WO2011062222A1 - Process for producing solder powder - Google Patents
Process for producing solder powder Download PDFInfo
- Publication number
- WO2011062222A1 WO2011062222A1 PCT/JP2010/070563 JP2010070563W WO2011062222A1 WO 2011062222 A1 WO2011062222 A1 WO 2011062222A1 JP 2010070563 W JP2010070563 W JP 2010070563W WO 2011062222 A1 WO2011062222 A1 WO 2011062222A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solder powder
- mixture
- aqueous solvent
- solder
- melting point
- Prior art date
Links
Classifications
-
- 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
-
- 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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
-
- 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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- 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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/042—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling using a particular milling fluid
-
- 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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/049—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by pulverising at particular temperature
Definitions
- the present invention relates to a method for producing solder powder having a fine particle size.
- the downsizing of electronic devices such as mobile communication devices is progressing, and the downsizing of electronic components and electronic circuits incorporated therein is expected, and this trend will continue in the future.
- the size of parts and circuits that use solder paste mixed with solder powder is becoming smaller, and it is necessary for fine pitch soldering technology that supports line widths and diameters of about 100 ⁇ m in substrate through holes and IC chip wiring.
- a suitable solder paste is needed.
- the average particle size of the solder powder blended in the solder paste used may be desired to be 5 ⁇ m or less.
- solder powder having an average particle size of less than 3 ⁇ m and an average particle size of less than 1 ⁇ m is required as a solder powder to be blended in the solder paste. Is thought to increase.
- solder powders have been manufactured by a disk atomizing method or a gas atomizing method, but it has been difficult to obtain a solder powder having an average particle size of 10 ⁇ m or less by these methods.
- Patent Document 1 describes that solder powder having an average particle size of 5 ⁇ m or less can be obtained by adjusting the manufacturing conditions even in the gas atomization method.
- solder powder having an average particle size of 4 ⁇ m or less was obtained by the disk atomizing method or the gas atomizing method.
- Patent Document 2 describes a method of obtaining solder powder by stirring oil and solder melt.
- Patent Document 3 describes a method for producing a reflow solder having a fine particle shape, but no solder powder having an average particle diameter of less than 3 ⁇ m is obtained in any of the documents.
- JP 2004-098118 A Japanese translation of PCT publication No. 2002-519509 German Patent Application Publication No. 4402042
- an object of the present invention is to provide a method for producing solder powder, which can efficiently obtain solder powder having an average particle size of 0.05 ⁇ m or more and less than 3 ⁇ m with a stable yield.
- the present inventors put a solid or liquid metal, a non-aqueous solvent, and a grinding ball having a diameter of 0.05 mm to 5 mm in a container, The mixture is heated to 150 ° C. or higher and stirred, and then the balls for pulverization are separated from the mixture to obtain a mixture of solder powder and non-aqueous solvent, and the mixture of solder powder and non-aqueous solvent.
- a solder powder having an average particle size of 0.05 ⁇ m or more and less than 3 ⁇ m can be obtained, and the present invention has been completed.
- a method for producing solder powder which includes a step of solid-liquid separation of a mixture of solder powder and a non-aqueous solvent to obtain solder powder.
- the boiling point of the non-aqueous solvent may be 150 ° C. or higher.
- the non-aqueous solvent may be an organic solvent having an aldehyde group or a hydroxy group.
- the non-aqueous solvent may be an organic solvent containing at least one of a primary amino group, a secondary amino group, or a tertiary amino group.
- the stirring step may be performed by rotating the blade at a peripheral speed of 200 cm / second to 20000 cm / second.
- the solid-liquid separation may be performed by centrifugation or a filter press. Further, after solid-liquid separation of the mixture of the solder powder and the non-aqueous solvent, the solder powder may be washed with an organic solvent having a boiling point of 150 ° C. or less.
- the volume of the metal may be 0.1 volume% to 20 volume% of the volume of the non-aqueous solvent.
- the solder powder that can be used as a solder paste material that meets the requirements of fine pitch soldering technology, which has an average particle size of less than 3 ⁇ m and is expected to become more sophisticated in the future, is stable. Can be obtained efficiently with a high yield.
- alloy composition of the solder powder in the present invention various solder alloys can be used.
- an alloy containing 90 mass% to 99.9 mass% of Sn and 0.05 mass% to 10 mass% of Ag can be cited. In this case, it is also possible to obtain lead-free solder powder that does not contain lead.
- an alloy containing 50 mass% to 90 mass% of Sn and 10 mass% to 50 mass% of Pb can be mentioned.
- solder powder having a low melting point can be obtained. The low melting point is advantageous in applying the production method of the present invention in which stirring is performed in a solvent.
- the alloy may contain one or more elements such as copper, zinc, bismuth, indium, and antimony as necessary.
- the average particle size of the solder powder is preferably 0.05 ⁇ m or more and less than 3 ⁇ m. If it is 3 ⁇ m or more, it may not fully meet the requirements of fine pitch soldering technology, and solder powder of less than 0.05 ⁇ m has high surface activity and may cause problems due to alteration such as oxidation. In order to meet the demand level of fine pitch soldering technology due to further miniaturization of electronic components and electronic circuits, the average particle size of the solder powder is more preferably less than 1 ⁇ m, and 0.7 ⁇ m or less. More preferably.
- solder powder having an average particle size of less than 3 ⁇ m can be efficiently produced with a stable yield by going through the following steps.
- a solder alloy having the same metal composition as the solder powder to be obtained for example, Sn containing 90 mass% to 99.9 mass% and Ag containing 0.05 mass% to 10 mass%, A solder alloy containing 50% by mass to 90% by mass of Sn and 10% by mass to 50% by mass of Pb, or a mixture of metals used as raw materials for these solder alloys can be used.
- an alloy In order to make it easier to obtain solder powder having a uniform metal composition, it is preferable to use an alloy.
- the non-aqueous solvent in the present invention preferably has a boiling point of 150 ° C. or higher, and particularly preferably has a boiling point of 200 ° C. or higher.
- a boiling point higher than the melting point of the solder powder to be obtained it is preferable to have a boiling point higher than the melting point of the solder powder to be obtained as a non-aqueous solvent, but by using a pressure vessel as a vessel for stirring, the atmospheric pressure It is possible to use a non-aqueous solvent whose boiling point at normal pressure is lower than the melting point of the solder powder.
- the boiling point is desirably higher by 10 ° C. than the melting temperature of the solder powder to be obtained.
- the solder powder reacts with oxygen and easily forms an oxide on the surface, so that a solvent having a reducing property is more preferable.
- an alcohol solvent having a boiling point in the range of 150 ° C. to 400 ° C. is an example of such a non-aqueous solvent.
- a non-aqueous solvent has a boiling point of 220 in order to obtain finely divided solder powder. It is preferable that the temperature is higher than or equal to ° C, more preferably higher than or equal to 250 ° C.
- the non-aqueous solvent includes a monohydric alcohol or a dihydric alcohol glycol.
- the monohydric alcohol include butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, decyl alcohol, nonyl alcohol, cyclopentanol, benzyl alcohol, and cinnamyl alcohol.
- glycol solvents include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, benzpinacol, hydro Benzoyl, cyclopentadiol, cyclohexanediol, cyclohexanediol, glycolic acid amide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monoethyl ether, diethylene glycol dibutyl ether, acetic acid diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, etc.
- glycol solvents include glycerin, ethylene glycol, diethylene glycol, triethylene glyco
- glycols and diols are preferable because they have two hydroxyl groups and thus have polarity and contribute to the dispersibility of the powder.
- examples of such a solvent include —CH 2 —CHOH, or —CHR—CHOH, —CR 1 R 2 —CHOH, ⁇ CHCHOH, ⁇ CRCHOH (R, R 1 , R 2 : side chain) in the molecule.
- the boiling point of the solvent is at least 100 ° C. or higher.
- organic compounds having an aldehyde group —CHO have the same effect.
- aliphatic saturated aldehydes such as lauric aldehyde, tridecyl aldehyde, myristic aldehyde, capron aldehyde, heptaldehyde, pentadecyl aldehyde, palmitic aldehyde, marga aldehyde
- aliphatic aldehydes such as succindialdehyde, aliphatic unsaturated aldehydes such as crotonaldehyde, and aromatic aldehydes such as benzaldehyde, tolualdehyde, salicylaldehyde, and cinnamaldehyde.
- amine-based reducing solvents include hexylamine, hebutinamine, octylamine, undecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, dibutylamine, diamylamine, cyclohexylamine, aniline, naphthylamine, and toluidine. is there.
- ⁇ Crushing ball> As the grinding balls used in the present invention, alumina balls, zirconia balls, mullite balls, glass balls, metallic stainless balls, iron balls, etc. using ceramics can be used, and the material is not particularly limited. Nonetheless, zirconia, alumina, and stainless steel are particularly suitable as the material for the ball for pulverization, which has the advantages of high durability and low contamination of solder powder.
- the grinding balls preferably have a particle size of 0.05 mm to 5 mm. If only pulverizing balls having a particle diameter of more than 15 mm are used, it becomes difficult to obtain solder powder having a desired fine particle diameter. If only pulverizing balls having a particle diameter of less than 0.05 mm are used, solidification after stirring is difficult. Liquid separation may take time.
- the particle diameter of the ball for grinding is more preferably 0.1 to 5 mm, still more preferably 0.1 to 3 mm, and still more preferably 0.1 to 1 mm. . It is also possible to use a pulverizing ball in combination of a large particle size and a small particle size.
- the large ball size need not be particularly concerned with the particle size of 15 mm, and may be, for example, a particle size of 30 mm. It is necessary that at least 50% by mass of grinding balls having a particle size of 0.05 mm to 15 mm be contained.
- Diamond-like carbon (DLC) or a compound such as B, C, or N, which is a material to which solder is difficult to adhere, can be formed on the surface of the grinding ball.
- the volume ratio of the mixture is preferably 0.1% by volume to 20% by volume, and more preferably 0.1% by volume to 10% by volume with respect to the volume of the non-aqueous solvent used.
- the grinding balls are preferably 20% by volume to 600% by volume with respect to the volume of the non-aqueous solvent used.
- the metal raw material is less than 0.1% by volume, the productivity is low, and when it exceeds 20% by volume, the particle size of the obtained solder powder may not be sufficiently small.
- the pulverizing ball is less than 20% by volume, the particle size of the obtained solder powder may not be sufficiently small.
- the pulverizing ball is more than 600% by volume, a large amount of raw material metal adheres to the surface of the pulverizing ball.
- the volume ratio of the grinding ball to the non-aqueous solvent is set so that the height of the top surface of the grinding ball and the top surface of the non-aqueous solvent are substantially the same. By adjusting, it becomes easier to obtain fine solder powder, which is more preferable.
- the atmosphere for heating and stirring is preferably an inert gas or a reducing gas.
- the atmosphere is air, a thick oxide film may be formed on the surface of the generated solder powder, and it is preferable that the oxygen concentration in the atmosphere is low.
- the inert gas include nitrogen and argon
- the reducing gas include hydrogen or a mixed gas of hydrogen and an inert gas.
- the heating temperature of the mixture may be higher than the melting point of the alloy composition of the solder powder to be obtained, but it is heated to a temperature 5 ° C. lower than the melting point to 20 ° C. higher than the melting point. It is preferable to do. More preferably, the temperature may be the same temperature as the melting point to 17 ° C. higher than the melting point. More preferably, the temperature may be 7 ° C. higher than the melting point to 12 ° C. higher than the melting point.
- the heating temperature is set to a temperature lower than the boiling point of the non-aqueous solvent to be used (in the case of heating and stirring under pressure, the boiling point under pressure).
- Stirring can be performed by rotating a stirring blade, and may be performed using a pulverizer that can use pulverizing balls such as a mill.
- the pulverization conditions such as the number of revolutions may be appropriately selected according to the content of the mixture and the average particle diameter of the solder powder to be obtained.
- the particle size can be reduced.
- the rotational speed is 100 to 100,000.
- the range of rpm and the peripheral speed of the stirring blade can be set in the range of 100 to 5000 cm / sec.
- Solid-liquid separation of the mixture of the solder powder and non-aqueous solvent obtained in the above step is performed.
- Solid-liquid separation can be performed by a known method such as centrifugation or filtration with a filter press.
- the used non-aqueous solvent does not have a trouble as a dispersion medium of solder powder, it is not necessary to perform solid-liquid separation.
- the solid-liquid separated solder powder can be washed with a solvent.
