CN108602121A - The preparation method of the welding slurry of solder powder and its manufacturing method and the use powder - Google Patents
The preparation method of the welding slurry of solder powder and its manufacturing method and the use powder Download PDFInfo
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- CN108602121A CN108602121A CN201680080194.8A CN201680080194A CN108602121A CN 108602121 A CN108602121 A CN 108602121A CN 201680080194 A CN201680080194 A CN 201680080194A CN 108602121 A CN108602121 A CN 108602121A
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- powder
- nickel
- tin
- copper
- solder powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
Abstract
The metal salt that mixed Ni is added into the dispersion liquid of copper powders, obtains dissolved with the metal salt and is dispersed with the 1st lysate of copper powders.After carrying out pH adjustment to the lysate, addition the 1st reducing agent of mixing makes nickel ion restore, obtains the nickel coated copper powders of precipitation and the dispersion liquid of dispersion.The liquid is separated by solid-liquid separation, and drying solid ingredient, to obtain metal powder made of the barrier layer coated copper core being made of nickel.Into the dispersion liquid of metal powder, the metal salt of addition mixing tin, obtains dissolved with the metal salt and is dispersed with the 2nd lysate of metal powder.After carrying out pH adjustment to the lysate, addition the 2nd reducing agent of mixing makes tin ion restore, and obtains the tin cladding metal powder of precipitation and the dispersion liquid of dispersion.The liquid is separated by solid-liquid separation, and drying solid ingredient, to obtain the solder powder that metal powder is coated by tin layers.
Description
Technical field
The present invention relates to a kind of for the weldering installing electronic building brick etc., centronucleus is made of copper and clad includes tin layers
The preparation method of feed powder end and its manufacturing method and the welding slurry using the powder.In addition, this international application advocates base
The priority of Japanese patent application the 244270th (patent application 2015-244270) filed in 15 days December in 2015, will
All the elements of patent application 2015-244270 are applied in this international application.
Background technology
In the past, it has been disclosed that have the average grain diameter that a kind of centronucleus is made of copper and clad is made of tin below for 5 μm
Solder powder (for example, referenced patent document 1).The solder powder in terms of the environmental protection for be unleaded and fine, therefore printing
It is excellent.Also, by the way that the metallic element for constituting centronucleus is set as copper, in reflow, not only clad melts, centronucleus
It melts and forms Cu-Sn alloys, therefore the mechanical strength of solder is improved because being formed by Cu-Sn alloys.
However, being made of copper for centronucleus recorded in patent document 1 and solder powder that clad is made of tin
For, if being taken care of for a long time after manufacturing solder powder, since copper is more than diffusion system of the tin to copper to the diffusion coefficient of tin
Number forms Cu it is therefore possible to cause the copper of centronucleus to be spread to the tin of clad between centronucleus and clad3Sn、
Cu6Sn5All copper of the high intermetallic compounds layer or centronucleus of equal fusing points are spread into the tin of clad and clad is whole
Be formed as the intermetallic compound of copper and tin.
To solve the point, a kind of Cu caryospheres (for example, referenced patent document 2) are disclosed, which has by Cu ball structures
At stratum nucleare and coat the stratum nucleare using tin as the welding layer of principal component, and be formed between Cu balls and welding layer and be made of Ni
Barrier layer.The barrier layer prevents the Cu for constituting Cu balls from being spread to welding layer.In the patent document 2, as on Cu balls
The method for forming welding layer shows the electrolytic plating methods such as known barrel plating, is made in electroplating bath by being connected to the pump of electroplating bath
Electroplate liquid generate high velocity turbulent flow, to using electroplate liquid turbulent flow is formed on Cu balls be electroplated overlay film method and pass through
Oscillating plate is set in electroplating bath and it is made to be vibrated with defined frequency, so that electroplate liquid high velocity turbulent flow is stirred, and utilize plating
The turbulent flow of liquid forms the method etc. of plating overlay film on Cu balls, discloses and is formed in welding layer after coating Ni coating to Cu balls
Hold.
Also, the Sn that welding layer contains 40% or more is recorded in patent document 2, and contains 20ppm or more and 220ppm
Ge below forms the Sn- of 18 μm of film thickness (unilateral side) after the Ni coating of 100 μm of 2 μm of Cu balls cladding film thickness (unilateral side) of diameter
Ag-Cu-Ge welding plating overlay films, show the Cu caryospheres that diameter is about 140 μm.
Patent document 1：Japanese Unexamined Patent Publication 2008-138266 bulletins (claim 1, specification [0005] section,
[0014] section)
Patent document 2：No. 5652560 bulletins of Japanese Patent No. (claim 1, specification [0033] section, [0035]
Section, [0067] section, [0068] section)
However, as recorded in Patent Document 2 like that, the non-proliferation being made of Ni is being utilized by the nickel plating of tumble-plating process etc.
In the method for layer cladding Cu balls, has and be easy to form the ball of cohesion because ball is adhering to each other, and the film thickness that overlay film is electroplated is easy production
The unfavorable condition of raw deviation.Also, when the radius of Cu balls (copper core) is set as 1, Cu caryospheres by Ni shown in patent document 2
The thickness of the barrier layer of composition be 0.02 ratio, therefore it is in distress to prevent Cu from being spread to tin the problem of.
Invention content
The present invention the 1st is designed to provide a kind of method manufacturing solder powder and the welding slurry using the powder,
Solder powder copper of centronucleus in keeping powder will not be spread to the tin of tin layers, and powder does not adhere to each other, and is made of nickel
Barrier layer thickness deviation it is small.Even if also, the 2nd of the present invention is designed to provide one kind before keeping or during keeping
Reflow is carried out to the solder powder taken care of for a long time at a temperature of short solder powder melting, will not be generated because solder is not fully molten
Melt the preparation method of the caused undesirable solder powder of engagement and its manufacturing method and the welding slurry using the powder.
Moreover, the 3rd of the present invention the be designed to provide a kind of reflow after be not susceptible to remelted and bond strength reduction, be especially suitable for
Installation is exposed the solder powder of electronic building brick etc. and its manufacturing method in a high temperauture environment and is used using the welding of the powder
The preparation method of slurry.
