Patent Publication Number: US-2017355043-A1

Title: Solder alloy, solder paste and electronic circuit board

Description:
TECHNICAL FIELD 
     The present invention relates to a solder alloy, a solder paste, and an electronic circuit board, to be specific, to a solder alloy, a solder paste containing the solder alloy, and furthermore, an electronic circuit board obtained by using the solder paste. 
     BACKGROUND ART 
     In metal connection in electrical and electronic devices or the like, solder connection using a solder paste has been generally used and in such a solder paste, a solder alloy containing lead has been conventionally used. 
     However, in view of environmental load, the use of lead has been recently required to be suppressed and thus, the development of a solder alloy without containing lead (lead-free solder alloy) has been promoted. 
     As such a lead-free solder alloy, for example, a tin-copper alloy, a tin-silver-copper alloy, a tin-silver-indium-bismuth alloy, a tin-bismuth alloy, and a tin-zinc alloy have been well known and among all, a tin-silver-copper alloy, a tin-silver-indium-bismuth alloy, and the like have been widely used. 
     To be more specific, for example, for such a tin-silver-copper alloy, Patent Document 1 below has proposed a solder material containing 3.4 mass % of silver, 0.7 mass % of copper, 0.04 mass % of nickel, 3.0 mass % of antimony, 3.2 mass % of bismuth, and 0.01 mass % of cobalt, and Sn of the remaining portion. 
     CITATION LIST 
     Patent Document 
     
         
         Patent Document 1: WO2014/163167 
       
    
     SUMMARY OF THE INVENTION 
     Problem to be Solved by the Invention 
     Meanwhile, soldering with such a solder alloy may cause damages on solder connection portion by shock such as dropping vibration. Therefore, improvement in shock resistance after soldering is required for the solder alloy. 
     Furthermore, a component soldered with a solder alloy may be used under relatively severe temperature cycle conditions (e.g., temperature cycle between −40 to 125° C. etc.) such as an engine room of automobiles. Therefore, the solder alloy has been required to keep shock resistance even if it is exposed to relatively severe temperature cycle conditions. 
     An object of the present invention is to provide a solder alloy having excellent shock resistance and which can keep excellent shock resistance even under exposure to relatively severe temperature cycle conditions, a solder paste containing the solder alloy, and an electronic circuit board produced by using the solder paste. 
     Means for Solving the Problem 
     A solder alloy according to one aspect of the present invention is a solder alloy consisting essentially of tin, silver, copper, bismuth, antimony, and cobalt, wherein relative to a total amount of the solder alloy, the silver content is 2 mass % or more and 4 mass % or less, the copper content is 0.3 mass % or more and 1 mass % or less, the bismuth content is more than 4.8 mass % and 10 mass % or less, the antimony content is 3 mass % or more and 10 mass % or less, the cobalt content is 0.001 mass % or more and 0.3 mass % or less, the tin content is the remaining proportion. 
     It is preferable that the solder alloy further contains at least one element selected from the group consisting of nickel, indium, gallium, germanium, and phosphorus, and relative to a total amount of the solder alloy, more than 0 mass % and 1 mass % or less of the element is contained. 
     It is preferable that in the solder alloy, the copper content is 0.5 mass % or more and 0.7 mass % or less. 
     It is preferable that the bismuth content is more than 4.8 mass % and 7 mass % or less. 
     It is preferable that the antimony content is 5 mass % or more and 7 mass % or less. 
     It is preferable that the cobalt content is 0.003 mass % or more and 0.01 mass % or less. 
     A solder paste according to another aspect of the present invention contains a solder powder composed of the above-described solder alloy and flux. 
     An electronic circuit board according to further another aspect of the present invention includes a soldering portion soldered with the above-described solder paste. 
     Effect of the Invention 
     In the solder alloy according to one aspect of the present invention, the solder alloy consisting essentially of tin, silver, copper, bismuth, antimony, and cobalt is designed to contain the components in the above-described amounts. 
     Therefore, the solder alloy according to one aspect of the present invention achieves excellent shock resistance, and can keep excellent shock resistance even under exposure to relatively severe temperature cycle conditions. 
     The solder paste according to another aspect of the present invention contains the above-described solder alloy, and therefore achieves excellent shock resistance, and can keep excellent shock resistance even under exposure to relatively severe temperature cycle conditions. 
     In the electronic circuit board according to still another aspect of the present invention, the above-described solder paste are used in soldering, and therefore excellent shock resistance can be achieved, and excellent shock resistance can be kept even under exposure to relatively severe temperature cycle conditions. 
    