- a solvent is an organic solvent of alcohol having a low boiling point such as methanol or ethanol. After washing, drying by a method that does not perform high-temperature heating, such as vacuum drying, can yield a solder powder with little residual non-aqueous solvent used.
- Example 1 10 g of solder alloy wire 1 mm ⁇ having a composition of Sn 99% by mass, Ag 0.3% by mass and Cu 0.7% by mass was weighed, and this solder wire was put into a 300 mL separable flask. As a result of measuring the melting point of the solder alloy wire with a differential scanning calorimeter (DSC) (manufactured by Rigaku Corporation, Thermo plus DSC 8230), the melting point was 218 ° C. Next, 300 g of 0.3 mm ⁇ zirconia balls were charged into the separable flask, and 100 mL of tetraethylene glycol was further charged to obtain a mixture.
- DSC differential scanning calorimeter
- the upper lid of the separable flask was sealed and sealed, and nitrogen gas was allowed to flow at 100 mL / min to perform gas replacement for 10 minutes.
- the mixture was subjected to 14 kinds of temperatures (heating temperature) shown in Table 1 ). The temperature of the mixture was measured with a thermocouple installed in a separable flask. After maintaining the mixture at the heating temperature for 1 hour, the mixture was cooled at a cooling rate of 5 ° C./min while maintaining the stirring state. When the mixture became 40 ° C. or lower, the rotation of the stirring blade was stopped.
- the mixture was then passed through a mesh of 250 mesh nylon fabric to separate 0.3 mm ⁇ zirconia balls from the mixture.
- a solvent tetraethylene glycol
- finely divided solder powder was dispersed was recovered.
- the solvent in which the solder powder was dispersed was centrifuged at 3000 rpm for 5 minutes and subjected to solid-liquid separation, and the supernatant liquid was removed to collect the solder powder. Thereafter, cleaning was performed in the following manner.
- the collected solder powder was stirred and mixed with 100 mL of ethanol and redispersed, and then centrifuged at 3000 rpm for 5 minutes to perform solid-liquid separation, and the supernatant liquid was removed to collect the solder powder.
- the collected solder powder was dispersed in ethanol and then subjected to solid-liquid separation by centrifugation five times.
- the obtained solder powder was vacuum-dried at 60 ° C. to obtain 14 types of dried solder powder having different heating temperatures.
- the average particle diameter D50 of the dried solder powder is shown in Table 1.
- 0.3 g of a solder powder sample is placed in 30 mL of isopropyl alcohol, treated with a 45 W ultrasonic cleaner for 5 minutes, and then treated with the microtrac 9320-X100 (Honeywell-Nikkiso Co., Ltd.).
- the cumulative 50% by mass particle diameter (D50) when the diameter was measured was defined as the average particle diameter of the silver powder.
- the average particle diameter D50 will be described.
- the cumulative curve is, for example, 10%, 50%, and 90% when the cumulative curve is obtained with the total volume of the silver powder as 100%.
- D50 which is an accumulation median diameter (Median diameter) is made into the average particle diameter.
- the yield of the solder powder was calculated by dividing the mass of the obtained dried solder powder by the mass of the solder alloy wire used. The results are shown in Table 1.
- Example 2 The composition of the solder alloy wire was changed from Sn 99 mass%, Ag 0.3 mass%, Cu 0.7 mass% to Sn 96.5 mass%, Ag 3.0 mass%, Cu 0.5 mass%, and the heating temperature was changed to Table 1.
- the dry solder powder was obtained by the same method as in Example 1 except that the 14 types were changed from 13 types to 13 types shown in Table 2, and evaluated.
- fusing point of a solder alloy wire it was 223 degreeC.
- the dried solder powder was examined for the presence or absence of a hydroxy group peak of tetraethylene glycol by a reflective FT-IR, but the peak was not observed.
- Example 3 The composition of the solder alloy wire was changed from Sn 99 mass%, Ag 0.3 mass%, Cu 0.7 mass% to five types shown in Table 3, and the heating temperature was changed from 14 types in Table 1 to Table 3, Table 4, A dried solder powder was obtained in the same manner as in Example 1 except that the heating temperatures in Table 5 were changed (melting point of solder alloy + 5 ° C., melting point of solder alloy ⁇ 10 ° C., melting point of solder alloy ⁇ 10 ° C.). And evaluated. Tables 3 to 5 show the results of measuring the melting points of the solder alloy wires having five compositions. Tables 3 to 5 show the yield of solder powder and the average particle diameter D50 of the solder powder in each sample.
- the dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
- the particle shape was spherical.
- Table 3 shows the average particle diameter D50 of the dried solder powder and the yield of the solder powder. As shown in Tables 4 and 5, when the heating temperatures were the melting point ⁇ 10 ° C. and the melting point + 30 ° C., the yield of the solder powder was less than 1%.
- Example 4 Solder that has been dried in the same manner as in Example 1 except that the mass of the solder alloy wire was changed from 10 g to the value shown in Table 6, and the heating temperature was changed from the value shown in Table 1 to the value shown in Table 6. Powder was obtained and evaluated.
- the dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
- Table 6 shows the average particle diameter D50 of the dried solder powder and the yield of the solder powder. From the results in Table 6, it was found that the heating temperature range for obtaining a suitable solder powder yield did not change even when the alloy concentration during pulverization was changed.
- Example 5 The heating temperature was changed from the value shown in Table 1 to 250 ° C., and the cooling rate was changed from 5 ° C./min to 0.2 ° C./min until reaching 200 ° C., as in Example 1.
- the dried solder powder was obtained by the method and evaluated.
- the dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
- the average particle diameter D50 of the dried solder powder was 0.9 ⁇ m, and the yield of the solder powder was 30% by mass.
- Example 6 The heating temperature was changed from the value described in Table 2 to 255 ° C, and the cooling rate was changed from 5 ° C / min to 0.2 ° C / min until reaching 210 ° C, which was the same as in Example 2.
- the dried solder powder was obtained by the method and evaluated.
- the dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
- the average particle diameter D50 of the dried solder powder was 0.9 ⁇ m, and the yield of the solder powder was 32% by mass.
- the present invention can be applied to a method for producing solder powder having a fine particle size.
Abstract
A process for producing a solder powder is provided by which it is possible to efficiently obtain a solder powder having an average particle diameter of 0.05 µm or larger but less than 3 µm in a stable yield.
The process for producing a solder powder comprises: a step in which a solid or liquid metal, a nonaqueous solvent, and balls for pulverization that have a diameter of 0.05-5 mm are introduced into a vessel to obtain a mixture; a step in which the mixture is heated to a temperature between (melting point of the metal)-5ºC and (melting point of the metal)+20ºC and stirred; a step in which the balls for pulverization are separated from the stirred mixture to obtain a mixture of a solder powder and the nonaqueous solvent; and a step in which the mixture of a solder powder and the nonaqueous solvent is subjected to solid-liquid separation to obtain the solder powder.
Description
本発明は、粒径が微細であるはんだ粉の製造方法に関する。
The present invention relates to a method for producing solder powder having a fine particle size.
携帯通信機器等の電子機器の小型化か進んでおり、それに組み込まれる電子部品・電子回路の小型化が進み、今後もこの傾向は続くものと考えられる。はんだ粉を配合したはんだペーストが使用される部品・回路のサイズは小さくなっており、基板のスルーホールやＩＣチップの配線において１００μｍ程度の線幅または径に対応したファインピッチソルダリング技術の要求に適合したはんだペーストが必要となってきている。この場合、用いるはんだペーストに配合するはんだ粉の平均粒径は、５μｍ以下であることが望まれる場合がある。今後予想される電子部品や回路の更なる小型化の要請に対応するために、はんだペーストに配合するはんだ粉として、平均粒径３μｍ未満、更には平均粒径１μｍ未満のはんだ粉が要望されることが増加すると考えられる。
The downsizing of electronic devices such as mobile communication devices is progressing, and the downsizing of electronic components and electronic circuits incorporated therein is expected, and this trend will continue in the future. The size of parts and circuits that use solder paste mixed with solder powder is becoming smaller, and it is necessary for fine pitch soldering technology that supports line widths and diameters of about 100 μm in substrate through holes and IC chip wiring. A suitable solder paste is needed. In this case, the average particle size of the solder powder blended in the solder paste used may be desired to be 5 μm or less. In order to meet the demand for further miniaturization of electronic components and circuits, solder powder having an average particle size of less than 3 μm and an average particle size of less than 1 μm is required as a solder powder to be blended in the solder paste. Is thought to increase.
従来よりはんだ粉は、ディスクアトマイズ法やガスアトマイズ法にてその多くが製造されているが、これらの方法では平均粒径１０μｍ以下のはんだ粉を得ることが困難であった。特許文献１には、ガスアトマイズ法でも製造条件を調整することにより、平均粒径５μｍ以下のはんだ粉が得られることが記載されている。しかし、ディスクアトマイズ法やガスアトマイズ法で平均粒径４μｍ以下のはんだ粉が得られた報告例はない。
Conventionally, many solder powders have been manufactured by a disk atomizing method or a gas atomizing method, but it has been difficult to obtain a solder powder having an average particle size of 10 μm or less by these methods. Patent Document 1 describes that solder powder having an average particle size of 5 μm or less can be obtained by adjusting the manufacturing conditions even in the gas atomization method. However, there is no report example in which solder powder having an average particle size of 4 μm or less was obtained by the disk atomizing method or the gas atomizing method.
また、ディスクアトマイズ法、ガスアトマイズ法以外のはんだ粉の製法としては、特許文献２に、オイルとハンダ溶融物を攪拌することによりはんだ粉を得る方法が記載されている。特許文献３には、微細粒状にされたリフローはんだを製造する方法が記載されているが、いずれの文献でも、平均粒径３μｍ未満のはんだ粉は得られていない。
As a method for producing solder powder other than the disk atomizing method and the gas atomizing method, Patent Document 2 describes a method of obtaining solder powder by stirring oil and solder melt. Patent Document 3 describes a method for producing a reflow solder having a fine particle shape, but no solder powder having an average particle diameter of less than 3 μm is obtained in any of the documents.
上述したように、平均粒径３μｍ未満のはんだ粉は得られていない。そこで、本発明の目的は、平均粒径が０．０５μｍ以上、３μｍ未満のはんだ粉を安定した収率でもって効率的に得ることができるはんだ粉の製造方法を提供することにある。
As described above, solder powder having an average particle size of less than 3 μm has not been obtained. Therefore, an object of the present invention is to provide a method for producing solder powder, which can efficiently obtain solder powder having an average particle size of 0.05 μm or more and less than 3 μm with a stable yield.
前記の目的を達成するため、本発明者らは、鋭意研究の結果、容器中に、固体または液体の金属と、非水系溶媒と、直径０．０５ｍｍ～５ｍｍの粉砕用ボールとを入れ、混合物を得て、前記混合物を１５０℃以上に加熱し、攪拌した後、前記混合物から粉砕用ボールを分離して、はんだ粉と非水系溶媒の混合物を得て、前記はんだ粉と非水系溶媒の混合物を固液分離することにより、平均粒径０．０５μｍ以上、３μｍ未満のはんだ粉を得られることを知見し、本発明を完成するに至った。
In order to achieve the above-mentioned object, the present inventors, as a result of diligent research, put a solid or liquid metal, a non-aqueous solvent, and a grinding ball having a diameter of 0.05 mm to 5 mm in a container, The mixture is heated to 150 ° C. or higher and stirred, and then the balls for pulverization are separated from the mixture to obtain a mixture of solder powder and non-aqueous solvent, and the mixture of solder powder and non-aqueous solvent. As a result of the solid-liquid separation, it was found that a solder powder having an average particle size of 0.05 μm or more and less than 3 μm can be obtained, and the present invention has been completed.
かかる知見に基づく本発明によれば、容器中に、固体または液体の金属と、非水系溶媒と、直径０．０５ｍｍ～５ｍｍの粉砕用ボールとを入れ、混合物を得る工程と、前記混合物を前記金属の融点－５℃～前記金属の融点＋２０℃に加熱し、攪拌する工程と、攪拌後の前記混合物から粉砕用ボールを分離して、はんだ粉と非水系溶媒の混合物を得る工程と、前記はんだ粉と非水系溶媒の混合物を固液分離して、はんだ粉を得る工程を有する、はんだ粉の製造方法が提供される。
According to the present invention based on such knowledge, a step of obtaining a mixture by putting a solid or liquid metal, a non-aqueous solvent, and a pulverizing ball having a diameter of 0.05 mm to 5 mm in a container; and Heating to a melting point of the metal from −5 ° C. to the melting point of the metal + 20 ° C., stirring, separating the grinding balls from the stirred mixture to obtain a mixture of solder powder and a non-aqueous solvent; Provided is a method for producing solder powder, which includes a step of solid-liquid separation of a mixture of solder powder and a non-aqueous solvent to obtain solder powder.