As shown in Figure 1, the 1st viewpoint of the present invention is a kind of manufacturing method of solder powder comprising：Preparation is dispersed with copper
The process S1 of 1st dispersion liquid of powder；The metal salt addition of nickel is mixed in the 1st dispersion liquid of copper powders and prepares and is dissolved with
The metal salt of nickel and be dispersed with copper powders the 1st lysate process S2；Adjust the process S3 of the pH of the 1st lysate；Pass through to
The 1st reducing agent of addition mixing in the 1st lysate of pH is had adjusted, so that nickel ion is restored, to prepare the nickel coated copper powder of precipitation
The process S4 of 2nd dispersion liquid of end and dispersion；2nd dispersion liquid is separated by solid-liquid separation, and the solid constituent of drying solid-liquid separation,
To make the process S5 of metal powder made of the barrier layer coated copper core being made of nickel；Preparation is dispersed with the metal powder
The 3rd dispersion liquid process S6；The metal salt addition of tin is mixed in the 3rd dispersion liquid of metal powder and prepares and is dissolved with tin
Metal salt and be dispersed with metal powder the 2nd lysate process S7；Adjust the process S8 of the pH of the 2nd lysate；Pass through to
This has adjusted the 2nd reducing agent of addition mixing in the 2nd lysate of pH, and tin ion is made to restore, and the tin to prepare precipitation coats gold
Belong to the process S9 of powder and the 4th dispersion liquid of dispersion；And the 4th dispersion liquid is separated by solid-liquid separation, and drying solid-liquid separation consolidate
Body ingredient, to make the process S10 for the solder powder that metal powder is coated by tin layers.
As shown in Fig. 2, the 2nd viewpoint of the present invention is gold made of a kind of 12 coated copper core 11 of barrier layer being made of nickel
Belong to the solder powder 10 that powder 13 is coated by tin layers 14.It has the structure of feature and is, the average grain diameter of the solder powder is 1
μm or more and 30 μm hereinafter, 100 mass % of total amount relative to the solder powder, the content ratio of copper is 2 mass % or more
And 70 mass % hereinafter, when the radius of the copper core is set as 1, the thickness of the barrier layer being made of nickel is 0.04 or more
And 0.51 ratio below.
The 3rd viewpoint of the present invention is a kind of manufacturing method of welding slurry, by will be according to the method institute of the 1st viewpoint
The solder powder of the solder powder or the 2nd viewpoint that are fabricated mixes and is gelatinized to prepare welding with welding soldering flux
Use slurry.
The 4th viewpoint of the present invention is a kind of installation method of electronic building brick, manufactured by the method according to the 3rd viewpoint
Made of welding electronic building brick is installed with slurry.
The manufacturing method of the solder powder of the 1st viewpoint about the present invention, passes through the 1st lysate for making to be dispersed with copper powders
In nickel ion reduction, the barrier layer being made of nickel is formed in the surface of copper core, and tin layers are formed in and are made of nickel
Barrier layer coated copper core made of metal powder surface, thus manufacture solder powder.As a result, with patent document 2
The methods of recorded tumble-plating process difference, about the layer structure of solder powder, the deviation of each powder is small, and powder does not glue each other
It is attached, and the thickness deviation for the barrier layer being made of nickel is also small.
As shown in Fig. 2, in the solder powder 10 of the 2nd viewpoint of the present invention, the 12 coated copper core of barrier layer that is made of nickel
Metal powder 13 made of 11 is coated by tin layers 14, when the radius of copper core is set as 1, by the thickness for the barrier layer 12 that nickel is constituted
For 0.04 or more and 0.51 ratio below.That is, in the solder powder 10 of the present invention, due between copper core 11 and tin layers 14
It is clamped with the barrier layer 12 of specific thickness being made of nickel, therefore will not substantially be changed previous by copper core and coated copper core
The welding characteristic for the solder powder that tin layers are constituted can not only prevent the copper of centronucleus from being spread to the tin of tin layers, additionally it is possible to prevent
The tin of tin layers is spread to the copper of centronucleus.As a result, playing following excellent effect：Even if short before keeping or during keeping
Solder powder melting at a temperature of to for a long time take care of solder powder carry out reflow, will not generate because solder does not melt fully
Caused engagement is bad.Also, after reflow, formed by Cu3Sn、Cu6Sn5、Ni3Sn、Ni3Sn2、Ni3Sn4、NiSn3、
(Ni,Cu)3Sn4、(Ni,Cu)6Sn5Therefore the bonding layer that equal fusing points high intermetallic compound and copper are constituted after reflow, is not easy
Remelted and bond strength reduction occurs, is especially suitable for installation exposure electronic building brick etc. in a high temperauture environment.
The solder powder of aforementioned present invention can be used with slurry for welding prepared by the method for the 3rd viewpoint through the invention
And it obtains.Therefore, which is melted rapidly with slurry in reflow, and meltbility is excellent.
In the method for the installation electronic building brick of the 4th viewpoint of the present invention, starched due to the use of the welding of aforementioned present invention
Material, therefore pass through the rapid of welding slurry when reflow and melt and excellent meltbility, it can easily install with high precision
Electronic building brick.About the conjugant for being equipped with the electronic building brick, in reflow not only clad melt, centronucleus also melt and
Cu-Sn alloys or Sn-Ni-Cu alloys are formed, therefore, by the Cu-Sn alloys or Sn-Ni-Cu alloys of formation, even if in solder
Conjugant exposure under high temperature environment, is not easy to cause remelted and bond strength reduction after engagement.
Description of the drawings
Fig. 1 is the figure of the manufacturing process for the solder powder for indicating present embodiment.
Fig. 2 is that metal powder made of the barrier layer coated copper core of present embodiment being made of nickel is coated by tin layers
The sectional structure chart of solder powder.
Specific implementation mode
Illustrate mode for carrying out the present invention below according to attached drawing.