    
     DESCRIPTION OF EMBODIMENTS 
     The solder alloy according to one aspect of the present invention contains, as essential components, tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), antimony (Sb), and cobalt (Co). In other words, the solder alloy consists essentially of tin, silver, copper, bismuth, antimony, and cobalt. In this specification, “essentially” means that allowing the above-described elements to be essential components and an optional component to be described later to be contained at a proportion to be described later. 
     In the solder alloy, the tin content is the remaining ratio relative to each of the components to be described later and is suitably set in accordance with the amount of the components blended. 
     The silver content relative to a total amount of the solder alloy is 2 mass % or more, preferably 3.0 mass % or more, more preferably 3.3 mass % or more, 4 mass % or less, preferably 3.8 mass % or less, more preferably 3.6 mass % or less. 
     When the silver content is within the above-described range, excellent shock resistance can be achieved, and excellent shock resistance can be kept even under exposure to relatively severe temperature cycle conditions. 
     Meanwhile, when the silver content is below the above-described lower limit, shock resistance is poor. When the silver content is more than the above-described upper limit as well, shock resistance is poor. 
     The copper content relative to a total amount of the solder alloy is 0.3 mass % or more, preferably 0.5 mass % or more, and 1 mass % or less, preferably 0.7 mass % or less. 
     When the copper content is within the above-described range, excellent shock resistance can be achieved, and excellent shock resistance can be kept even under exposure to relatively severe temperature cycle conditions. 
     Meanwhile, when the copper content is below the above-described lower limit, shock resistance is poor. When the copper content is more than the above-described upper limit as well, shock resistance is poor. 
     The bismuth content relative to a total amount of the solder alloy is more than 4.8 mass %, preferably 10 mass % or less, preferably 7 mass % or less. 
     When the bismuth content is within the above-described range, excellent shock resistance can be achieved, and excellent shock resistance can be kept even under exposure to relatively severe temperature cycle conditions. 
     Meanwhile, when the bismuth content is below the above-described lower limit, shock resistance is poor. When the bismuth content is more than the above-described upper limit as well, shock resistance is poor. 
     The antimony content relative to a total amount of the solder alloy is 3 mass % or more, preferably more than 3 mass %, more preferably 5 mass % or more, and 10 mass % or less, preferably 9.2 mass % or less, more preferably 7 mass % or less. 
     When the antimony content is within the above-described range, excellent shock resistance can be achieved, and excellent shock resistance can be kept even under exposure to relatively severe temperature cycle conditions. 
     Meanwhile, when the antimony content is below the above-described lower limit, shock resistance is poor. When the antimony content is more than the above-described upper limit as well, shock resistance is poor. 
     The cobalt content relative to a total amount of the solder alloy is 0.001 mass % or more, preferably 0.003 mass % or more, and 0.3 mass % or less, preferably 0.01 mass % or less, more preferably 0.007 mass % or less. 
     When the cobalt content is within the above-described range, excellent shock resistance can be achieved, and excellent shock resistance can be kept even under exposure to relatively severe temperature cycle conditions. 
     Meanwhile, when the cobalt content is below the above-described lower limit, shock resistance is poor. When the cobalt content is more than the above-described upper limit as well, shock resistance is poor. 
     The above-described solder alloy can further contain, as an optional component, nickel (Ni), indium (In), gallium (Ga), germanium (Ge), and phosphorus (P). 
     When the nickel is contained as an optional component, the nickel content is, for example, more than 0 mass % and, for example, 1.0 mass % or less relative to the total amount of the solder alloy. 
     When the nickel content is within the above-described range, excellent effects of the present invention can be retained. 
     When the indium is contained as an optional component, the indium content relative to a total amount of the solder alloy is, for example, more than 0 mass %, and for example, 1.0 mass % or less. 
     When the indium content is within the above-described range, excellent effects of the present invention can be retained. 
     When the gallium is contained as an optional component, the gallium content relative to the total amount of the solder alloy is, for example, more than 0 mass % and, for example, 1.0 mass % or less. 
     When the gallium content is within the above-described range, excellent effects of the present invention can be retained. 