前記非水系溶媒の沸点は１５０℃以上であってもよい。また、前記非水系溶媒はアルデヒド基またはヒドロキシ基を有する有機溶媒であってもよい。また、前記非水系溶媒は一級アミノ基、または二級アミノ基、または三級アミノ基の内の少なくとも一種以上を含む有機溶媒であってもよい。
The boiling point of the non-aqueous solvent may be 150 ° C. or higher. The non-aqueous solvent may be an organic solvent having an aldehyde group or a hydroxy group. The non-aqueous solvent may be an organic solvent containing at least one of a primary amino group, a secondary amino group, or a tertiary amino group.
また、羽根を周速２００ｃｍ／秒～２００００ｃｍ／秒で回転することにより前記攪拌する工程を行ってもよい。また、前記固液分離を遠心分離またはフィルタープレスにより行ってもよい。また、前記はんだ粉と非水系溶媒の混合物を固液分離した後、はんだ粉を沸点１５０℃以下の有機溶媒で洗浄してもよい。また、前記金属の体積が、前記非水系溶媒の体積の０．１体積％～２０体積％であってもよい。
Further, the stirring step may be performed by rotating the blade at a peripheral speed of 200 cm / second to 20000 cm / second. The solid-liquid separation may be performed by centrifugation or a filter press. Further, after solid-liquid separation of the mixture of the solder powder and the non-aqueous solvent, the solder powder may be washed with an organic solvent having a boiling point of 150 ° C. or less. The volume of the metal may be 0.1 volume% to 20 volume% of the volume of the non-aqueous solvent.
本発明によれば、平均粒径が３μｍ未満と小さく、今後ますます高度化することが予想されるファインピッチソルダリング技術の要求に適合したはんだペースト用材料として活用することができるはんだ粉が安定した収率でもって効率的に得られる。
According to the present invention, the solder powder that can be used as a solder paste material that meets the requirements of fine pitch soldering technology, which has an average particle size of less than 3 μm and is expected to become more sophisticated in the future, is stable. Can be obtained efficiently with a high yield.
以下、本発明の実施の形態について説明する。なお、本実施の形態は本発明を限定するものではない。
Hereinafter, embodiments of the present invention will be described. Note that this embodiment does not limit the present invention.
＜はんだ粉の合金組成＞
本発明におけるはんだ粉の合金組成としては、種々のはんだ合金を用いることが可能である。具体的な合金組成としては第１に、Ｓｎが９０質量％～９９．９質量％、Ａｇが０．０５質量％～１０質量％含有する合金が挙げられる。この場合、鉛を含有しない無鉛はんだ粉を得ることも可能である。第２に、Ｓｎが５０質量％～９０質量％、Ｐｂが１０質量％～５０質量％含有合金が挙げられる。これらの合金組成にすることにより、低融点のはんだ粉を得ることができ、低融点であることは、溶媒中で攪拌する本発明の製造方法を適用する上で、有利である。前記の合金は、必要に応じて、銅、亜鉛、ビスマス、インジウム、アンチモン等の元素のいずれか一種又は二種以上を含んでもよい。 <Alloy composition of solder powder>
As an alloy composition of the solder powder in the present invention, various solder alloys can be used. As a specific alloy composition, first, an alloy containing 90 mass% to 99.9 mass% of Sn and 0.05 mass% to 10 mass% of Ag can be cited. In this case, it is also possible to obtain lead-free solder powder that does not contain lead. Secondly, an alloy containing 50 mass% to 90 mass% of Sn and 10 mass% to 50 mass% of Pb can be mentioned. By using these alloy compositions, solder powder having a low melting point can be obtained. The low melting point is advantageous in applying the production method of the present invention in which stirring is performed in a solvent. The alloy may contain one or more elements such as copper, zinc, bismuth, indium, and antimony as necessary.
本発明におけるはんだ粉の合金組成としては、種々のはんだ合金を用いることが可能である。具体的な合金組成としては第１に、Ｓｎが９０質量％～９９．９質量％、Ａｇが０．０５質量％～１０質量％含有する合金が挙げられる。この場合、鉛を含有しない無鉛はんだ粉を得ることも可能である。第２に、Ｓｎが５０質量％～９０質量％、Ｐｂが１０質量％～５０質量％含有合金が挙げられる。これらの合金組成にすることにより、低融点のはんだ粉を得ることができ、低融点であることは、溶媒中で攪拌する本発明の製造方法を適用する上で、有利である。前記の合金は、必要に応じて、銅、亜鉛、ビスマス、インジウム、アンチモン等の元素のいずれか一種又は二種以上を含んでもよい。 <Alloy composition of solder powder>
As an alloy composition of the solder powder in the present invention, various solder alloys can be used. As a specific alloy composition, first, an alloy containing 90 mass% to 99.9 mass% of Sn and 0.05 mass% to 10 mass% of Ag can be cited. In this case, it is also possible to obtain lead-free solder powder that does not contain lead. Secondly, an alloy containing 50 mass% to 90 mass% of Sn and 10 mass% to 50 mass% of Pb can be mentioned. By using these alloy compositions, solder powder having a low melting point can be obtained. The low melting point is advantageous in applying the production method of the present invention in which stirring is performed in a solvent. The alloy may contain one or more elements such as copper, zinc, bismuth, indium, and antimony as necessary.
＜はんだ粉の平均粒径＞
はんだ粉の平均粒径は、０．０５μｍ以上、３μｍ未満であることが好ましい。３μｍ以上の場合には、ファインピッチソルダリング技術の要求に十分適合できない場合があり、０．０５μｍ未満のはんだ粉は、表面活性が高く、酸化等の変質による問題が生じることがある。
電子部品や電子回路の更なる小型化によるファインピッチソルダリング技術の要求水準高度化に対応するためには、はんだ粉の平均粒径は、１μｍ未満とすることが更に好ましく、０．７μｍ以下とすることが一層好ましい。 <Average particle size of solder powder>
The average particle size of the solder powder is preferably 0.05 μm or more and less than 3 μm. If it is 3 μm or more, it may not fully meet the requirements of fine pitch soldering technology, and solder powder of less than 0.05 μm has high surface activity and may cause problems due to alteration such as oxidation.
In order to meet the demand level of fine pitch soldering technology due to further miniaturization of electronic components and electronic circuits, the average particle size of the solder powder is more preferably less than 1 μm, and 0.7 μm or less. More preferably.
はんだ粉の平均粒径は、０．０５μｍ以上、３μｍ未満であることが好ましい。３μｍ以上の場合には、ファインピッチソルダリング技術の要求に十分適合できない場合があり、０．０５μｍ未満のはんだ粉は、表面活性が高く、酸化等の変質による問題が生じることがある。
電子部品や電子回路の更なる小型化によるファインピッチソルダリング技術の要求水準高度化に対応するためには、はんだ粉の平均粒径は、１μｍ未満とすることが更に好ましく、０．７μｍ以下とすることが一層好ましい。 <Average particle size of solder powder>
The average particle size of the solder powder is preferably 0.05 μm or more and less than 3 μm. If it is 3 μm or more, it may not fully meet the requirements of fine pitch soldering technology, and solder powder of less than 0.05 μm has high surface activity and may cause problems due to alteration such as oxidation.
In order to meet the demand level of fine pitch soldering technology due to further miniaturization of electronic components and electronic circuits, the average particle size of the solder powder is more preferably less than 1 μm, and 0.7 μm or less. More preferably.
本発明によれば、平均粒径３μｍ未満のはんだ粉は、以下の工程を経ることにより、安定した収率でもって効率的に製造することができる。
（１）容器中に、固体または液体の金属と、非水系溶媒と、直径０．０５ｍｍ～５ｍｍの粉砕用ボールとを入れ、混合物を得る工程。
（２）前記混合物を前記金属の融点より５℃低い温度（融点－５℃）～前記金属の融点より２０℃高い温度（融点＋２０℃）に加熱し、攪拌する工程。
（３）前記混合物から粉砕用ボールを分離して、はんだ粉と非水系溶媒の混合物を得る工程。
（４）前記はんだ粉と非水系溶媒の混合物を固液分離して、はんだ粉を得る工程。
必要に応じて、得られたはんだ粉に対して、洗浄、乾燥等を行ってもよい。 According to the present invention, solder powder having an average particle size of less than 3 μm can be efficiently produced with a stable yield by going through the following steps.
(1) A step of putting a solid or liquid metal, a non-aqueous solvent, and a grinding ball having a diameter of 0.05 mm to 5 mm into a container to obtain a mixture.
(2) A step of heating the mixture from a temperature 5 ° C. lower than the melting point of the metal (melting point −5 ° C.) to a temperature 20 ° C. higher than the melting point of the metal (melting point + 20 ° C.) and stirring.
(3) A step of separating the grinding balls from the mixture to obtain a mixture of solder powder and a non-aqueous solvent.
(4) A step of obtaining a solder powder by solid-liquid separation of the mixture of the solder powder and the non-aqueous solvent.
You may perform washing | cleaning, drying, etc. with respect to the obtained solder powder as needed.
（１）容器中に、固体または液体の金属と、非水系溶媒と、直径０．０５ｍｍ～５ｍｍの粉砕用ボールとを入れ、混合物を得る工程。
（２）前記混合物を前記金属の融点より５℃低い温度（融点－５℃）～前記金属の融点より２０℃高い温度（融点＋２０℃）に加熱し、攪拌する工程。
（３）前記混合物から粉砕用ボールを分離して、はんだ粉と非水系溶媒の混合物を得る工程。
（４）前記はんだ粉と非水系溶媒の混合物を固液分離して、はんだ粉を得る工程。
必要に応じて、得られたはんだ粉に対して、洗浄、乾燥等を行ってもよい。 According to the present invention, solder powder having an average particle size of less than 3 μm can be efficiently produced with a stable yield by going through the following steps.
(1) A step of putting a solid or liquid metal, a non-aqueous solvent, and a grinding ball having a diameter of 0.05 mm to 5 mm into a container to obtain a mixture.
(2) A step of heating the mixture from a temperature 5 ° C. lower than the melting point of the metal (melting point −5 ° C.) to a temperature 20 ° C. higher than the melting point of the metal (melting point + 20 ° C.) and stirring.
(3) A step of separating the grinding balls from the mixture to obtain a mixture of solder powder and a non-aqueous solvent.
(4) A step of obtaining a solder powder by solid-liquid separation of the mixture of the solder powder and the non-aqueous solvent.
You may perform washing | cleaning, drying, etc. with respect to the obtained solder powder as needed.
＜原料金属＞
はんだ粉の原料金属としては、得ようとするはんだ粉と同一の金属組成を持つ例えばＳｎが９０質量％～９９．９質量％、Ａｇが０．０５質量％～１０質量％含有するはんだ合金、Ｓｎが５０質量％～９０質量％、Ｐｂが１０質量％～５０質量％含有するはんだ合金またはこれらはんだ合金の原料となる金属の混合物を使用することができる。均一な金属組成を持つはんだ粉をより容易に得ることができるようにするためには、合金を使用することが好ましい。 <Raw metal>
As a raw material metal of the solder powder, a solder alloy having the same metal composition as the solder powder to be obtained, for example, Sn containing 90 mass% to 99.9 mass% and Ag containing 0.05 mass% to 10 mass%, A solder alloy containing 50% by mass to 90% by mass of Sn and 10% by mass to 50% by mass of Pb, or a mixture of metals used as raw materials for these solder alloys can be used. In order to make it easier to obtain solder powder having a uniform metal composition, it is preferable to use an alloy.
はんだ粉の原料金属としては、得ようとするはんだ粉と同一の金属組成を持つ例えばＳｎが９０質量％～９９．９質量％、Ａｇが０．０５質量％～１０質量％含有するはんだ合金、Ｓｎが５０質量％～９０質量％、Ｐｂが１０質量％～５０質量％含有するはんだ合金またはこれらはんだ合金の原料となる金属の混合物を使用することができる。均一な金属組成を持つはんだ粉をより容易に得ることができるようにするためには、合金を使用することが好ましい。 <Raw metal>
As a raw material metal of the solder powder, a solder alloy having the same metal composition as the solder powder to be obtained, for example, Sn containing 90 mass% to 99.9 mass% and Ag containing 0.05 mass% to 10 mass%, A solder alloy containing 50% by mass to 90% by mass of Sn and 10% by mass to 50% by mass of Pb, or a mixture of metals used as raw materials for these solder alloys can be used. In order to make it easier to obtain solder powder having a uniform metal composition, it is preferable to use an alloy.