(manufacturing method of solder powder)
Copper powders are used to form centronucleus.First, as shown in the step S1 and S2 of Fig. 1, by by copper powders and point
Powder addition is mixed in solvent and prepares the 1st dispersion liquid for being dispersed with copper powders, and by being added to first dispersion liquid
It mixes nickel compound containing and prepares and be dispersed with copper powders point and the 1st lysate dissolved with nickel compound containing.The copper powders are preferred
With 0.1 μm or more and 27 μm of average grain diameters below.If the average grain diameter of the copper powders is less than the lower limiting value, solder powder
Average grain diameter is easy to be less than 1 μm, and specific surface area is got higher, and the meltbility of solder reduces due to the influence of the surface oxide layer of powder.
If also, the average grain diameter of the copper powders is more than upper limit value, and the average grain diameter of solder powder is well over 30 μm.If solder powder
The average grain diameter at end is more than 30 μm, then when forming convex block the coplanarity reduction of generation convex block unfavorable condition, also, with weldering
Expect to generate crawling when coated pattern surface, it can not the equably entire unfavorable condition of coated pattern to generate.Copper powders
Average grain diameter be more preferably 2~20 μm.The copper powders are obtained in addition to that can utilize the chemical method based on reduction reaction
In addition, it can also be obtained by the physical method as atomization.In addition, in the present specification, the average grain diameter of powder is
(hole field makes institute (HORIBA, Ltd.) and manufactures the particle size distribution device for referring to by using laser diffraction scattering method, and laser spreads out
Penetrate/scatter formula particle size distribution analyzer LA-950) the volume-cumulative meso-position radius (Median diameters, the D that are measured50)。
The ratio of copper powders and nickel compound in 1st lysate is adjusted to, after manufacturing solder powder, each metallic element
Content ratio become aftermentioned range.As nickel compound, nickel chloride (II), nickel sulfate (II), nickel nitrate (II) can be enumerated
Deng.As solvent, water, alcohol, ether, ketone, ester etc. can be enumerated.Also, as dispersant, cellulose-based, ethylene base system, more can be enumerated
First alcohol etc. can use gelatin, casein etc. in addition to this.
As shown in the step S3 of Fig. 1, the pH adjustment of the 1st prepared lysate is carried out.Consider the solder powder generated
Be redissolved etc., range of the preferred adjustment of pH 0.1~2.0.In addition, can also add above-mentioned nickel compound to solvent and make it dissolve
Afterwards, after addition complexing agent carries out complexing processing to nickel, then dispersant is added.By adding complexing agent, even if pH is in alkali side, nickel
Ion will not precipitate, and can carry out the synthesis of wide scope.As complexing agent, succinic acid, tartaric acid, glycolic, breast can be enumerated
Acid, phthalic acid, malic acid, citric acid, oxalic acid, ethylenediamine tetra-acetic acid, iminodiacetic acid, nitrilotriacetic acid or its salt
Deng.
Then, the aqueous solution dissolved with reducing agent is prepared, the pH of the aqueous solution is adjusted to journey identical with the 1st lysate
Degree.As reducing agent, can enumerate the boron hydrides such as the phosphoric acid such as phosphinic acids sodium based compound, Sodium Borohydride, dimethyamine borane,
Metal ions such as the nitrogen compounds such as hydrazine, trivalent titanium ion or bivalent chromium ion etc..
Then, water-soluble by adding reducing agent into the 1st lysate of above-mentioned nickeliferous ion as shown in the step S4 of Fig. 1
Liquid is simultaneously mixed, and the nickel ion in the 1st lysate is reduced, and the to prepare the nickel coated copper powders of precipitation and disperse the 2nd
Dispersion liquid.As the method for the 1st lysate and reducing agent aqueous solution of mixing, can enumerate in the lysate into container with defined
Reducing agent aqueous solution, and the method being stirred using blender etc. is added dropwise in adding speed；Or it uses with specified diameter
Reaction tube, the method etc. that biliquid is injected with defined flow into the reaction tube and them is made to mix.
Then, as shown in the step S5 of Fig. 1, the 2nd dispersion liquid is separated by solid-liquid separation by decantation etc., using water or is incited somebody to action
PH is adjusted to 0.5~2 aqueous hydrochloric acid solution, aqueous solution of nitric acid, aqueous sulfuric acid or methanol, ethyl alcohol, acetone etc. to clean back
The solid constituent of receipts.After cleaning, it is separated by solid-liquid separation again and recycles solid constituent.It is preferred that repeat 2~5 times from cleaning to
The process of separation of solid and liquid.It is dried in vacuo, makes by centronucleus (copper core) and is coated in this by the solid constituent to recycling
What the nickel layer (barrier layer being made of nickel) of heart core was constituted carries Cu cores and Ni layers of metal powder, and the centronucleus is by copper structure
At.
Then, as shown in the step S6 and S7 of Fig. 1, by the way that above-mentioned metal powder and dispersant addition are mixed in solvent
And prepare and be dispersed with the 3rd dispersion liquid with Cu cores and Ni layers of metal powder, and it is mixed by being added to the third dispersion liquid
It closes sn-containing compound and prepares the 2nd dissolving being dispersed with Cu cores and Ni layers of metal powder and dissolved with sn-containing compound
Liquid.As tin compound, stannic chloride (II), STANNOUS SULPHATE CRYSTALLINE (II), tin acetate (II), tin oxalate (II) etc. can be enumerated.Stanniferous chemical combination
The adding proportion of object is adjusted to, and after manufacturing solder powder, the content ratio of each metallic element becomes aftermentioned range.About point
Dispersion media and solvent use decentralized medium and solvent same as described above.
As shown in the step S8 of Fig. 1, the pH of the 2nd prepared lysate is adjusted.Consider the solder powder generated
Redissolution etc., range of the preferred adjustment of pH 0.1~2.0.In addition, can also add above-mentioned tin compound into solvent and make it
After dissolving, after addition complexing agent carries out complexing processing to tin, then dispersant is added.By adding complexing agent, even if pH is in alkali
Side, tin ion will not precipitate, and can carry out the synthesis of wide scope.As complexing agent, using identical with above-mentioned complexing agent
Complexing agent.
Then, as shown in the step S9 of Fig. 1, by using method same as the above-mentioned method to above-mentioned stanniferous ion
Mixed dissolution is added in 2nd lysate the reducing agent aqueous solution of reducing agent identical with above-mentioned reducing agent, makes the 2nd lysate
In tin ion reduction, to prepare 4th dispersion liquid of the tin cladding with Cu cores and Ni layer of metal powder and dispersion of precipitation.
