001-01-31 | 2001-12-21 | Heat resistant film, its manufacturing method, and electrical and electronic parts |
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| JP (1) | JP2002226982A (en) |
| CN (3) | CN100528550C (en) |
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| JP2002226982A (en) * | 2001-01-31 | 2002-08-14 | Dowa Mining Co Ltd | Heat resistant film, its manufacturing method, and electrical and electronic parts |
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| JP4461268B2 (en) * | 2004-03-30 | 2010-05-12 | Ｄｏｗａメタルテック株式会社 | Semiconductor device component, manufacturing method thereof, and semiconductor device using the same |
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| JP5185759B2 (en) * | 2008-10-03 | 2013-04-17 | Ｄｏｗａメタルテック株式会社 | Conductive material and manufacturing method thereof |
| JP5464869B2 (en) * | 2009-03-02 | 2014-04-09 | Ｄｏｗａメタルテック株式会社 | Sn-coated copper or copper alloy and method for producing the same |
| JP5464876B2 (en) * | 2009-03-17 | 2014-04-09 | Ｄｏｗａメタルテック株式会社 | Sn-coated copper or copper alloy and method for producing the same |
| JP5479789B2 (en) * | 2009-07-03 | 2014-04-23 | 古河電気工業株式会社 | Metal materials for connectors |
| DE102011006899A1 (en) | 2011-04-06 | 2012-10-11 | Tyco Electronics Amp Gmbh | Process for the production of contact elements by mechanical application of material layer with high resolution and contact element |
| JP5956240B2 (en) * | 2012-05-01 | 2016-07-27 | Ｄｏｗａメタルテック株式会社 | Plating material and method for producing the same |
| CN103834946B (en) * | 2012-11-26 | 2016-03-30 | 华为技术有限公司 | The preparation technology of coating, signal equipment and coating |
| CN103335942B (en) * | 2013-07-08 | 2015-06-10 | 大连理工大学 | Equipment and method used for measuring friction coefficient between plastic and metal mold |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1940137A (en) | 2007-04-04 |
| CN1368562A (en) | 2002-09-11 |
| JP2002226982A (en) | 2002-08-14 |
| CN101081554A (en) | 2007-12-05 |
| CN1325696C (en) | 2007-07-11 |
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