＜非水系溶媒＞
本発明での非水系溶媒とはその沸点が、１５０℃以上であるものが好適であり、２００℃以上であるものが特に好適である。後述するように、はんだ粉を得るためには、非水系溶媒として得ようとするはんだ粉の融点よりも高い沸点を持つものが好ましいが、攪拌をおこなう容器に圧力容器を用いることにより、雰囲気圧力を上げ、常圧の沸点がはんだ粉の融点より低い非水系溶媒でも、使用が可能である。しかしながら製造装置に耐圧性能が必要となるので、沸点は、得ようとするはんだ粉の溶融温度よりも１０℃以上高いことが望ましい。更に非水系溶媒として、はんだ粉が酸素と反応して、表面に酸化物を形成しやすいために、還元性を有する溶媒であることが更に好ましい。 <Non-aqueous solvent>
The non-aqueous solvent in the present invention preferably has a boiling point of 150 ° C. or higher, and particularly preferably has a boiling point of 200 ° C. or higher. As will be described later, in order to obtain solder powder, it is preferable to have a boiling point higher than the melting point of the solder powder to be obtained as a non-aqueous solvent, but by using a pressure vessel as a vessel for stirring, the atmospheric pressure It is possible to use a non-aqueous solvent whose boiling point at normal pressure is lower than the melting point of the solder powder. However, since the pressure resistance performance is required for the manufacturing apparatus, the boiling point is desirably higher by 10 ° C. than the melting temperature of the solder powder to be obtained. Further, as the non-aqueous solvent, the solder powder reacts with oxygen and easily forms an oxide on the surface, so that a solvent having a reducing property is more preferable.
本発明での非水系溶媒とはその沸点が、１５０℃以上であるものが好適であり、２００℃以上であるものが特に好適である。後述するように、はんだ粉を得るためには、非水系溶媒として得ようとするはんだ粉の融点よりも高い沸点を持つものが好ましいが、攪拌をおこなう容器に圧力容器を用いることにより、雰囲気圧力を上げ、常圧の沸点がはんだ粉の融点より低い非水系溶媒でも、使用が可能である。しかしながら製造装置に耐圧性能が必要となるので、沸点は、得ようとするはんだ粉の溶融温度よりも１０℃以上高いことが望ましい。更に非水系溶媒として、はんだ粉が酸素と反応して、表面に酸化物を形成しやすいために、還元性を有する溶媒であることが更に好ましい。 <Non-aqueous solvent>
The non-aqueous solvent in the present invention preferably has a boiling point of 150 ° C. or higher, and particularly preferably has a boiling point of 200 ° C. or higher. As will be described later, in order to obtain solder powder, it is preferable to have a boiling point higher than the melting point of the solder powder to be obtained as a non-aqueous solvent, but by using a pressure vessel as a vessel for stirring, the atmospheric pressure It is possible to use a non-aqueous solvent whose boiling point at normal pressure is lower than the melting point of the solder powder. However, since the pressure resistance performance is required for the manufacturing apparatus, the boiling point is desirably higher by 10 ° C. than the melting temperature of the solder powder to be obtained. Further, as the non-aqueous solvent, the solder powder reacts with oxygen and easily forms an oxide on the surface, so that a solvent having a reducing property is more preferable.
例えば、このような非水系溶媒の一例として、沸点が１５０℃から４００℃の範囲のアルコール系溶媒が挙げられる。具体的にはＳｎ－Ａｇ－Ｃｕ系はんだの融点が２１８℃の場合、且つ常圧下で以下に述べる攪拌操作を行ない、微粉化されたはんだ粉を得るためには、非水系溶媒の沸点は２２０℃以上であることが好ましく、２５０℃以上であることが更に好ましい。
For example, an alcohol solvent having a boiling point in the range of 150 ° C. to 400 ° C. is an example of such a non-aqueous solvent. Specifically, when the melting point of the Sn—Ag—Cu solder is 218 ° C. and the following stirring operation is performed under normal pressure, a non-aqueous solvent has a boiling point of 220 in order to obtain finely divided solder powder. It is preferable that the temperature is higher than or equal to ° C, more preferably higher than or equal to 250 ° C.
具体的には、非水系溶媒として、一価アルコール、または二価アルコールのグリコールがある。一価アルコールとしては、例えば、ブチルアルコール、アミルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、デシルアルコール、ノニルアルコール、シクロペンタノール、ベンジルアルコール、シンナミルアルコール等がある。グリコール系の溶媒としては、グリセリン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、トリメチレングリコール、ブタンジオール、ペンタンジオール、ヘキサンジオール、ヘプタンジオール、オクタンジオール、ノナンジオール、デカンジオール、ベンズピナコール、ヒドロベンゾイル、シクロペンダジオール、シクロヘキサンジオール、シクロヘキサンジオール、グリコール酸アミド、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールジブチルエーテル、酢酸ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセタート等があり、分子量の大きいものではポリエチレングリコール、ポリエチレングリコールエステル、ポリエチレングリコールエーテルがある。特にグリコール、ジオール系のものは水酸基を二つ持つものであるため、極性を持ち、粉の分散性に寄与するので望ましい。このような溶媒としては、例えば－ＣＨ２－ＣＨＯＨ、または－ＣＨＲ－ＣＨＯＨ、－ＣＲ１Ｒ２－ＣＨＯＨ、＝ＣＨＣＨＯＨ、＝ＣＲＣＨＯＨ（Ｒ、Ｒ１、Ｒ２：側鎖）を分子中に含まれるもので、且つ溶媒の沸点は少なくとも１００℃以上のものである。更にはアルデヒド基－ＣＨＯを持つ有機化合物も同様な効果を持ち、例えば、脂肪族飽和アルデヒドとして、ラウリンアルデヒド、トリデシルアルデヒド、ミリスチンアルデヒド、カプロンアルデヒド、ヘプトアルデヒド、ペンタデシルアルデヒド、パルミチンアルデヒド、マルガリンアルデヒド、ステアリンアルデヒドが挙げられ、脂肪族ジアルデヒドとしては例えばスクシンジアルデヒドがあり、脂肪族不飽和アルデヒドとして、クロトンアルデヒド、更には芳香族アルデヒドには、ベンズアルデヒド、トルアルデヒド、サリチルアルデヒド、シンナムアルデヒド、ナフトアルデヒド等があり、複素環式アルデヒドにはフルフラールが挙げられる。アミン系の還元性溶媒としては、ヘキシルアミン、ヘブチンアミン、オクチルアミン、ウンデシルアミン、トリデシルアミン、テトラデシルアミン、ペンタデシルアミン、セチルアミン、ジブチルアミン、ジアミルアミン、シクロヘキシルアミン、アニリン、ナフチルアミン、トルイジン等がある。
Specifically, the non-aqueous solvent includes a monohydric alcohol or a dihydric alcohol glycol. Examples of the monohydric alcohol include butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, decyl alcohol, nonyl alcohol, cyclopentanol, benzyl alcohol, and cinnamyl alcohol. Examples of glycol solvents include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, benzpinacol, hydro Benzoyl, cyclopentadiol, cyclohexanediol, cyclohexanediol, glycolic acid amide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monoethyl ether, diethylene glycol dibutyl ether, acetic acid diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, etc. big Intended polyethylene glycol, polyethylene glycol esters, polyethylene glycol ethers. In particular, glycols and diols are preferable because they have two hydroxyl groups and thus have polarity and contribute to the dispersibility of the powder. Examples of such a solvent include —CH 2 —CHOH, or —CHR—CHOH, —CR 1 R 2 —CHOH, ═CHCHOH, ═CRCHOH (R, R 1 , R 2 : side chain) in the molecule. The boiling point of the solvent is at least 100 ° C. or higher. Furthermore, organic compounds having an aldehyde group —CHO have the same effect. For example, aliphatic saturated aldehydes such as lauric aldehyde, tridecyl aldehyde, myristic aldehyde, capron aldehyde, heptaldehyde, pentadecyl aldehyde, palmitic aldehyde, marga aldehyde Examples include aliphatic aldehydes such as succindialdehyde, aliphatic unsaturated aldehydes such as crotonaldehyde, and aromatic aldehydes such as benzaldehyde, tolualdehyde, salicylaldehyde, and cinnamaldehyde. And naphthaldehyde, and the heterocyclic aldehyde includes furfural. Examples of amine-based reducing solvents include hexylamine, hebutinamine, octylamine, undecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, dibutylamine, diamylamine, cyclohexylamine, aniline, naphthylamine, and toluidine. is there.
＜粉砕用ボール＞
本発明に用いる粉砕用ボールとしては、材質としてセラミックス系を用いたアルミナボール、ジルコニアボール、ムライトボール、ガラスボール、金属系のステンレスボールや鉄ボール等を使用することができ、特に材質に制限はないが、粉砕用ボールの材質として、耐久性が高く、はんだ粉への不純物の混入が少ない利点のある、ジルコニア、アルミナ、ステンレス鋼が、特に好適である。 <Crushing ball>
As the grinding balls used in the present invention, alumina balls, zirconia balls, mullite balls, glass balls, metallic stainless balls, iron balls, etc. using ceramics can be used, and the material is not particularly limited. Nonetheless, zirconia, alumina, and stainless steel are particularly suitable as the material for the ball for pulverization, which has the advantages of high durability and low contamination of solder powder.
本発明に用いる粉砕用ボールとしては、材質としてセラミックス系を用いたアルミナボール、ジルコニアボール、ムライトボール、ガラスボール、金属系のステンレスボールや鉄ボール等を使用することができ、特に材質に制限はないが、粉砕用ボールの材質として、耐久性が高く、はんだ粉への不純物の混入が少ない利点のある、ジルコニア、アルミナ、ステンレス鋼が、特に好適である。 <Crushing ball>
As the grinding balls used in the present invention, alumina balls, zirconia balls, mullite balls, glass balls, metallic stainless balls, iron balls, etc. using ceramics can be used, and the material is not particularly limited. Nonetheless, zirconia, alumina, and stainless steel are particularly suitable as the material for the ball for pulverization, which has the advantages of high durability and low contamination of solder powder.
粉砕用ボールは、粒径が０．０５ｍｍ～５ｍｍであることが好ましい。粒径１５ｍｍ超の粉砕用ボールのみを使用すると、目的とする微細な粒径を持つはんだ粉を得ることが難しくなり、粒径０．０５ｍｍ未満の粉砕用ボールのみを使用すると、攪拌後の固液分離に時間を要することがある。
より粒径の小さいはんだ粉を容易に得るためには、粉砕用ボールの粒径は、０．１～５ｍｍが更に好ましく、０．１～３ｍｍが一層好ましく、０．１～１ｍｍが更に一層好ましい。粉砕用ボールを大きな粒径のものと小さな粒径のものとを組み合わせて使用することも可能である。この場合には、大きなボールサイズは特に粒径１５ｍｍにこだわる必要はなく、例えば、粒径３０ｍｍでも良い。少なくとも粒径０．０５ｍｍ～１５ｍｍの粉砕用ボールが５０質量％入っていることが必要である。 The grinding balls preferably have a particle size of 0.05 mm to 5 mm. If only pulverizing balls having a particle diameter of more than 15 mm are used, it becomes difficult to obtain solder powder having a desired fine particle diameter. If only pulverizing balls having a particle diameter of less than 0.05 mm are used, solidification after stirring is difficult. Liquid separation may take time.
In order to easily obtain a solder powder having a smaller particle diameter, the particle diameter of the ball for grinding is more preferably 0.1 to 5 mm, still more preferably 0.1 to 3 mm, and still more preferably 0.1 to 1 mm. . It is also possible to use a pulverizing ball in combination of a large particle size and a small particle size. In this case, the large ball size need not be particularly concerned with the particle size of 15 mm, and may be, for example, a particle size of 30 mm. It is necessary that at least 50% by mass of grinding balls having a particle size of 0.05 mm to 15 mm be contained.