Finally, it as shown in the step S10 of Fig. 1, cleans the 4th dispersion liquid using method same as the above-mentioned method and goes forward side by side
Row is separated by solid-liquid separation, and recycles solid constituent.It is preferred that repeating 2~5 processes from cleaning to separation of solid and liquid.By to recycling
Solid constituent is dried in vacuo, to make the solder powder coated by tin layers with Cu cores and Ni layers of metal powder.
(solder powder)
As shown in Fig. 2, about the solder powder 10 used made by the above method, the barrier layer 12 being made of nickel coats
Metal powder 13 is coated by tin layers 14 made of the copper core 11 of centronucleus.It is made of copper since the solder powder is formed as this
The structure that centronucleus is coated by the clad of low-melting tin layers, therefore meltbility when reflow is excellent.Also, constituting powder
A metallic in, including copper and tin, therefore be not susceptible to that melting when reflow is uneven and composition deviation, can get high
Bond strength.Moreover, solder powder has the barrier layer being made of nickel between centronucleus and clad, therefore can prevent
Diffusion and diffusion from tin to copper of the copper to tin.Moreover, because after reflow, formed by Cu3Sn、Cu6Sn5、Ni3Sn、Ni3Sn2、
Ni3Sn4、NiSn3、(Ni,Cu)3Sn4、(Ni,Cu)6Sn5The bonding layer that equal fusing points high intermetallic compound and copper are constituted, because
This, after reflow, is not susceptible to remelted and bond strength reduction, especially suitable to install the electronic building brick for being exposed to hot environment
Deng.
When the radius of copper core is set as 1, the thickness for the barrier layer 12 being made of nickel is 0.04 or more and 0.51 below
Ratio.Preferably 0.05 or more and 0.20 ratio below.If the thickness of the barrier layer 12 is less than 0.04, copper can not be prevented
Or the diffusion of tin, if the thickness of the barrier layer 12 is more than 0.51, the meltbility of solder powder reduces.
It is 1 μm or more and 30 μm or less to use the average grain diameter of the solder powder 10 made by the above method as a result,.It will weldering
The average grain diameter at feed powder end is defined in 1 μm or more and 30 μm hereinafter, being based on above-mentioned reason.
Also, using in the solder powder 10 made by the above method, relative to the 100 mass % of total amount of powder, copper
Content ratio is 2 mass % or more and 70 mass % or less.Since previous solder powder is used as Sn-Pb systems eutectic solder
(ratio of components Sn:Pb=63:37 mass %) substitute, therefore, and require eutectic composition the reasons why close from fusing point, considers, with
The ratio of 0.5~1.5 mass % contains copper.On the other hand, it states in use in the solder powder made by method, in contrast to this
Containing the copper higher than 2 mass %, thus after reflow, the Sn- with 880~600 DEG C or so of high solidification start temperature is formed
Cu alloys or the Sn-Ni-Cu alloys that start temperature is solidified with 800~400 DEG C or so of height.In addition, even if copper containing than
Example is few, after reflow, also forms solidification start temperature Sn-Cu alloys more higher than tin or Sn-Ni-Cu alloys, but by making it
It solidifies start temperature containing more copper and further increases, this is because changing between there is dystectic metal in alloy process
The ratio for closing object further increases.It is convex that solder is formed by by the reflow of the slurry of the welding comprising the solder powder as a result,
In block, heat resistance greatly improves, and can prevent remelted and bond strength reduction.Therefore, more particularly to being suitable as being used for
Installation is exposed to the high-temperature solder of electronic building brick of hot environment etc..If the content ratio of copper is less than 2 mass %, due to solidification
Start temperature is lower, therefore is formed by after reflow in solder projection and can not obtain sufficient heat resistance, makes under high temperature environment
Used time generation is remelted, is not used as high-temperature solder.On the other hand, if the content ratio of copper is more than 70 mass %, solidification is opened
Beginning temperature is excessively high, the insufficient melting of solder, therefore generates and occur to engage undesirable unfavorable condition.Wherein, total amount of the copper in powder
Shared content ratio is preferably set to 10~60 mass % in 100 mass %.
Also, relative to 100 mass % of the total amount of solder powder, the content ratio of the nickel in solder powder is 1 mass %
Less than 15 mass %, preferably 2~10 mass %.According to the content ratio, the aforementioned non-proliferation being made of nickel is determined
The thickness of layer.If the content ratio of nickel is less than 1 mass %, it is difficult to prevent the diffusion of copper or tin, if the content ratio of nickel is more than
15 mass % then generate the unfavorable condition that the meltbility of solder powder reduces.
Moreover, the 100 mass % of total amount of solder powder, the above-mentioned copper in content ratio, that is, powder of the tin in solder powder
And the remainder other than nickel be 29 mass % less than 97 mass %, preferably 40~90 mass %.If this is because
The content ratio of tin is less than 29 mass %, then does not show the required low melting point of solder powder in reflow.Also, if tin contains
Proportional is 97 mass % or more, then the content ratio of its result copper is reduced, and the heat resistance of solder projection is formed by after reflow
It reduces.That is, if the solder exposure after installation is under high temperature environment, the solder progress after installation is remelted, or the one of solder
Liquid phase is generated in part, it is possible to the bond strength of solder and substrate etc. be caused to reduce.
(welding slurry and preparation method thereof)
It can be suitable as using the solder powder made by the above method by mixing and being pasted with welding soldering flux
Change to obtain the material of welding slurry.The preparation of welding slurry be by by solder powder with welding soldering flux to provide
Ratio mix and be gelatinized to carry out.Welding welding soldering flux used in the preparation of slurry is not particularly limited,
The scaling powder prepared by mixing each ingredient of solvent, rosin, thixotropic agent and activating agent etc. can be used.
As the suitable solvent for preparing above-mentioned welding soldering flux, diethylene glycol monohexyl ether, diethylene glycol mono butyl can be enumerated
The boiling points such as ether, butyl carbitol acetate, tetraethylene glycol, 2- ethyl -1,3- hexylene glycols, α-terpineol are 180 DEG C or more
Organic solvent.Also, as rosin, gum rosin, hydrogenated rosin, newtrex, ester rosin etc. can be enumerated.