     When the germanium is contained as an optional component, the germanium content relative to the total amount of the solder alloy is, for example, more than 0 mass % and, for example, 1.0 mass % or less. 
     When the germanium content is within the above-described range, excellent effects of the present invention can be retained. 
     When the phosphorus is contained as an optional component, the phosphorus content relative to the total amount of the solder alloy is, for example, more than 0 mass % and, for example, 1.0 mass % or less. 
     When the phosphorus content is within the above-described range, excellent effects of the present invention can be retained. 
     These optional components can be used singly or in combination of two or more. 
     When the above-described element is contained as an optional component, the content ratio thereof (in the case of being used in combination of two or more, the total amount thereof) relative to the total amount of the solder alloy is adjusted to be, for example, more than 0 mass % and, for example, 1.0 mass % or less. 
     When the total amount of the optional component content is within the above-described range, excellent effects of the present invention can be retained. 
     In view of improvement in shock resistance, in the above-described solder alloy, preferably, iron (Fe) is intentionally not contained. In other words, the solder alloy preferably contains no iron (Fe) except for iron (Fe) as impurity to be described later. 
     Such a solder alloy can be obtained by alloying the above-described metal components by a known method such as melting the metal components in a melting furnace to be unified. 
     The above-described metal components used in the production of the solder alloy can contain a small amount of impurities (inevitable impurities) as long as the excellent effects of the present invention are not inhibited. 
     Examples of the impurities include aluminum (Al), iron (Fe), zinc (Zn), and gold (Au). 
     The melting point of the solder alloy obtained in this manner measured by a DSC method (measurement conditions: temperature rising rate of 0.5° C./min.) is, for example, 190° C. or more, or preferably 200° C. or more, and, for example, 250° C. or less, or preferably 240° C. or less. 
     When the melting point of the solder alloy is within the above-described range, in a case where the solder alloy is used in the solder paste, metal connection can be easily performed with excellent workability. 
     In the above-described solder alloy, the solder alloy consisting essentially of tin, silver, copper, bismuth, antimony, and cobalt is designed to contain the components in the above-described predetermined amounts. 
     Therefore, the above-described solder alloy achieves excellent shock resistance, and excellent shock resistance can be kept even under exposure to relatively severe temperature cycle conditions. 
     Thus, the solder alloy is preferably contained in the solder paste (solder paste connecting material). 
     To be specific, the solder paste according to another aspect of the present invention contains the above-described solder alloy and flux. 
     The solder alloy in a powdered shape is preferably contained in the solder paste. 
     The powdered shape is not particularly limited and examples thereof include a substantially complete sphere shape, a flat block shape, a needle shape, and an amorphous shape. The powdered shape is suitably set in accordance with the properties (e.g., thixotropy, viscosity, etc.) required for the solder paste. 
     The average particle size (in the case of sphere shape) or the average longitudinal length (in the case of not sphere shape) of the powder of the solder alloy is, for example, 5 μm or more, or preferably 15 μm or more and, for example, 100 μm or less, or preferably 50 μm or less in measurement by using a particle diameter and particle size distribution analyzer by a laser diffraction method. 
     The flux is not particularly limited and known solder flux can be used. 
     To be specific, the flux is mainly composed of, for example, a base resin (rosin, acrylic resin, or the like), an activator (for example, hydrohalogenic acid salt of amine such as ethylamine and propylamine, and organic carboxylic acids such as lactic acid, citric acid, and benzoic acid), and a thixotropic agent (hardened castor oil, bees wax, carnauba wax, or the like) and can further contain an organic solvent when liquid flux is used. 
     The solder paste can be obtained by mixing the powder made from the above-described solder alloy with the above-described flux by a known method. 
     The mixing ratio of the solder alloy to the flux (solder alloy:flux (mass ratio)), is, for example, 70:30 to 95:5. 
     The above-described solder paste contains the above-described solder alloy, and therefore excellent shock resistance can be achieved, and excellent shock resistance can be kept even under exposure to relatively severe temperature cycle conditions. 
     The present invention includes an electronic circuit board including a soldering portion soldered with the above-described solder paste. 
     That is, the above-described solder paste is preferably used in, for example, soldering (metal connection) of an electrode of an electronic circuit board of, for example, an electrical and electronic device with an electronic component. 