より粒径の小さいはんだ粉を容易に得るためには、粉砕用ボールの粒径は、０．１～５ｍｍが更に好ましく、０．１～３ｍｍが一層好ましく、０．１～１ｍｍが更に一層好ましい。粉砕用ボールを大きな粒径のものと小さな粒径のものとを組み合わせて使用することも可能である。この場合には、大きなボールサイズは特に粒径１５ｍｍにこだわる必要はなく、例えば、粒径３０ｍｍでも良い。少なくとも粒径０．０５ｍｍ～１５ｍｍの粉砕用ボールが５０質量％入っていることが必要である。 The grinding balls preferably have a particle size of 0.05 mm to 5 mm. If only pulverizing balls having a particle diameter of more than 15 mm are used, it becomes difficult to obtain solder powder having a desired fine particle diameter. If only pulverizing balls having a particle diameter of less than 0.05 mm are used, solidification after stirring is difficult. Liquid separation may take time.
In order to easily obtain a solder powder having a smaller particle diameter, the particle diameter of the ball for grinding is more preferably 0.1 to 5 mm, still more preferably 0.1 to 3 mm, and still more preferably 0.1 to 1 mm. . It is also possible to use a pulverizing ball in combination of a large particle size and a small particle size. In this case, the large ball size need not be particularly concerned with the particle size of 15 mm, and may be, for example, a particle size of 30 mm. It is necessary that at least 50% by mass of grinding balls having a particle size of 0.05 mm to 15 mm be contained.
粉砕用ボールの表面に、はんだが付着しにくい材質であるダイヤモンドライクカーボン（ＤＬＣ）やＢ，Ｃ，Ｎ等の化合物を形成することができる。
Diamond-like carbon (DLC) or a compound such as B, C, or N, which is a material to which solder is difficult to adhere, can be formed on the surface of the grinding ball.
＜混合物の体積比＞
前記混合物の体積比は、用いる非水系溶媒の体積に対して、金属原料は、０．１体積％～２０体積％が好ましく、０．１体積％～１０体積％が一層好ましい。粉砕用ボールは、用いる非水系溶媒の体積に対して、２０体積％～６００体積％が好ましい。金属原料が０．１体積％未満の場合、生産性が低くなり、２０体積％超の場合には、得られるはんだ粉の粒径が十分小さくならないことがある。粉砕用ボールが２０体積％未満の場合には、得られるはんだ粉の粒径が十分小さくならないことがあり、６００体積％超の場合は、粉砕用ボールの表面に原料用金属が多く付着した状態となることがある。前記混合物を容器中で静置したときに、前記粉砕用ボールの上面と前記非水系溶媒の上面の高さが、略同一となるように、前記粉砕用ボールの前記非水系溶媒に対する体積比率を調整することにより、微粒子のはんだ粉が得やすくなるので、更に好ましい。 <Volume ratio of the mixture>
The volume ratio of the mixture is preferably 0.1% by volume to 20% by volume, and more preferably 0.1% by volume to 10% by volume with respect to the volume of the non-aqueous solvent used. The grinding balls are preferably 20% by volume to 600% by volume with respect to the volume of the non-aqueous solvent used. When the metal raw material is less than 0.1% by volume, the productivity is low, and when it exceeds 20% by volume, the particle size of the obtained solder powder may not be sufficiently small. When the pulverizing ball is less than 20% by volume, the particle size of the obtained solder powder may not be sufficiently small. When the pulverizing ball is more than 600% by volume, a large amount of raw material metal adheres to the surface of the pulverizing ball. It may become. When the mixture is allowed to stand in a container, the volume ratio of the grinding ball to the non-aqueous solvent is set so that the height of the top surface of the grinding ball and the top surface of the non-aqueous solvent are substantially the same. By adjusting, it becomes easier to obtain fine solder powder, which is more preferable.
前記混合物の体積比は、用いる非水系溶媒の体積に対して、金属原料は、０．１体積％～２０体積％が好ましく、０．１体積％～１０体積％が一層好ましい。粉砕用ボールは、用いる非水系溶媒の体積に対して、２０体積％～６００体積％が好ましい。金属原料が０．１体積％未満の場合、生産性が低くなり、２０体積％超の場合には、得られるはんだ粉の粒径が十分小さくならないことがある。粉砕用ボールが２０体積％未満の場合には、得られるはんだ粉の粒径が十分小さくならないことがあり、６００体積％超の場合は、粉砕用ボールの表面に原料用金属が多く付着した状態となることがある。前記混合物を容器中で静置したときに、前記粉砕用ボールの上面と前記非水系溶媒の上面の高さが、略同一となるように、前記粉砕用ボールの前記非水系溶媒に対する体積比率を調整することにより、微粒子のはんだ粉が得やすくなるので、更に好ましい。 <Volume ratio of the mixture>
The volume ratio of the mixture is preferably 0.1% by volume to 20% by volume, and more preferably 0.1% by volume to 10% by volume with respect to the volume of the non-aqueous solvent used. The grinding balls are preferably 20% by volume to 600% by volume with respect to the volume of the non-aqueous solvent used. When the metal raw material is less than 0.1% by volume, the productivity is low, and when it exceeds 20% by volume, the particle size of the obtained solder powder may not be sufficiently small. When the pulverizing ball is less than 20% by volume, the particle size of the obtained solder powder may not be sufficiently small. When the pulverizing ball is more than 600% by volume, a large amount of raw material metal adheres to the surface of the pulverizing ball. It may become. When the mixture is allowed to stand in a container, the volume ratio of the grinding ball to the non-aqueous solvent is set so that the height of the top surface of the grinding ball and the top surface of the non-aqueous solvent are substantially the same. By adjusting, it becomes easier to obtain fine solder powder, which is more preferable.
＜加熱・攪拌工程＞
前記金属原料と、前記非水系溶媒と、前記粉砕用ボールの混合物を加熱・攪拌することにより、平均粒径が０．０５μｍ以上、３μｍ未満であるはんだ粉を生成することができる。 <Heating and stirring process>
By heating and stirring the mixture of the metal raw material, the non-aqueous solvent, and the grinding balls, a solder powder having an average particle size of 0.05 μm or more and less than 3 μm can be generated.
前記金属原料と、前記非水系溶媒と、前記粉砕用ボールの混合物を加熱・攪拌することにより、平均粒径が０．０５μｍ以上、３μｍ未満であるはんだ粉を生成することができる。 <Heating and stirring process>
By heating and stirring the mixture of the metal raw material, the non-aqueous solvent, and the grinding balls, a solder powder having an average particle size of 0.05 μm or more and less than 3 μm can be generated.
加熱・攪拌する雰囲気は、不活性ガスまたは還元性ガスとすることが好ましい。雰囲気を空気とした場合、生成したはんだ粉の表面に厚い酸化膜が生成することがあり、雰囲気中の酸素濃度は低いほうが好ましい。不活性ガスとしては、窒素、アルゴン等が挙げられ、還元性ガスとしては、水素または水素と不活性ガスの混合ガスが挙げられる。
The atmosphere for heating and stirring is preferably an inert gas or a reducing gas. When the atmosphere is air, a thick oxide film may be formed on the surface of the generated solder powder, and it is preferable that the oxygen concentration in the atmosphere is low. Examples of the inert gas include nitrogen and argon, and examples of the reducing gas include hydrogen or a mixed gas of hydrogen and an inert gas.
加熱・攪拌する際、混合物の加熱温度は、得ようとするはんだ粉の合金組成物の融点より高い温度とすればよいが、前記融点より５℃低い温度～前記融点より２０℃高い温度に加熱することが好ましい。より好ましくは、前記融点と同じ温度～前記融点より１７℃高い温度とすればよい。また、さらに好ましくは、前記融点より７℃高い温度～前記融点より１２℃高い温度とすればよい。合金組成物の融点近傍の温度で加熱・攪拌を行うことではんだ粉の収率（はんだ粉収量／はんだ合金原料投入量）が好適なものとなる。前記加熱温度は、使用する非水系溶媒の沸点（加圧下で加熱・攪拌する場合には、該加圧下での沸点）未満の温度とする。
When heating / stirring, the heating temperature of the mixture may be higher than the melting point of the alloy composition of the solder powder to be obtained, but it is heated to a temperature 5 ° C. lower than the melting point to 20 ° C. higher than the melting point. It is preferable to do. More preferably, the temperature may be the same temperature as the melting point to 17 ° C. higher than the melting point. More preferably, the temperature may be 7 ° C. higher than the melting point to 12 ° C. higher than the melting point. By heating and stirring at a temperature near the melting point of the alloy composition, the yield of solder powder (solder powder yield / solder alloy raw material input amount) becomes suitable. The heating temperature is set to a temperature lower than the boiling point of the non-aqueous solvent to be used (in the case of heating and stirring under pressure, the boiling point under pressure).
攪拌は、攪拌羽根を回転することによりおこなうことができ、ミル等の粉砕用ボールを用いることができる粉砕機を用いておこなってもよい。回転数等の粉砕条件は、混合物の内容と得ようとするはんだ粉の平均粒径に応じて、適宜選択すれば良く、攪拌羽根等の回転数を上昇させることにより、得られるはんだ粉の平均粒径を小さくすることができる。例えば、攪拌羽根を用いる場合、その回転数は、１００～１０００００
ｒｐｍの範囲、攪拌羽根の周速は、１００～５０００ｃｍ／ｓｅｃの範囲に設定することができる。 Stirring can be performed by rotating a stirring blade, and may be performed using a pulverizer that can use pulverizing balls such as a mill. The pulverization conditions such as the number of revolutions may be appropriately selected according to the content of the mixture and the average particle diameter of the solder powder to be obtained. By increasing the number of revolutions of the stirring blade, the average of the obtained solder powder The particle size can be reduced. For example, when a stirring blade is used, the rotational speed is 100 to 100,000.
The range of rpm and the peripheral speed of the stirring blade can be set in the range of 100 to 5000 cm / sec.
ｒｐｍの範囲、攪拌羽根の周速は、１００～５０００ｃｍ／ｓｅｃの範囲に設定することができる。 Stirring can be performed by rotating a stirring blade, and may be performed using a pulverizer that can use pulverizing balls such as a mill. The pulverization conditions such as the number of revolutions may be appropriately selected according to the content of the mixture and the average particle diameter of the solder powder to be obtained. By increasing the number of revolutions of the stirring blade, the average of the obtained solder powder The particle size can be reduced. For example, when a stirring blade is used, the rotational speed is 100 to 100,000.
The range of rpm and the peripheral speed of the stirring blade can be set in the range of 100 to 5000 cm / sec.
＜粉砕用ボールの分離＞
加熱・攪拌後、混合物は、攪拌をおこなった状態で、はんだ粉の融点より１０℃以上低い温度まで冷却する。その後、混合物から粉砕用ボールをメッシュを通す等の公知の手段により分離して、はんだ粉と非水系溶媒の混合物を得る。 <Separation of balls for grinding>
After the heating / stirring, the mixture is cooled to a temperature lower by 10 ° C. or more than the melting point of the solder powder in a state of stirring. Thereafter, the mixture is separated from the mixture by a known means such as passing a pulverizing ball through a mesh to obtain a mixture of solder powder and a non-aqueous solvent.
加熱・攪拌後、混合物は、攪拌をおこなった状態で、はんだ粉の融点より１０℃以上低い温度まで冷却する。その後、混合物から粉砕用ボールをメッシュを通す等の公知の手段により分離して、はんだ粉と非水系溶媒の混合物を得る。 <Separation of balls for grinding>
After the heating / stirring, the mixture is cooled to a temperature lower by 10 ° C. or more than the melting point of the solder powder in a state of stirring. Thereafter, the mixture is separated from the mixture by a known means such as passing a pulverizing ball through a mesh to obtain a mixture of solder powder and a non-aqueous solvent.
＜固液分離＞
前記工程で得られたはんだ粉と非水系溶媒の混合物の固液分離をおこなう。固液分離は、遠心分離、フィルタープレスによるろ過等の公知の方法によりおこなうことができる。なお、用いた非水系溶媒が、はんだ粉の分散媒として支障ない場合には、固液分離をおこなう必要はない。 <Solid-liquid separation>
Solid-liquid separation of the mixture of the solder powder and non-aqueous solvent obtained in the above step is performed. Solid-liquid separation can be performed by a known method such as centrifugation or filtration with a filter press. In addition, when the used non-aqueous solvent does not have a trouble as a dispersion medium of solder powder, it is not necessary to perform solid-liquid separation.