Also, as thixotropic agent, hardened castor oil, fatty acid amide, natural oil, Synthetic Oil, N can be enumerated, N '-is sub-
Double -12- the hydroxystearics of ethyl, 12- hydroxy stearic acids, 1,2,3,4- dibenzylidene-D- D-sorbites and its derivative etc..
Also, as activating agent, preferably halogen acids amine salt, it can specifically enumerate triethanolamine, diphenylguanidine, ethyl alcohol
Amine, butylamine, aminopropanol, polyoxyethylene oil base amine, polyoxyethylene laural base amine, polyoxyethylene stearyl amide, diethylamine, three second
Amine, methoxy propanamine, dimethylamino propylamine, dibutyl amino propyl amine, ethylhexylamine, ethoxy propylamine, ethyl hexyl oxy
Propylamine, isopropylamine, diisopropylamine, sends pyridine, 2,6- dimethyl to send pyridine, aniline, methylamine, ethamine, butylamine, 3- amino -1- at di-n-propylamine
The hydrogen chlorate of the amine such as propylene, isopropylamine, dimethylhexylamine, cyclohexylamine or hydrobromate.
Welding soldering flux can by by above-mentioned each ingredient with defined ratio mixes by obtain.Solvent is in scaling powder total amount
Shared ratio is preferably set to 30~60 mass % in 100 mass %, and thixotropic agent is shared in 100 mass % of scaling powder total amount
Ratio is preferably set to 1~10 mass %, and activating agent ratio shared in 100 mass % of scaling powder total amount is preferably set to 0.1~
10 mass %.If the ratio of solvent is less than lower limiting value, since the viscosity of scaling powder is excessively high, starched using the welding of the scaling powder
The viscosity of material is also got higher therewith, and generating the printings such as the fillibility reduction that solder frequently occurs or crawling sometimes reduces not
Good situation.On the other hand, if the ratio of solvent is more than upper limit value, the viscosity of scaling powder is too low, therefore uses the scaling powder
The viscosity of welding slurry is also lower therewith, to generate the bad feelings of solder powder and flux ingredients precipitation separation sometimes
Condition.If also, the ratio of thixotropic agent is less than lower limiting value, welds too low with the viscosity of slurry, therefore generates solder powder sometimes
With the unfavorable condition of flux ingredients precipitation separation.On the other hand, if the ratio of thixotropic agent is more than upper limit value, welding slurry
Viscosity it is excessively high, therefore sometimes generate the printings such as fill solder or crawling reduce unfavorable condition.If also, activity
The ratio of agent is less than lower limiting value, then solder powder will not melt, and generates the bad feelings that can not obtain sufficient bond strength sometimes
Condition, on the other hand, if the ratio of activating agent is more than upper limit value, activating agent is easy to carry out with solder powder anti-in management process
The unfavorable condition that the storage stability answered, therefore generate welding slurry sometimes reduces.In addition, can also add in welding soldering flux
Add viscosity stabiliser.As viscosity stabiliser, the Polyphenols that can be dissolved in solvent, phosphoric acid based compound, sulphur system can be enumerated
Close the derivative etc. of object, tocopherol, the derivative of tocopherol, ascorbic acid, ascorbic acid.When viscosity stabiliser is excessive, sometimes
A problem that generating the meltbility of solder powder reduces, therefore it is preferably set to 10 mass % or less.
The combined amount of welding soldering flux when preparing welding slurry is preferably set to make slurry of the scaling powder after preparation
Expect that ratio shared in 100 mass % becomes the amount of 5~30 mass %.If this is because the combined amount of the welding soldering flux
Less than lower limiting value, then it is difficult to be gelatinized because of scaling powder deficiency, on the other hand, if the combined amount of the welding soldering flux is more than
Upper limit value, then the content ratio of the scaling powder in slurry is excessive, causes the content ratio of metal to reduce, is difficult in melt solder
Obtain the solder projection of desired size.
Since the welding uses slurry using the solder powder of aforementioned present invention as material, when reflow, melts rapidly, melts
Melting property is excellent, and on the other hand, after reflow, the solder powder of melting forms dystectic intermetallic compound, and heat resistance rises,
Therefore it is not easy to cause remelted caused by heat.Therefore, welding slurry of the invention is sudden and violent more particularly to be suitable for installation
Reveal electronic building brick etc. in a high temperauture environment.
(installation method and conjugant that have used the electronic building brick of welding slurry)
The electronic building brick of silicon chip, LED chip etc. is installed on respectively with slurry using the welding prepared by the above method
When the substrates such as kind heat-radiating substrate, FR4 (Flame Retardant Type 4) substrate, kovar (Kovar), existed by pin-array printing method
The specified position of aforesaid substrate transfers welding slurry, or prints welding slurry in specified position by print process.Then, exist
It has carried out loading the chip component as electronic building brick on transfer or the slurry printed.In this state, using reflow oven, in nitrogen
It is kept for 5~120 minutes at a temperature of 250~400 DEG C in atmosphere, reflow is carried out to solder powder.It according to circumstances, also can be to core
It is engaged while piece and substrate are while being pressurizeed.Conjugant is obtained by so that chip component is engaged with substrate as a result,
And electronic building brick is installed on substrate.
Embodiment
Then, the embodiment that the present invention will be described in detail together with comparative example.
1 ＞ of ＜ embodiments
First, 4.35 × 10 are added into 50mL water-3The nickel sulfate (II) of mol, 9.66 × 10-4The phosphinic acids sodium of mol,
3.29×10-4The sodium citrate of mol is stirred 5 minutes with rotary speed 300rpm using blender, prepares lysate.It utilizes
After the lysate is adjusted to pH5.0 by sulfuric acid, adding the polyvinyl alcohol 500 as dispersant of 0.2g, (average molecular weight is
500 polyvinyl alcohol), further stirred 10 minutes with rotary speed 300rpm.Then, the work of 0.2g will be dissolved in 50mL water
For dispersant polyvinyl alcohol 500 (polyvinyl alcohol that average molecular weight is 500) and be dispersed with the copper that average grain diameter is 0.18 μm
The dispersion liquid of powder 3.40g is added in the lysate, is stirred 10 minutes with rotary speed 500rpm, obtaining to be dispersed with makes nickel
The dispersion liquid of nickel coated copper powders made of being precipitated on copper powders surface.It is repeated four times following operation and is cleaned：It should
After dispersion liquid standing makes the powder precipitation of generation in 60 minutes, gives up supernatant, 100mL water is added to it and with rotary speed
300rpm is stirred 10 minutes.The dispersion liquid is dried finally by using vacuum drier, obtains the core centered on copper
And using nickel as the powder of the 1st clad (barrier layer).