     The electronic component is not particularly limited and an example thereof includes a known electronic component such as chip components (IC chip or the like), resistors, diodes, condensers, and transistors. 
     In the electronic circuit board, the above-described solder paste is used in soldering, and therefore excellent shock resistance can be achieved, and excellent shock resistance can be kept even under exposure to relatively severe temperature cycle conditions. 
     The method for using the above-described solder alloy is not limited to the above-described solder paste, and for example, the above-described solder alloy can be also used in, for example, the production of a resin flux cored solder connecting material. To be specific, for example, the above-described solder alloy is formed into a linear shape with the above-described flux as a core by a known method (for example, extrusion molding or the like), so that the resin flux cored solder connecting material can be also obtained. 
     Such a resin flux cored solder connecting material is also preferably used in, for example, soldering (metal connection) of an electronic circuit board of, for example, an electrical and electronic device in the same manner as that of the solder paste. 
     EXAMPLES 
     The present invention will hereinafter be described based on Examples and Comparative Examples. The present invention is however not limited by the following Examples. The specific numerical values in mixing ratio (content), property value, and parameter used in the following description can be replaced with upper limits (numerical values defined with “or less” or “below”) or lower limits (numerical values defined with “or more” or “more than”) of corresponding numerical values in mixing ratio (content), property value, and parameter described in the above-described “DESCRIPTION OF EMBODIMENTS”. 
     Examples 1 to 24 and Comparative Examples 1 to 16 
     Preparation of Solder Alloy 
     The powder of each of the metals described in Tables 1 to 2 was mixed at the mixing ratio described in Tables 1 to 2 and each of the obtained metal mixtures was melted to be unified in a melting furnace, thereby preparing solder alloys. 
     The tin (Sn) content in the mixing formulation of Examples and Comparative Examples is the remaining portion deducting the metals (silver (Ag), copper (Cu), bismuth (Bi), antimony (Sb), cobalt (Co), nickel (Ni), indium (In), gallium (Ga), germanium (Ge), phosphorus (P) and iron (Fe)) (mass %) shown in Tables 1 to 2 from the total amount of the solder alloy. 
     In the solder alloy of Example 1, metals of Ag, Cu, Bi, Sb, and Co are blended at the ratio shown in Table 1. The remaining portion is Sn. 
     In Examples 2 to 4, the Ag content was increased/decreased relative to the formulation in Example 1. 
     In Examples 5 to 7, the Cu content was increased/decreased relative to the formulation in Example 1. 
     In Examples 8 to 10, the Bi content was increased/decreased relative to the formulation in Example 1. 
     In Examples 11 to 14, the Sb content was increased/decreased relative to the formulation in Example 1. 
     In Examples 15 to 18, the Co content was increased/decreased relative to the formulation in Example 1. 
     In Examples 19 to 23, one of Ni, In, Ga, Ge, and P was added at the ratio shown in Table 1 relative to the formulation in Example 1, and in Example 24, all of Ni, In, Ga, Ge, and P was added at the ratio shown in Table 1 relative to the formulation in Example 1. 
     In Comparative Examples 1 to 2, the amount of Ag blended was increased/decreased relative to the formulation in Example 1 to make Ag excessive or insufficient. 
     In Comparative Examples 3 to 4, the amount of Cu blended was increased/decreased relative to the formulation in Example 1 to make Cu excessive or insufficient. 
     In Comparative Examples 5 to 6, the amount of Bi blended was increased/decreased relative to the formulation in Example 1 to make Bi excessive or insufficient. 
     In Comparative Examples 7 to 8, the amount of Sb blended was increased/decreased relative to the formulation in Example 1 to make Sb excessive or insufficient. 
     In Comparative Examples 9 to 10, the amount of Co blended was increased/decreased relative to the formulation in Example 1 to make Co excessive or insufficient. 
     In Comparative Example 11, the amounts of Bi and Sb blended were decreased to make both of Bi and Sb insufficient relative to the formulation in Example 17, and Ni was blended in the amount shown in Table 1. 
     In Comparative Example 12, the amounts of Bi and Sb blended were decreased to make both of Bi and Sb insufficient relative to the formulation in Example 17. 
     In Comparative Example 13, relative to the formulation in Example 17, Fe (0.01 mass %) was blended instead of Co (0.01 mass %). 
     In Comparative Example 14, the amount of Bi blended was decreased to make Bi insufficient relative to the formulation in Example 17.
     In Comparative Example 15, the amount of Sb blended was decreased to make Sb insufficient relative to the formulation in Example 17.   