前記工程で得られたはんだ粉と非水系溶媒の混合物の固液分離をおこなう。固液分離は、遠心分離、フィルタープレスによるろ過等の公知の方法によりおこなうことができる。なお、用いた非水系溶媒が、はんだ粉の分散媒として支障ない場合には、固液分離をおこなう必要はない。 <Solid-liquid separation>
Solid-liquid separation of the mixture of the solder powder and non-aqueous solvent obtained in the above step is performed. Solid-liquid separation can be performed by a known method such as centrifugation or filtration with a filter press. In addition, when the used non-aqueous solvent does not have a trouble as a dispersion medium of solder powder, it is not necessary to perform solid-liquid separation.
＜洗浄・乾燥＞
固液分離したはんだ粉は、溶媒で洗浄することができる。前記溶媒としては、メタノール、エタノール等の低沸点であるアルコールの有機溶媒が好適な例としてあげられる。洗浄後、真空乾燥等の高温加熱をおこなわない方法で乾燥することにより、使用した非水系溶媒の残留が少ないはんだ粉を得ることができる。 <Washing and drying>
The solid-liquid separated solder powder can be washed with a solvent. A suitable example of the solvent is an organic solvent of alcohol having a low boiling point such as methanol or ethanol. After washing, drying by a method that does not perform high-temperature heating, such as vacuum drying, can yield a solder powder with little residual non-aqueous solvent used.
固液分離したはんだ粉は、溶媒で洗浄することができる。前記溶媒としては、メタノール、エタノール等の低沸点であるアルコールの有機溶媒が好適な例としてあげられる。洗浄後、真空乾燥等の高温加熱をおこなわない方法で乾燥することにより、使用した非水系溶媒の残留が少ないはんだ粉を得ることができる。 <Washing and drying>
The solid-liquid separated solder powder can be washed with a solvent. A suitable example of the solvent is an organic solvent of alcohol having a low boiling point such as methanol or ethanol. After washing, drying by a method that does not perform high-temperature heating, such as vacuum drying, can yield a solder powder with little residual non-aqueous solvent used.
［実施例１］
Ｓｎ９９質量％、Ａｇ０．３質量％、Ｃｕ０．７質量％である組成のはんだ合金線１ｍｍΦを１０ｇ秤量し、このはんだ線を３００ｍＬのセパラブルフラスコに投入した。前記はんだ合金線の融点を示差走査熱量計（ＤＳＣ）（株式会社リガク製、Ｔｈｅｒｍｏ ｐｌｕｓ ＤＳＣ８２３０）で測定した結果、融点は、２１８℃であった。次に０．３ｍｍΦのジルコニアボール３００ｇを前記セパブルフラスコに投入し、更に、テトラエチレングリコール１００ｍＬを投入して、混合物を得た。この後、セパラブルフラスコの上蓋をして密封し、窒素ガスを１００ｍＬ／ｍｉｎで流し、１０分間ガス置換をした。次に、セパブルフラスコ内に設置してあった回転径が６ｃｍのステンレス製の攪拌羽根を７００ｒｐｍ回転させることにより攪拌をおこなった状態で、混合物を表１に記載の１４種類の温度（加熱温度）まで加熱した。なお、混合物の温度は、セパブルフラスコ内に設置された熱電対により測定した。混合物を前記加熱温度で１時間保持した後、前記攪拌状態を維持したまま、前記混合物を５℃／ｍｉｎの冷却速度で冷却した。混合物が４０℃以下になった段階で攪拌羽根の回転を止めた。次にこの混合物を２５０メッシュのナイロン生地の網を通過させて、０．３ｍｍΦのジルコニアボールを混合物から分離した。ろ過された側には微粉化したはんだ粉が分散した溶媒（テトラエチレングリコール）が回収された。テトラエチレングリコールを洗浄除去するために、前記はんだ粉が分散した溶媒を３０００ｒｐｍ、５分間の処理条件で遠心分離して固液分離し、上澄みの液体を除去して、はんだ粉を回収した。この後、下記の要領で、洗浄を行った。回収したはんだ粉を１００ｍLのエタノール中と攪拌混合し、再分散した後、３０００ｒｐｍ、５分間の処理条件で遠心分離して固液分離し、上澄みの液体を除去して、はんだ粉を回収した。この回収したはんだ粉をエタノール中に分散後、遠心分離による固液分離する操作を５回繰返しおこなった。得られたはんだ粉を６０℃で真空乾燥して、加熱温度が異なる１４種類の乾燥済みのはんだ粉を得た。 [Example 1]
10 g of solder alloy wire 1 mmΦ having a composition of Sn 99% by mass, Ag 0.3% by mass and Cu 0.7% by mass was weighed, and this solder wire was put into a 300 mL separable flask. As a result of measuring the melting point of the solder alloy wire with a differential scanning calorimeter (DSC) (manufactured by Rigaku Corporation, Thermo plus DSC 8230), the melting point was 218 ° C. Next, 300 g of 0.3 mmφ zirconia balls were charged into the separable flask, and 100 mL of tetraethylene glycol was further charged to obtain a mixture. Thereafter, the upper lid of the separable flask was sealed and sealed, and nitrogen gas was allowed to flow at 100 mL / min to perform gas replacement for 10 minutes. Next, in a state where stirring was performed by rotating a stainless steel stirring blade having a rotational diameter of 6 cm installed in the separable flask at 700 rpm, the mixture was subjected to 14 kinds of temperatures (heating temperature) shown in Table 1 ). The temperature of the mixture was measured with a thermocouple installed in a separable flask. After maintaining the mixture at the heating temperature for 1 hour, the mixture was cooled at a cooling rate of 5 ° C./min while maintaining the stirring state. When the mixture became 40 ° C. or lower, the rotation of the stirring blade was stopped. The mixture was then passed through a mesh of 250 mesh nylon fabric to separate 0.3 mmΦ zirconia balls from the mixture. On the filtered side, a solvent (tetraethylene glycol) in which finely divided solder powder was dispersed was recovered. In order to wash away tetraethylene glycol, the solvent in which the solder powder was dispersed was centrifuged at 3000 rpm for 5 minutes and subjected to solid-liquid separation, and the supernatant liquid was removed to collect the solder powder. Thereafter, cleaning was performed in the following manner. The collected solder powder was stirred and mixed with 100 mL of ethanol and redispersed, and then centrifuged at 3000 rpm for 5 minutes to perform solid-liquid separation, and the supernatant liquid was removed to collect the solder powder. The collected solder powder was dispersed in ethanol and then subjected to solid-liquid separation by centrifugation five times. The obtained solder powder was vacuum-dried at 60 ° C. to obtain 14 types of dried solder powder having different heating temperatures.
Ｓｎ９９質量％、Ａｇ０．３質量％、Ｃｕ０．７質量％である組成のはんだ合金線１ｍｍΦを１０ｇ秤量し、このはんだ線を３００ｍＬのセパラブルフラスコに投入した。前記はんだ合金線の融点を示差走査熱量計（ＤＳＣ）（株式会社リガク製、Ｔｈｅｒｍｏ ｐｌｕｓ ＤＳＣ８２３０）で測定した結果、融点は、２１８℃であった。次に０．３ｍｍΦのジルコニアボール３００ｇを前記セパブルフラスコに投入し、更に、テトラエチレングリコール１００ｍＬを投入して、混合物を得た。この後、セパラブルフラスコの上蓋をして密封し、窒素ガスを１００ｍＬ／ｍｉｎで流し、１０分間ガス置換をした。次に、セパブルフラスコ内に設置してあった回転径が６ｃｍのステンレス製の攪拌羽根を７００ｒｐｍ回転させることにより攪拌をおこなった状態で、混合物を表１に記載の１４種類の温度（加熱温度）まで加熱した。なお、混合物の温度は、セパブルフラスコ内に設置された熱電対により測定した。混合物を前記加熱温度で１時間保持した後、前記攪拌状態を維持したまま、前記混合物を５℃／ｍｉｎの冷却速度で冷却した。混合物が４０℃以下になった段階で攪拌羽根の回転を止めた。次にこの混合物を２５０メッシュのナイロン生地の網を通過させて、０．３ｍｍΦのジルコニアボールを混合物から分離した。ろ過された側には微粉化したはんだ粉が分散した溶媒（テトラエチレングリコール）が回収された。テトラエチレングリコールを洗浄除去するために、前記はんだ粉が分散した溶媒を３０００ｒｐｍ、５分間の処理条件で遠心分離して固液分離し、上澄みの液体を除去して、はんだ粉を回収した。この後、下記の要領で、洗浄を行った。回収したはんだ粉を１００ｍLのエタノール中と攪拌混合し、再分散した後、３０００ｒｐｍ、５分間の処理条件で遠心分離して固液分離し、上澄みの液体を除去して、はんだ粉を回収した。この回収したはんだ粉をエタノール中に分散後、遠心分離による固液分離する操作を５回繰返しおこなった。得られたはんだ粉を６０℃で真空乾燥して、加熱温度が異なる１４種類の乾燥済みのはんだ粉を得た。 [Example 1]
10 g of solder alloy wire 1 mmΦ having a composition of Sn 99% by mass, Ag 0.3% by mass and Cu 0.7% by mass was weighed, and this solder wire was put into a 300 mL separable flask. As a result of measuring the melting point of the solder alloy wire with a differential scanning calorimeter (DSC) (manufactured by Rigaku Corporation, Thermo plus DSC 8230), the melting point was 218 ° C. Next, 300 g of 0.3 mmφ zirconia balls were charged into the separable flask, and 100 mL of tetraethylene glycol was further charged to obtain a mixture. Thereafter, the upper lid of the separable flask was sealed and sealed, and nitrogen gas was allowed to flow at 100 mL / min to perform gas replacement for 10 minutes. Next, in a state where stirring was performed by rotating a stainless steel stirring blade having a rotational diameter of 6 cm installed in the separable flask at 700 rpm, the mixture was subjected to 14 kinds of temperatures (heating temperature) shown in Table 1 ). The temperature of the mixture was measured with a thermocouple installed in a separable flask. After maintaining the mixture at the heating temperature for 1 hour, the mixture was cooled at a cooling rate of 5 ° C./min while maintaining the stirring state. When the mixture became 40 ° C. or lower, the rotation of the stirring blade was stopped. The mixture was then passed through a mesh of 250 mesh nylon fabric to separate 0.3 mmΦ zirconia balls from the mixture. On the filtered side, a solvent (tetraethylene glycol) in which finely divided solder powder was dispersed was recovered. In order to wash away tetraethylene glycol, the solvent in which the solder powder was dispersed was centrifuged at 3000 rpm for 5 minutes and subjected to solid-liquid separation, and the supernatant liquid was removed to collect the solder powder. Thereafter, cleaning was performed in the following manner. The collected solder powder was stirred and mixed with 100 mL of ethanol and redispersed, and then centrifuged at 3000 rpm for 5 minutes to perform solid-liquid separation, and the supernatant liquid was removed to collect the solder powder. The collected solder powder was dispersed in ethanol and then subjected to solid-liquid separation by centrifugation five times. The obtained solder powder was vacuum-dried at 60 ° C. to obtain 14 types of dried solder powder having different heating temperatures.
加熱温度が２１５℃～２３５℃である６種類の前記乾燥済みのはんだ粉を、反射型のＦＴ－ＩＲ（PerkinElmer社製、Spectrum 100）でテトラエチレングリコールのヒドロキシ基のピークの有無について調べたが、前記ピークは認められなかった。
Six types of the dried solder powder having a heating temperature of 215 ° C. to 235 ° C. were examined with a reflection type FT-IR (manufactured by PerkinElmer, Spectrum® 100) for the presence or absence of a hydroxy group peak of tetraethylene glycol. The peak was not observed.
加熱温度が２１５℃～２３５℃である６種類の前記乾燥済みのはんだ粉について、ＳＥＭ観察を行った結果、粒子形状は球状であった。前記乾燥済みのはんだ粉の平均粒径Ｄ５０を表１に示した。
なお、本願では、はんだ粉試料０．３ｇをイソプロピルアルコール３０ｍＬに入れ、４５Ｗ超音波洗浄器にて５分間処理後、当該処理液に対しマイクロトラック９３２０－Ｘ１００（ハネウエル－日機装製）を用いて粒径測定した際の、累積５０質量％粒径（Ｄ５０）を銀粉の平均粒径とした。ここで、平均粒径Ｄ５０について説明する。測定対象であるはんだ粉全体の粒度分布が求められたとき、その銀紛全体積を１００％として累積カーブを求めたとき、その累積カーブが、例えば、１０％、５０％、９０％となる点の粒子径をそれぞれＤ１０、Ｄ５０、Ｄ９０と表記した。そして、累積中位径（Ｍｅｄｉａｎ径）であるＤ５０を、平均粒径としている。
得られた乾燥済みのはんだ粉の質量を、使用したはんだ合金線の質量で除することにより、はんだ粉の収率を計算した。その結果を、表１に示す。
As a result of SEM observation of the six types of the dried solder powder having a heating temperature of 215 ° C. to 235 ° C., the particle shape was spherical. The average particle diameter D50 of the dried solder powder is shown in Table 1.