Then, above-mentioned powder 0.37g is made to be scattered in 50mL water and prepare dispersion liquid.2.56 are added into the dispersion liquid
×10-2The STANNOUS SULPHATE CRYSTALLINE (II) of mol is stirred 5 minutes with rotary speed 300rpm using blender, prepares mixed liquor.Utilize sulphur
After the mixed liquor is adjusted to pH0.5 by acid, (the average molecular weight 500 of polyvinyl alcohol 500 as dispersant of 0.5g is added
Polyvinyl alcohol), further stirred 10 minutes with rotary speed 300rpm.Then, pH is adjusted with adding speed 50mL/min
Bivalent chromium ion aqueous solution 50mL for 0.5 1.58mol/L is added in the mixed liquor, and is stirred with rotary speed 500rpm
Mixing 10 minutes makes tin ion restore, thereby is achieved be dispersed with make tin nickel coated copper powders surface be precipitated made of outermost layer be
The dispersion liquid of the nickel coated copper powders of tin.It is repeated four times following operation and is cleaned：The dispersion liquid, which is stood 60 minutes, to be made
After the powder precipitation of generation, give up supernatant, 100mL water is added to it and is stirred 10 minutes with rotary speed 300rpm.Finally
The dispersion liquid is dried by using vacuum drier, obtain average grain diameter be 1.1 μm and be respectively formed as be with copper
Centronucleus take nickel as the 1st clad (barrier layer) and with solder powder that tin is the 2nd clad (outermost layer).
＜ embodiments 2~28,5 ＞ of the Comparative Examples 1 to 5
In embodiment 2~28, the Comparative Examples 1 to 55, also by the grain size and copper powders of copper powders used in adjustment
The ratio of additive amount, the additive amount of nickel sulfate (II) and STANNOUS SULPHATE CRYSTALLINE (II) and other compositions, to control into defined copper
The solder powder of center nuclear radius, anti-nickel diffusion layer and the outermost thickness of tin and defined grain size, in addition to this, with
1 same mode of embodiment obtains solder powder.
56 ＞ of ＜ comparative examples
First, 4.35 × 10 are added into 50mL water-3The nickel sulfate (II) of mol, 9.66 × 10-4The phosphinic acids sodium of mol,
3.29×10-4The sodium citrate of mol is stirred 5 minutes with rotary speed 300rpm using blender, prepares lysate.It utilizes
After the lysate is adjusted to pH5.0 by sulfuric acid, adding the polyvinyl alcohol 500 as dispersant of 0.2g, (average molecular weight is
500 polyvinyl alcohol), further stirred 10 minutes with rotary speed 300rpm.Then, the work of 0.2g will be dissolved in 50mL water
For dispersant polyvinyl alcohol 500 (polyvinyl alcohol that average molecular weight is 500) and be dispersed with the copper that average grain diameter is 0.18 μm
The dispersion liquid of powder 3.40g is added in the lysate, is stirred 10 minutes with rotary speed 500rpm, obtaining to be dispersed with makes nickel
The dispersion liquid of nickel coated copper powders made of being precipitated on copper powders surface.It is repeated four times following operation and is cleaned：It should
After dispersion liquid standing makes the powder precipitation of generation in 60 minutes, gives up supernatant, 100mL water is added to it and with rotary speed
300rpm is stirred 10 minutes.The dispersion liquid is dried finally by using vacuum drier, obtains the core centered on copper
And using nickel as the powder of the 1st clad (barrier layer).
Then, it is filled using the small-sized roller that gold-plated exerciser Co., Ltd. in Yamamoto (YAMAMOTO-MS Co., LTD.) makes
It sets, has been carried out to the above-mentioned core centered on copper and using nickel as the powder of barrier layer tin plating.It is formed as the electroplate liquid used,
It has used and has been dispersed with 5.0g powder in the electroplate liquid 150mL of sodium stannate 100g/L, sodium hydroxide 10g/L and sodium acetate 15g/L
Solution.Moreover, as electroplating processes condition, anode using tin, bath temperature be set as 50 DEG C, drum rotation speed be set as 19rpm, electricity
Pressure is set as 0.8V.It about tin plating film thickness, is adjusted by processing time, in the comparative example, is handled by carrying out 0.3 hour,
Tin outermost layer made of the precipitation of nickel coated copper powders surface is set to be point of the nickel coated copper powders of tin to obtain to be dispersed with
Dispersion liquid.It is repeated four times following operation and is cleaned：After dispersion liquid standing is made the powder precipitation of generation in 60 minutes, give up
Supernatant is added it in 100mL water and is stirred 10 minutes with rotary speed 300rpm.Finally by utilization vacuum drier to this
Dispersion liquid is dried, and obtains average grain diameter and is 3.3 μm and is respectively formed as centered on copper core, is the 1st clad with nickel
(barrier layer) and it is the solder powder of the 2nd clad (outermost layer) with tin.
57~65 ＞ of ＜ comparative examples
In comparative example 57~65, also by the grain size of copper powders used in adjustment and additive amount, the sulfuric acid of copper powders
The ratio and treatment conditions of the additive amount and other compositions of nickel (II) and STANNOUS SULPHATE CRYSTALLINE (II), to control into defined copper
The solder powder of center nuclear radius, anti-nickel diffusion layer and the outermost thickness of tin and defined grain size, in addition to this, with
56 same mode of comparative example obtains solder powder.