     In Comparative Example 16, Fe was further blended relative to the formulation in Examples 17. 
     Preparation of Solder Paste 
     The obtained solder alloy was powdered so that the particle size thereof was 25 to 38 μm. The obtained powder of the solder alloy was mixed with known flux, thereby producing a solder paste. 
     Evaluation of Solder Paste 
     The obtained solder paste was printed on a print board for mounting chip components and a chip component was mounted thereon by a reflow method. The printing conditions of the solder paste at the time of mounting, the size of the chip component, and the like were suitably set in accordance with each of the evaluations to be described later. 
     
       
         
           
               
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                   
                 Mixing formulation (mass %) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 No. 
                 Ag 
                 Cu 
                 Bi 
                 Sb 
                 Co 
                 Ni 
                 In 
                 Ga 
                 Ge 
                 P 
                 Fe 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Example 1 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 2 
                 2.0 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 3 
                 3.0 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 4 
                 4.0 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 5 
                 3.5 
                 0.3 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 6 
                 3.5 
                 0.5 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 7 
                 3.5 
                 1.0 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 8 
                 3.5 
                 0.7 
                 4.9 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 9 
                 3.5 
                 0.7 
                 7.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 10 
                 3.5 
                 0.7 
                 10.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 11 
                 3.5 
                 0.7 
                 5.0 
                 3.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 12 
                 3.5 
                 0.7 
                 5.0 
                 7.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 13 
                 3.5 
                 0.7 
                 5.0 
                 8.5 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 14 
                 3.5 
                 0.7 
                 5.0 
                 10.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 15 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.001 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 16 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.003 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 17 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.010 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 18 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.300 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 19 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 0.5 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 20 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 0.5 
                 — 
                 — 
                 — 
                 — 
               
               
                 Example 21 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 0.5 
                 — 
                 — 
                 — 
               
               
                 Example 22 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 0.5 
                 — 
                 — 
               
               
                 Example 23 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 0.5 
                 — 
               