In the present application, 0.3 g of a solder powder sample is placed in 30 mL of isopropyl alcohol, treated with a 45 W ultrasonic cleaner for 5 minutes, and then treated with the microtrac 9320-X100 (Honeywell-Nikkiso Co., Ltd.). The cumulative 50% by mass particle diameter (D50) when the diameter was measured was defined as the average particle diameter of the silver powder. Here, the average particle diameter D50 will be described. When the particle size distribution of the entire solder powder to be measured is obtained, the cumulative curve is, for example, 10%, 50%, and 90% when the cumulative curve is obtained with the total volume of the silver powder as 100%. Were expressed as D10, D50, and D90, respectively. And D50 which is an accumulation median diameter (Median diameter) is made into the average particle diameter.
The yield of the solder powder was calculated by dividing the mass of the obtained dried solder powder by the mass of the solder alloy wire used. The results are shown in Table 1.
なお、本願では、はんだ粉試料０．３ｇをイソプロピルアルコール３０ｍＬに入れ、４５Ｗ超音波洗浄器にて５分間処理後、当該処理液に対しマイクロトラック９３２０－Ｘ１００（ハネウエル－日機装製）を用いて粒径測定した際の、累積５０質量％粒径（Ｄ５０）を銀粉の平均粒径とした。ここで、平均粒径Ｄ５０について説明する。測定対象であるはんだ粉全体の粒度分布が求められたとき、その銀紛全体積を１００％として累積カーブを求めたとき、その累積カーブが、例えば、１０％、５０％、９０％となる点の粒子径をそれぞれＤ１０、Ｄ５０、Ｄ９０と表記した。そして、累積中位径（Ｍｅｄｉａｎ径）であるＤ５０を、平均粒径としている。
得られた乾燥済みのはんだ粉の質量を、使用したはんだ合金線の質量で除することにより、はんだ粉の収率を計算した。その結果を、表１に示す。
In the present application, 0.3 g of a solder powder sample is placed in 30 mL of isopropyl alcohol, treated with a 45 W ultrasonic cleaner for 5 minutes, and then treated with the microtrac 9320-X100 (Honeywell-Nikkiso Co., Ltd.). The cumulative 50% by mass particle diameter (D50) when the diameter was measured was defined as the average particle diameter of the silver powder. Here, the average particle diameter D50 will be described. When the particle size distribution of the entire solder powder to be measured is obtained, the cumulative curve is, for example, 10%, 50%, and 90% when the cumulative curve is obtained with the total volume of the silver powder as 100%. Were expressed as D10, D50, and D90, respectively. And D50 which is an accumulation median diameter (Median diameter) is made into the average particle diameter.
The yield of the solder powder was calculated by dividing the mass of the obtained dried solder powder by the mass of the solder alloy wire used. The results are shown in Table 1.
［実施例２］
はんだ合金線の組成をＳｎ９９質量％、Ａｇ０．３質量％、Ｃｕ０．７質量％から、Ｓｎ９６．５質量％、Ａｇ３．０質量％、Ｃｕ０．５質量％に変更し、前記加熱温度を表１の１４種類から表２の１３種類に変更した以外は、実施例１と同様の方法で乾燥済みはんだ粉を得て、評価をおこなった。なお、はんだ合金線の融点を測定した結果、２２３℃であった。 [Example 2]
The composition of the solder alloy wire was changed from Sn 99 mass%, Ag 0.3 mass%, Cu 0.7 mass% to Sn 96.5 mass%, Ag 3.0 mass%, Cu 0.5 mass%, and the heating temperature was changed to Table 1. The dry solder powder was obtained by the same method as in Example 1 except that the 14 types were changed from 13 types to 13 types shown in Table 2, and evaluated. In addition, as a result of measuring melting | fusing point of a solder alloy wire, it was 223 degreeC.
はんだ合金線の組成をＳｎ９９質量％、Ａｇ０．３質量％、Ｃｕ０．７質量％から、Ｓｎ９６．５質量％、Ａｇ３．０質量％、Ｃｕ０．５質量％に変更し、前記加熱温度を表１の１４種類から表２の１３種類に変更した以外は、実施例１と同様の方法で乾燥済みはんだ粉を得て、評価をおこなった。なお、はんだ合金線の融点を測定した結果、２２３℃であった。 [Example 2]
The composition of the solder alloy wire was changed from Sn 99 mass%, Ag 0.3 mass%, Cu 0.7 mass% to Sn 96.5 mass%, Ag 3.0 mass%, Cu 0.5 mass%, and the heating temperature was changed to Table 1. The dry solder powder was obtained by the same method as in Example 1 except that the 14 types were changed from 13 types to 13 types shown in Table 2, and evaluated. In addition, as a result of measuring melting | fusing point of a solder alloy wire, it was 223 degreeC.
前記乾燥済みのはんだ粉を、反射型のＦＴ－ＩＲでテトラエチレングリコールのヒドロキシ基のピークの有無について調べたが、前記ピークは認められなかった。
The dried solder powder was examined for the presence or absence of a hydroxy group peak of tetraethylene glycol by a reflective FT-IR, but the peak was not observed.
加熱温度が２１５℃～２３５℃である６種類の前記乾燥済みのはんだ粉について、ＳＥＭ観察を行った結果、粒子形状は球状であった。前記乾燥済みのはんだ粉の平均粒径Ｄ５０とはんだ粉の収率を表２に示した。
As a result of SEM observation of the six types of the dried solder powder having a heating temperature of 215 ° C. to 235 ° C., the particle shape was spherical. Table 2 shows the average particle diameter D50 of the dried solder powder and the yield of the solder powder.
［実施例３］
はんだ合金線の組成をＳｎ９９質量％、Ａｇ０．３質量％、Ｃｕ０．７質量％から、表３に記載の５種類に変更し、前記加熱温度を表１の１４種類から表３、表４、表５の加熱温度（はんだ合金の融点＋５℃、はんだ合金の融点－１０℃、はんだ合金の融点－１０℃）に変更した以外は、実施例１と同様の方法で乾燥済みはんだ粉を得て、評価をおこなった。なお、５種類の組成のはんだ合金線について、融点を測定した結果を表３～表５に示した。また、表３～表５には各試料におけるはんだ粉の収率とはんだ粉の平均粒径Ｄ５０を示した。
[Example 3]
The composition of the solder alloy wire was changed from Sn 99 mass%, Ag 0.3 mass%, Cu 0.7 mass% to five types shown in Table 3, and the heating temperature was changed from 14 types in Table 1 to Table 3, Table 4, A dried solder powder was obtained in the same manner as in Example 1 except that the heating temperatures in Table 5 were changed (melting point of solder alloy + 5 ° C., melting point of solder alloy−10 ° C., melting point of solder alloy−10 ° C.). And evaluated. Tables 3 to 5 show the results of measuring the melting points of the solder alloy wires having five compositions. Tables 3 to 5 show the yield of solder powder and the average particle diameter D50 of the solder powder in each sample.
はんだ合金線の組成をＳｎ９９質量％、Ａｇ０．３質量％、Ｃｕ０．７質量％から、表３に記載の５種類に変更し、前記加熱温度を表１の１４種類から表３、表４、表５の加熱温度（はんだ合金の融点＋５℃、はんだ合金の融点－１０℃、はんだ合金の融点－１０℃）に変更した以外は、実施例１と同様の方法で乾燥済みはんだ粉を得て、評価をおこなった。なお、５種類の組成のはんだ合金線について、融点を測定した結果を表３～表５に示した。また、表３～表５には各試料におけるはんだ粉の収率とはんだ粉の平均粒径Ｄ５０を示した。
The composition of the solder alloy wire was changed from Sn 99 mass%, Ag 0.3 mass%, Cu 0.7 mass% to five types shown in Table 3, and the heating temperature was changed from 14 types in Table 1 to Table 3, Table 4, A dried solder powder was obtained in the same manner as in Example 1 except that the heating temperatures in Table 5 were changed (melting point of solder alloy + 5 ° C., melting point of solder alloy−10 ° C., melting point of solder alloy−10 ° C.). And evaluated. Tables 3 to 5 show the results of measuring the melting points of the solder alloy wires having five compositions. Tables 3 to 5 show the yield of solder powder and the average particle diameter D50 of the solder powder in each sample.
前記乾燥済みのはんだ粉を、反射型のＦＴ－ＩＲでテトラエチレングリコールのヒドロキシ基のピークの有無について調べたが、前記ピークは認められなかった。
加熱温度が融点＋５℃である５種類の前記乾燥済みのはんだ粉について、ＳＥＭ観察を行った結果、粒子形状は球状であった。この乾燥済みのはんだ粉の平均粒径Ｄ５０とはんだ粉の収率を表３に示した。そして、表４および表５に示すように、加熱温度が、融点－１０℃および融点＋３０℃である場合には、いずれもはんだ粉の収率は１％未満であった。 The dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
As a result of SEM observation of the five types of dried solder powder having a heating temperature of the melting point + 5 ° C., the particle shape was spherical. Table 3 shows the average particle diameter D50 of the dried solder powder and the yield of the solder powder. As shown in Tables 4 and 5, when the heating temperatures were the melting point −10 ° C. and the melting point + 30 ° C., the yield of the solder powder was less than 1%.
加熱温度が融点＋５℃である５種類の前記乾燥済みのはんだ粉について、ＳＥＭ観察を行った結果、粒子形状は球状であった。この乾燥済みのはんだ粉の平均粒径Ｄ５０とはんだ粉の収率を表３に示した。そして、表４および表５に示すように、加熱温度が、融点－１０℃および融点＋３０℃である場合には、いずれもはんだ粉の収率は１％未満であった。 The dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
As a result of SEM observation of the five types of dried solder powder having a heating temperature of the melting point + 5 ° C., the particle shape was spherical. Table 3 shows the average particle diameter D50 of the dried solder powder and the yield of the solder powder. As shown in Tables 4 and 5, when the heating temperatures were the melting point −10 ° C. and the melting point + 30 ° C., the yield of the solder powder was less than 1%.
［実施例４］
はんだ合金線の質量を１０ｇから、表６に記載の値に、加熱温度を表１に記載の値から表６に記載の値に変更した以外は、実施例１と同様の方法で乾燥済みはんだ粉を得て、評価をおこなった。 [Example 4]
Solder that has been dried in the same manner as in Example 1 except that the mass of the solder alloy wire was changed from 10 g to the value shown in Table 6, and the heating temperature was changed from the value shown in Table 1 to the value shown in Table 6. Powder was obtained and evaluated.
はんだ合金線の質量を１０ｇから、表６に記載の値に、加熱温度を表１に記載の値から表６に記載の値に変更した以外は、実施例１と同様の方法で乾燥済みはんだ粉を得て、評価をおこなった。 [Example 4]
Solder that has been dried in the same manner as in Example 1 except that the mass of the solder alloy wire was changed from 10 g to the value shown in Table 6, and the heating temperature was changed from the value shown in Table 1 to the value shown in Table 6. Powder was obtained and evaluated.
前記乾燥済みのはんだ粉を、反射型のＦＴ－ＩＲでテトラエチレングリコールのヒドロキシ基のピークの有無について調べたが、前記ピークは認められなかった。
前記乾燥済みのはんだ粉の平均粒径Ｄ５０とはんだ粉の収率を表６に示した。表６の結果から粉砕時の合金濃度が変化しても、好適なはんだ粉収率を得るための加熱温度の範囲は変わらないことが分かった。
The dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
Table 6 shows the average particle diameter D50 of the dried solder powder and the yield of the solder powder. From the results in Table 6, it was found that the heating temperature range for obtaining a suitable solder powder yield did not change even when the alloy concentration during pulverization was changed.
前記乾燥済みのはんだ粉の平均粒径Ｄ５０とはんだ粉の収率を表６に示した。表６の結果から粉砕時の合金濃度が変化しても、好適なはんだ粉収率を得るための加熱温度の範囲は変わらないことが分かった。
Table 6 shows the average particle diameter D50 of the dried solder powder and the yield of the solder powder. From the results in Table 6, it was found that the heating temperature range for obtaining a suitable solder powder yield did not change even when the alloy concentration during pulverization was changed.