＜ comparative tests and evaluation ＞
By method as described below, weldering is determined to the solder powder obtained in Examples 1 to 28 and comparative example 1~65
The content ratio [quality %] of copper in feed powder end, average grain diameter [μm], the mean radius [μm] for the centronucleus being made of copper, by
The average thickness [μm] for the barrier layer that nickel is constituted and the average thickness [μm] for the clad being made of tin.By these results
It is shown in following table 1~table 5.Also, welding slurry is prepared respectively using these solder powders, is had rated when changing reflow most
Bond strength when big holding temperature.These results are shown in following table 6~table 10.In addition, by the centronucleus being made of copper
The sum of mean radius, the average thickness for the barrier layer being made of nickel, average thickness of clad for being made of tin are used as solder
The mean radius of powder.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
(1) analysis of the content ratio of the copper in solder powder：Utilize inductance coupling plasma emissioning spectral analysis (island
Tianjin makes the ICP emission spectrographic analysis devices that institute (Shimadzu Corporation) makes：ICPS-7510), solder powder has been carried out
The analysis of the content ratio of copper in end.
(2) average grain diameter of solder powder：By using particle size distribution device (the hole field system of laser diffraction scattering method
Make made, laser diffraction/scattering formula particle size distribution analyzer LA-950) particle diameter distribution is measured, and by position in its volume-cumulative
Average grain diameter of the diameter (Median diameters, D50) as solder powder.
(3) radius for the centronucleus being made of copper, the thickness for the barrier layer being made of nickel and the clad that is made of tin
Thickness measurement：Solder powder is embedded in thermosetting epoxy resin, after the section of solder powder is carried out dry grinding, is made
It is observed with electron microscope (Scanning Electron Microscope, SEM), to 30 semiconductor particles, is surveyed respectively
Surely the thickness of the radius for the centronucleus being made of copper, the thickness for the barrier layer being made of nickel and the clad being made of tin, is asked
Go out respective average value.Moreover, according to the thickness of the barrier layer being made of nickel obtained by said determination and being made of copper
The average value of radius of centronucleus calculate the ratio (radius of barrier layer thickness/centronucleus) of the average value of thickness.
(4) coherency of solder powder：Judged using following methods：By using the grain of laser diffraction scattering method
It spends distribution measurement device and measures grain size (manufactured by the making of hole field, laser diffraction/scattering formula particle size distribution analyzer LA-950)
Distribution has in addition to the distribution of peaks of desired grain size, by the grading curve obtained in the grain more than the grain size
There is the case where more than two grain size curves of distribution of peaks to be set as " having " cohesion for diameter side, will not observe and be set the case where that peak
It is agglomerated for "None".
(5) bond strength：By the way that the diethylene glycol monohexyl ether of 50 mass % of solvent will be used as, as 46 matter of rosin
Measure the newtrex (95 DEG C of softening point) of %, as the 1.0 mass % of cyclohexylamine hydrobromide of activating agent and as thixotropic agent
3.0 mass % of hardened castor oil is mixed, to be prepared into scaling powder.Then, by by the scaling powder and embodiment 1~
28 and comparative example 1~65 obtained in solder powder, with the ratio that scaling powder is 88 mass %, solder powder is 12 mass %
Mixing, to be prepared into welding slurry respectively.
By pin-array printing method, using 100 μm of needle of point diameter, the slurry of above-mentioned preparation is needed on 0.5mm thickness
The specified position of kovar (Fe-Ni-Co systems alloy) substrate.In addition, carrying out nickel plating on kovar substrate, and then carry out on it
Au flash.Then, the LED chip of 0.9mm × 0.9mm is loaded on the slurry transferred.In turn, on one side using pressurization
It is pressurizeed with the pressure of 1.0MPa to LED chip and substrate with fixture, utilizes infrared furnace on one side, in nitrogen atmosphere, with
0.17 hour, defined maximum holding temperature progress reflow, make LED chip be engaged with kovar substrate, engagement sample thereby is achieved
Product.In addition, maximum when by above-mentioned reflow keeps temperature to be set as 250 DEG C, 300 DEG C, 350 DEG C of different temperatures, by each reality
It applies example or each comparative example respectively obtains three joined samples.
About the kovar substrate of above-mentioned engagement and the bond strength of LED chip, recorded in JIS Z 3198-7
" the shear strength assay method of solder in chip assembly engagement " of lead-free solder test method-the 7, at room temperature and
Engagement shear strength is measured under conditions of after being taken care of 0 day and 30 days at 300 DEG C respectively, and finds out and will take care of 0 day and 30 at room temperature
When shear strength after it is set as 100, the relative shear intensity after being taken care of 0 day and 30 days at 300 DEG C.It is " excellent " to indicate in table
The situation that relative shear intensity is 90 or more, " good " represent less than 90 to 80 or more situation, "available" represent less than 80 to 70 with
On situation, " can not " the case where representing less than 70.
[table 6]
[table 7]
[table 8]
[table 9]
[table 10]
By 6~table of table, 10 comparing embodiment 1~28 and comparative example 1~65, following result can be known.
In the comparative example that the average grain diameter of solder powder is 0.5 μm, since grain size is too small, because of the oxygen on powder surface
The influence for changing film, from before keeping solder powder, solder powder does not melt.When the radius of the copper core is set as 1, by nickel
The thickness of the barrier layer of composition be 0.03 comparative example in, since the thickness of barrier layer is excessively thin, can not prevent copper or
The diffusion of tin, have bond strength be can not the case where.Also, in the comparative example that the content of copper is 75 mass % or so, due to
The content of copper is excessive, therefore solidification start temperature is excessively high, to there is the case where solder does not melt in reflow.Also, in copper
Content is in the comparative example of 1.5 mass % or so, and since the content of copper is very few, solidification start temperature is lower, and can not obtain fully
Heat resistance, therefore have bond strength be can not the case where.