               
                 Example 24 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 — 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                   
                 Mixing formulation (mass %) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 No. 
                 Ag 
                 Cu 
                 Bi 
                 Sb 
                 Co 
                 Ni 
                 In 
                 Ga 
                 Ge 
                 P 
                 Fe 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Comp. Ex. 1 
                 1.5 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 2 
                 4.5 
                 0.7 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 3 
                 3.5 
                 0.1 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 4 
                 3.5 
                 1.5 
                 5.0 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 5 
                 3.5 
                 0.7 
                 4.5 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 6 
                 3.5 
                 0.7 
                 10.5 
                 5.0 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 7 
                 3.5 
                 0.7 
                 5.0 
                 2.5 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 8 
                 3.5 
                 0.7 
                 5.0 
                 10.5 
                 0.005 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 9 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.000 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 10 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.400 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 11 
                 3.5 
                 0.7 
                 3.2 
                 3.0 
                 0.01 
                 0.04 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 12 
                 3.5 
                 0.7 
                 3.2 
                 3.0 
                 0.01 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 13 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.01 
               
               
                 Comp. Ex. 14 
                 3.5 
                 0.7 
                 3.2 
                 5.0 
                 0.01 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 15 
                 3.5 
                 0.7 
                 5.0 
                 2.8 
                 0.01 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Comp. Ex. 16 
                 3.5 
                 0.7 
                 5.0 
                 5.0 
                 0.01 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.01 
               
               
                   
               
            
           
         
       
     
     &lt;Evaluation&gt; 
     The solder paste using the alloy produced in Examples and Comparative Example was printed on a printed board for mounting chip components, and a chip component was mounted thereon by a reflow method. The thickness of the printed solder paste was adjusted using a metal mask having a thickness of 150 μm. After printing of the solder paste, an aluminum electrolytic capacitor (5 mmφ, height 5.8 mm) was mounted on a predetermined position on the above-described printed circuit board, and they were heated in a reflow oven, thereby mounting the chip component. The reflow conditions were set as follows: preheating of 170 to 190° C., peak temperature of 245° C., time for the oven being at 220° C. or more to be 45 seconds, and cooling rate at the time when the temperature decreased from the peak temperature to 200° C. to be 3 to 8° C./sec. 
     Furthermore, the above-described printed circuit board was subjected to a cooling/heating cycle test in which it was kept under the environment of 125° C. for 30 minutes, and then, kept under the environment of −40° C. for 30 minutes. The results are shown in Table 3 and Table 4. 
     &lt;Drop/Shock&gt; 
     The printed circuit board immediately after mounting the components was dropped from a height of 1 m for 5 times, and evaluation was conducted by observing its appearance: it was checked if the connection portion between the component and the board was broken or not. 
     To be specific, of the 100 components mounted, those with dropped components of 5 or less were evaluated as rank A++ (5 points), those with dropped components of 6 to 10 were evaluated as rank A+ (4 points), those with dropped components of 11 to 15 were evaluated as rank A (3 points), those with dropped components of 16 to 30 were evaluated as rank B (2 points), those with dropped components of 31 to 50 were evaluated as rank C (1 point), and those with dropped components of 51 or more was evaluated as rank D (0 point). 
     Those printed circuit boards that went through the repeated cooling/heating cycles of 1000 cycles were evaluated in the same manner as described above. 
     &lt;Comprehensive Evaluation&gt; 
     In “Drop/shock” and “Shock resistance after cooling/heating cycle”, those with a total point of 10 was evaluated comprehensively as A++, a total point of 8 or 9 were evaluated comprehensively as A+, a total point of 6 or 7 points were evaluated comprehensively as A, a total point of 4 or 5 points were evaluated comprehensively as B, a total point of 2 or 3 points were evaluated comprehensively as C, and a total point of 0 or 1 point were evaluated comprehensively as D. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
               
                   
                 Shock 
                 Shock resistance after 
                 Comprehensive 
               
               
                 No. 
                 resistance 
                 cooling/heating cycle 
                 Evaluation 
               