［実施例５］
加熱温度を表１に記載の値から２５０℃に変更し、冷却速度を５℃／ｍｉｎから、２００℃に到達するまでは０．２℃／ｍｉｎに変更した以外は、実施例１と同様の方法で乾燥済みはんだ粉を得て、評価をおこなった。 [Example 5]
The heating temperature was changed from the value shown in Table 1 to 250 ° C., and the cooling rate was changed from 5 ° C./min to 0.2 ° C./min until reaching 200 ° C., as in Example 1. The dried solder powder was obtained by the method and evaluated.
加熱温度を表１に記載の値から２５０℃に変更し、冷却速度を５℃／ｍｉｎから、２００℃に到達するまでは０．２℃／ｍｉｎに変更した以外は、実施例１と同様の方法で乾燥済みはんだ粉を得て、評価をおこなった。 [Example 5]
The heating temperature was changed from the value shown in Table 1 to 250 ° C., and the cooling rate was changed from 5 ° C./min to 0.2 ° C./min until reaching 200 ° C., as in Example 1. The dried solder powder was obtained by the method and evaluated.
前記乾燥済みのはんだ粉を、反射型のＦＴ－ＩＲでテトラエチレングリコールのヒドロキシ基のピークの有無について調べたが、前記ピークは認められなかった。
前記乾燥済みのはんだ粉の平均粒径Ｄ５０は、０．９μｍであり、はんだ粉の収率は、３０質量％であった。 The dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
The average particle diameter D50 of the dried solder powder was 0.9 μm, and the yield of the solder powder was 30% by mass.
前記乾燥済みのはんだ粉の平均粒径Ｄ５０は、０．９μｍであり、はんだ粉の収率は、３０質量％であった。 The dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
The average particle diameter D50 of the dried solder powder was 0.9 μm, and the yield of the solder powder was 30% by mass.
［実施例６］
加熱温度を表２に記載の値から２５５℃に変更し、冷却速度を５℃／ｍｉｎから、２１０℃に到達するまでは０．２℃／ｍｉｎに変更した以外は、実施例２と同様の方法で乾燥済みはんだ粉を得て、評価をおこなった。 [Example 6]
The heating temperature was changed from the value described in Table 2 to 255 ° C, and the cooling rate was changed from 5 ° C / min to 0.2 ° C / min until reaching 210 ° C, which was the same as in Example 2. The dried solder powder was obtained by the method and evaluated.
加熱温度を表２に記載の値から２５５℃に変更し、冷却速度を５℃／ｍｉｎから、２１０℃に到達するまでは０．２℃／ｍｉｎに変更した以外は、実施例２と同様の方法で乾燥済みはんだ粉を得て、評価をおこなった。 [Example 6]
The heating temperature was changed from the value described in Table 2 to 255 ° C, and the cooling rate was changed from 5 ° C / min to 0.2 ° C / min until reaching 210 ° C, which was the same as in Example 2. The dried solder powder was obtained by the method and evaluated.
前記乾燥済みのはんだ粉を、反射型のＦＴ－ＩＲでテトラエチレングリコールのヒドロキシ基のピークの有無について調べたが、前記ピークは認められなかった。
前記乾燥済みのはんだ粉の平均粒径Ｄ５０は、０．９μｍであり、はんだ粉の収率は、３２質量％であった。 The dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
The average particle diameter D50 of the dried solder powder was 0.9 μm, and the yield of the solder powder was 32% by mass.
前記乾燥済みのはんだ粉の平均粒径Ｄ５０は、０．９μｍであり、はんだ粉の収率は、３２質量％であった。 The dried solder powder was examined by reflection-type FT-IR for the presence or absence of a tetraethylene glycol hydroxy group peak, but the peak was not observed.
The average particle diameter D50 of the dried solder powder was 0.9 μm, and the yield of the solder powder was 32% by mass.
本発明は、粒径が微細であるはんだ粉の製造方法に適用できる。
The present invention can be applied to a method for producing solder powder having a fine particle size.
Claims (8)
- 容器中に、固体または液体の金属と、非水系溶媒と、直径０．０５ｍｍ～５ｍｍの粉砕用ボールとを入れ、混合物を得る工程と、
前記混合物を前記金属の融点－５℃～前記金属の融点＋２０℃に加熱し、攪拌する工程と、
攪拌後の前記混合物から粉砕用ボールを分離して、はんだ粉と非水系溶媒の混合物を得る工程と、
前記はんだ粉と非水系溶媒の混合物を固液分離して、はんだ粉を得る工程を有する、はんだ粉の製造方法。 Placing a solid or liquid metal, a non-aqueous solvent, and a grinding ball having a diameter of 0.05 mm to 5 mm in a container to obtain a mixture;
Heating the mixture to a melting point of the metal of −5 ° C. to a melting point of the metal of + 20 ° C. and stirring;
Separating the grinding balls from the mixture after stirring to obtain a mixture of solder powder and a non-aqueous solvent;
A method for producing solder powder, comprising solid-liquid separation of a mixture of the solder powder and a non-aqueous solvent to obtain solder powder. - 前記非水系溶媒の沸点は１５０℃以上である、請求項１に記載のはんだ粉の製造方法。 The method for producing solder powder according to claim 1, wherein the non-aqueous solvent has a boiling point of 150 ° C. or higher.
- 前記非水系溶媒はアルデヒド基またはヒドロキシ基を有する有機溶媒である、請求項２に記載のはんだ粉の製造方法。 The method for producing solder powder according to claim 2, wherein the non-aqueous solvent is an organic solvent having an aldehyde group or a hydroxy group.
- 前記非水系溶媒は一級アミノ基、または二級アミノ基、または三級アミノ基の内の少なくとも一種以上を含む有機溶媒である、請求項２に記載のはんだ粉の製造方法。 The method for producing solder powder according to claim 2, wherein the non-aqueous solvent is an organic solvent containing at least one of a primary amino group, a secondary amino group, or a tertiary amino group.
- 羽根を周速２００ｃｍ／秒～２００００ｃｍ／秒で回転することにより前記攪拌する工程を行う、請求項１に記載のはんだ粉の製造方法。 The method for producing solder powder according to claim 1, wherein the stirring step is performed by rotating a blade at a peripheral speed of 200 cm / sec to 20000 cm / sec.
- 前記固液分離を遠心分離またはフィルタープレスにより行う、請求項１に記載のはんだ粉の製造方法。 The method for producing solder powder according to claim 1, wherein the solid-liquid separation is performed by centrifugation or a filter press.
- 前記はんだ粉と非水系溶媒の混合物を固液分離した後、はんだ粉を沸点１５０℃以下の有機溶媒で洗浄する、請求項１に記載のはんだ粉の製造方法。 The method for producing solder powder according to claim 1, wherein after the mixture of the solder powder and the non-aqueous solvent is solid-liquid separated, the solder powder is washed with an organic solvent having a boiling point of 150 ° C. or lower.
- 前記金属の体積が、前記非水系溶媒の体積の０．１体積％～２０体積％である、請求項１に記載のはんだ粉の製造方法。 The method for producing solder powder according to claim 1, wherein the volume of the metal is 0.1 vol% to 20 vol% of the volume of the non-aqueous solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009263519A JP5813917B2 (en) | 2009-11-19 | 2009-11-19 | Solder powder manufacturing method |
| JP2009-263519 | 2009-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2011062222A1 true WO2011062222A1 (en) | 2011-05-26 |
Family
ID=44059696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2010/070563 WO2011062222A1 (en) | 2009-11-19 | 2010-11-18 | Process for producing solder powder |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5813917B2 (en) |
| WO (1) | WO2011062222A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111432980A (en) * | 2017-12-22 | 2020-07-17 | 积水化学工业株式会社 | Solder particle, conductive material, method for storing solder particle, method for storing conductive material, method for producing conductive material, connection structure, and method for producing connection structure |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6126426B2 (en) * | 2013-03-28 | 2017-05-10 | 新日鉄住金化学株式会社 | Joining method |
| KR102535911B1 (en) * | 2022-08-12 | 2023-05-30 | 오컴퍼니 주식회사 | Solder Particle With Active Coating, Mixture With Solder Particle For Making Film, Film For Connecting Terminals |
| KR102489828B1 (en) * | 2022-08-12 | 2023-01-18 | 오컴퍼니 주식회사 | Method For Form An Active Coating On Solder Particle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS64204A (en) * | 1987-06-22 | 1989-01-05 | Fukuda Metal Foil & Powder Co Ltd | Production of low melting point metal powder |
| JPH0533017A (en) * | 1991-07-15 | 1993-02-09 | Minnesota Mining & Mfg Co <3M> | Preparation of low melting point metal fine particle and composition containing it |
| WO2009011981A2 (en) * | 2007-05-31 | 2009-01-22 | The Administrators Of The Tulane Educational Fund | Method of forming stable functionalized nanoparticles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4063005B2 (en) * | 2002-07-31 | 2008-03-19 | 住友金属鉱山株式会社 | Rare earth-transition metal-nitrogen based magnet powder and method for producing the same |
-
2009
- 2009-11-19 JP JP2009263519A patent/JP5813917B2/en not_active Expired - Fee Related
-
2010
- 2010-11-18 WO PCT/JP2010/070563 patent/WO2011062222A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS64204A (en) * | 1987-06-22 | 1989-01-05 | Fukuda Metal Foil & Powder Co Ltd | Production of low melting point metal powder |
| JPH0533017A (en) * | 1991-07-15 | 1993-02-09 | Minnesota Mining & Mfg Co <3M> | Preparation of low melting point metal fine particle and composition containing it |
| WO2009011981A2 (en) * | 2007-05-31 | 2009-01-22 | The Administrators Of The Tulane Educational Fund | Method of forming stable functionalized nanoparticles |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111432980A (en) * | 2017-12-22 | 2020-07-17 | 积水化学工业株式会社 | Solder particle, conductive material, method for storing solder particle, method for storing conductive material, method for producing conductive material, connection structure, and method for producing connection structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5813917B2 (en) | 2015-11-17 |
| JP2011104634A (en) | 2011-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10458004B2 (en) | Silver-bismuth powder, conductive paste and conductive film | |
| WO2012066664A1 (en) | Solder powder and process for producing solder powder | |
| WO2013031588A1 (en) | Solder powder, and solder paste using solder powder | |
| JP5813917B2 (en) | Solder powder manufacturing method | |
| JP5895344B2 (en) | Method for producing solder powder and method for producing solder paste using solder powder produced by this method | |
| CN110434350A (en) | A kind of metal powder with low melting point and its preparation method and application | |
| JP5962461B2 (en) | Au-Ge-Sn solder alloy | |
| TW201736605A (en) | Silver alloy powder and method for producing same | |
| JP5750913B2 (en) | Solder powder and solder paste using this powder | |
| JP5478193B2 (en) | Solder powder manufacturing method | |
| EP2716387A1 (en) | Coated cobalt powder and preparation method thereof | |
| JP5878284B2 (en) | Method for producing metal or alloy nanoparticles | |
| JP5661540B2 (en) | Cu-Ga based alloy powder having low oxygen content, Cu-Ga based alloy target material, and method for producing target material | |
| JP5484722B2 (en) | Method for separating and regenerating components of waste solder paste | |
| KR101014281B1 (en) | method for manufacturing ultrafine lead-free solder powder for lead-free solder paste | |
| JP2014213337A (en) | Solder alloy | |
| JP2019038002A (en) | Material for metal junction | |
| TW201619399A (en) | Au-sn-ag-based solder alloy, electronic device sealed or joined using the same, and electronic apparatus equipped with the electronic device | |
| JP2006002176A (en) | Spherical fine copper powder and method for manufacturing spherical fine copper powder | |
| JP2017100145A (en) | Method for production of solder powder | |
| CN114496342B (en) | Preparation method of low-melting-point metal particles, conductive paste and preparation method thereof | |
| KR20100098481A (en) | Apparatus for manufacturing ultrafine lead-free solder powder for lead-free solder paste | |
| JP2011235314A (en) | Pb-FREE SOLDER ALLOY HAVING ZN AS MAIN COMPONENT | |
| JP2022022743A (en) | Method for producing metal powder | |
| EP2548677B1 (en) | Solder powder-cleaning agent and method for making solder powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10831615 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 10831615 Country of ref document: EP Kind code of ref document: A1 |