In the comparative example that the average grain diameter of solder powder is 40 μm or so, since grain size is excessive, tool is formed after reflow
Have a bonding layer of larger hole (gap) and fine and close bonding layer can not be obtained, therefore, have bond strength be can not the case where.And
And in comparative example of the ratio of the radius of the thickness and centronucleus of barrier layer less than 0.04, since non-proliferation effect is small, because
This copper to be made of tin clad diffusion, cause the meltbility of solder powder to reduce, have bond strength for can not the case where.Phase
Instead, in the comparative example that the ratio of the thickness of barrier layer and the radius of centronucleus is more than 0.51, since the ratio of nickel is excessively high,
And the meltbility of solder powder reduces, thus have bond strength be can not the case where.It is made of tin being formed by barrel plating
Clad comparative example in, due to largely generating the powder agglomerated securely, about using laser diffraction scattering method
The average grain diameter of the solder powder obtained and the average grain diameter that obtained solder powder is measured by SEM observations
Value, obtains visibly different value, also, can not obtain good print film, to also can not measure engagement to any sample
Intensity.
In contrast, solder powder average grain diameter in 1 μm or more and 30 μm or less of range, relative to solder powder
The 100 mass % of total amount at end, the content ratio of copper is more than 2 mass % and in the range of 70 mass % or less, and by the copper
When the radius of core is set as 1, the embodiment 1 of the thickness of the barrier layer being made of nickel in 0.04 or more and 0.51 or less range
In~28, good print film can be obtained almost without the powder of cohesion, meanwhile, before by solder powder keeping and take care of
Each 250 DEG C after 30 days, 300 DEG C, under 350 DEG C of all reflow temperatures, bond strength be can, it is good or excellent.
Industrial availability
The present invention can be suitable for the solder powder that manufacture will take care of for a long time sometimes.Further, it is possible to suitable for installation
Electronic building brick is especially suitable for installation exposure electronic building brick in a high temperauture environment.
Claims (4)
1. a kind of manufacturing method of solder powder comprising：
The process for preparing the 1st dispersion liquid of copper powders；
The addition of the metal salt of nickel is mixed in the 1st dispersion liquid of the copper powders and prepare the metal salt dissolved with the nickel and
The process for being dispersed with the 1st lysate of the copper powders；
The process for adjusting the pH of the 1st lysate；
By adding the 1st reducing agent of mixing into the 1st lysate for have adjusted pH, nickel ion is set to restore, to prepare analysis
The process of the nickel coated copper powders and the 2nd dispersion liquid of dispersion that go out；
2nd dispersion liquid is separated by solid-liquid separation, and the solid constituent of the dry separation of solid and liquid, is made of nickel to make
Barrier layer coated copper core made of metal powder process；
The process for preparing the 3rd dispersion liquid of the metal powder；
The metal salt addition of tin is mixed in the 3rd dispersion liquid of the metal powder and prepares the metal salt dissolved with the tin
And the process for being dispersed with the 2nd lysate of the metal powder；
The process for adjusting the pH of the 2nd lysate；
By adding the 2nd reducing agent of mixing into the 2nd lysate for have adjusted pH, tin ion is set to restore, to prepare analysis
The process that the tin gone out coats the metal powder and the 4th dispersion liquid of dispersion；And
4th dispersion liquid is separated by solid-liquid separation, and the solid constituent of the dry separation of solid and liquid, to make the metal
The process for the solder powder that powder is coated by tin layers.
2. a kind of solder powder is the weldering that metal powder is coated by tin layers made of the barrier layer coated copper core being made of nickel
Feed powder is last, which is characterized in that,
The average grain diameter of the solder powder be 1 μm or more and 30 μm hereinafter,
Relative to the 100 mass % of total amount of the solder powder, the content ratio of copper be 2 mass % or more and 70 mass % with
Under,
When the radius of the copper core is set as 1, the thickness of the barrier layer being made of nickel is 0.04 or more and 0.51 or less
Ratio.
3. a kind of manufacturing method of welding slurry, by by the method according to claim 11 it is manufactured made of weld
Solder powder described in feed powder end or claim 2 mixes and is gelatinized to manufacture welding slurry with welding soldering flux
Material.
4. a kind of installation method of electronic building brick is welded made of using the method according to claim 11 manufactured and is used
Slurry installs electronic building brick.
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| JP2015244270A JP6587099B2 (en) | 2015-12-15 | 2015-12-15 | Solder powder, method for producing the same, and method for preparing solder paste using the powder |
| PCT/JP2016/086694 WO2017104562A1 (en) | 2015-12-15 | 2016-12-09 | Solder powder, method for manufacturing same, and method for preparing solder paste using this powder |
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| KR (1) | KR102189367B1 (en) |
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| CN113751922A (en) * | 2021-10-11 | 2021-12-07 | 中国科学院电工研究所 | Lead-free solder and preparation method and application thereof |
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| KR102489331B1 (en) * | 2019-12-31 | 2023-01-17 | 덕산하이메탈(주) | Solder ball and the manufacturing method thereof |
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- 2016-12-06 TW TW105140255A patent/TWI668065B/en active
- 2016-12-09 WO PCT/JP2016/086694 patent/WO2017104562A1/en active Application Filing
- 2016-12-09 CN CN201680080194.8A patent/CN108602121B/en active Active
- 2016-12-09 KR KR1020187019019A patent/KR102189367B1/en active IP Right Grant
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| CN113574687A (en) * | 2019-03-19 | 2021-10-29 | 株式会社Kelk | Thermoelectric module and optical module |
| CN113574687B (en) * | 2019-03-19 | 2024-02-20 | 株式会社Kelk | Thermoelectric module and optical module |
| CN111036897A (en) * | 2019-12-24 | 2020-04-21 | 深圳第三代半导体研究院 | Preparation method of interconnection material with micro-nano core-shell structure |
| CN112475313A (en) * | 2020-11-11 | 2021-03-12 | 昆明理工大学 | Method for preparing nano-scale solder additive through chemical reaction |
| CN112475313B (en) * | 2020-11-11 | 2023-04-28 | 昆明理工大学 | Method for preparing nanoscale solder additive through chemical reaction |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2017104562A1 (en) | 2017-06-22 |
| JP6587099B2 (en) | 2019-10-09 |
| KR20180093979A (en) | 2018-08-22 |
| KR102189367B1 (en) | 2020-12-09 |
| TW201739545A (en) | 2017-11-16 |
| TWI668065B (en) | 2019-08-11 |
| CN108602121B (en) | 2020-08-04 |
| JP2017110251A (en) | 2017-06-22 |
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