               
                   
               
             
            
               
                 Example 1 
                 A++ 
                 A++ 
                 A++ 
               
               
                 Example 2 
                 A+ 
                 A 
                 A 
               
               
                 Example 3 
                 A++ 
                 A+ 
                 A+ 
               
               
                 Example 4 
                 A+ 
                 A 
                 A 
               
               
                 Example 5 
                 A 
                 A 
                 A 
               
               
                 Example 6 
                 A+ 
                 A+ 
                 A+ 
               
               
                 Example 7 
                 A 
                 A 
                 A 
               
               
                 Example 8 
                 A++ 
                 A+ 
                 A+ 
               
               
                 Example 9 
                 A+ 
                 A 
                 A 
               
               
                 Example 10 
                 A 
                 B 
                 B 
               
               
                 Example 11 
                 A 
                 B 
                 B 
               
               
                 Example 12 
                 A+ 
                 A+ 
                 A+ 
               
               
                 Example 13 
                 A 
                 A 
                 A 
               
               
                 Example 14 
                 B 
                 B 
                 B 
               
               
                 Example 15 
                 A 
                 A 
                 A 
               
               
                 Example 16 
                 A++ 
                 A+ 
                 A+ 
               
               
                 Example 17 
                 A+ 
                 A+ 
                 A+ 
               
               
                 Example 18 
                 A 
                 B 
                 B 
               
               
                 Example 19 
                 A++ 
                 A++ 
                 A++ 
               
               
                 Example 20 
                 A++ 
                 A++ 
                 A++ 
               
               
                 Example 21 
                 A++ 
                 A++ 
                 A++ 
               
               
                 Example 22 
                 A++ 
                 A++ 
                 A++ 
               
               
                 Example 23 
                 A++ 
                 A++ 
                 A++ 
               
               
                 Example 24 
                 A++ 
                 A++ 
                 A++ 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                 TABLE 4 
               
               
                   
               
               
                   
                 Shock 
                 Shock resistance after 
                 Comprehensive 
               
               
                 No. 
                 resistance 
                 cooling/heating cycle 
                 Evaluation 
               
               
                   
               
             
            
               
                 Comp. Ex. 1 
                 B 
                 C 
                 C 
               
               
                 Comp. Ex. 2 
                 B 
                 C 
                 C 
               
               
                 Comp. Ex. 3 
                 B 
                 C 
                 C 
               
               
                 Comp. Ex. 4 
                 B 
                 C 
                 C 
               
               
                 Comp. Ex. 5 
                 D 
                 D 
                 D 
               
               
                 Comp. Ex. 6 
                 D 
                 D 
                 D 
               
               
                 Comp. Ex. 7 
                 D 
                 D 
                 D 
               
               
                 Comp. Ex. 8 
                 D 
                 D 
                 D 
               
               
                 Comp. Ex. 9 
                 D 
                 D 
                 D 
               
               
                 Comp. Ex. 10 
                 D 
                 D 
                 D 
               
               
                 Comp. Ex. 11 
                 D 
                 D 
                 D 
               
               
                 Comp. Ex. 12 
                 D 
                 D 
                 D 
               
               
                 Comp. Ex. 13 
                 D 
                 D 
                 D 
               
               
                 Comp. Ex. 14 
                 C 
                 D 
                 D 
               
               
                 Comp. Ex. 15 
                 C 
                 D 
                 D 
               
               
                 Comp. Ex. 16 
                 C 
                 C 
                 C 
               
               
                   
               
            
           
         
       
     
     While the illustrative embodiments of the present invention are provided in the above description, such is for illustrative purpose only and it is not to be construed as limiting in any manner. Modification and variation of the present invention that will be obvious to those skilled in the art is to be covered by the following claims. 
     INDUSTRIAL APPLICABILITY 
     The solder alloy, the solder composition, and the solder paste of the present invention are used in an electronic circuit board used for electrical and electronic devices or the like.