FLUX AND SOLDER PASTE

Information

  • Patent Application
  • 20230089879
  • Publication Number
    20230089879
  • Date Filed
    February 17, 2021
    3 years ago
  • Date Published
    March 23, 2023
    a year ago
Abstract
A flux containing an organic acid, an acrylic resin, a rosin, a thixotropic agent, and a solvent, but not containing water is adopted. In this flux, the organic acid includes 1,2,3-propanetricarboxylic acid, and the content of the 1,2,3-propanetricarboxylic acid is 0.1% by mass or more and 15% by mass or less with respect to the total amount of the entire flux. According to this flux, the wettability of solder can be enhanced, temperature cycle reliability is excellent, and scattering due to heating during reflow can be suppressed.
Description
TECHNICAL FIELD

The present invention relates to a flux and a solder paste.


Priority is claimed on Japanese Patent Application No. 2020-025678, filed in Japan on Feb. 18, 2020, the content of which is incorporated herein by reference.


BACKGROUND ART

Generally, fluxes used for soldering have efficacy of chemically removing a metal oxide present between a solder and the metallic surface of an object to be joined, which is an object of soldering, and of enabling the movement of a metal element in the boundary between the solder and the object. Therefore, soldering using the flux allows the formation of an intermetallic compound between the solder and the metallic surface of the object to be joined, and strong joining can be obtained.


Conventionally, in order to impart wettability to solder, there has been a case where fluxes to which an inorganic acid has been added are used. However, fluxes containing an inorganic acid had a problem of corroding lead frames that support and fix semiconductor chips and a problem of generating a waste liquid of the inorganic acid.


In contrast, there has been a proposal of a flux for which a polyvalent carboxylic acid is used instead of inorganic acids. For example, Patent Document 1 proposes a flux containing a polyvalent carboxylic acid such as diglycolic acid and rosin. In addition, Patent Document 2 proposes a water-soluble flux containing a polyvalent carboxylic acid compound and water and capable of easily washing a residue.


CITATION LIST
Patent Documents



  • [Patent Document 1]



Japanese Unexamined Patent Application, First Publication No. 2013-82004

  • [Patent Document 2]


PCT International Publication No. WO 2002/038328


SUMMARY OF INVENTION
Technical Problem

However, regarding the flux described in Patent Document 1, there is a concern that, when the flux is applied onto a substrate and heated in a reflow furnace, a crack may be generated in a residue (the temperature cycle reliability is low). In addition, regarding the flux described in Patent Document 2, there is a concern that the flux may be scattered when heated.


Therefore, an object of the present invention is to provide a flux capable of enhancing the wettability of solder, having excellent temperature cycle reliability, and capable of suppressing scattering due to heating during reflow and a solder paste using the same.


Solution to Problem

In order to solve the above-described problems, the present invention adopted the following configurations.


That is, a first aspect of the present invention is a flux containing an organic acid, an acrylic resin, a rosin, a thixotropic agent, and a solvent, in which the flux does not contain water, the organic acid includes 1,2,3-propanetricarboxylic acid, and a content of the 1,2,3-propanetricarboxylic acid is 0.1% by mass or more and 15% by mass or less with respect to a total amount of the entire flux.


In the flux according to the first aspect, a content of the acrylic resin is preferably 5% by mass or more and 45% by mass or less with respect to the total amount of the entire flux.


In the flux according to the first aspect, a content of the rosin is preferably 5% by mass or more and 45% by mass or less with respect to the total amount of the entire flux.


In the flux according to the first aspect, a ratio (mass ratio) of a content of the rosin to a content of the acrylic resin is preferably 1 or more and 9 or less.


In addition, in the flux according to the first aspect, a total content of the organic acid is preferably 0.1% by mass or more and 15% by mass or less with respect to the total amount of the entire flux.


In addition, the flux according to the first aspect further contains azoles, in which a content of the azoles is preferably 0.1% by mass or more and 10% by mass or less with respect to the total amount of the entire flux.


In addition, in the flux according to the first aspect, a ratio (mass ratio) of the total content of the organic acid to the content of the azoles is preferably 0.6 or more and 100 or less.


In addition, the flux according to the first aspect further contains a resin other than the acrylic resin and the rosin, in which a content of the resin other than the acrylic resin and the rosin is preferably more than 0% by mass and 10% by mass or less with respect to the total amount of the entire flux.


In addition, the flux according to the first aspect further contains a halogen compound, in which a content of the halogen compound is preferably more than 0% by mass and 5% by mass or less with respect to the total amount of the entire flux. In addition, the flux according to the first aspect further contains an antioxidant, in which a content of the antioxidant is preferably more than 0% by mass and 5% by mass or less with respect to the total amount of the entire flux.


In addition, a second aspect of the present invention is a solder paste containing the flux according to the first aspect and a solder powder.


In addition, in the solder paste according to the second aspect, the solder powder is preferably composed of a solder alloy having an alloy composition containing As: 25 to 300 mass ppm, Pb: more than 0 mass ppm and 5100 mass ppm or less, at least one of Sb: more than 0 mass ppm and 3000 mass ppm or less and Bi: more than 0 mass ppm and 10000 mass ppm or less, and a balance of Sn and satisfying the following formula (1) and formula (2).





275≤2As+Sb+Bi+Pb  (1)





0.01≤(2As+Sb)/(Bi+Pb)≤10.00  (2)


In the formula (1) and the formula (2), As, Sb, Bi, and Pb each represent a content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the second aspect, the alloy composition preferably further satisfies the following formula (1a).





275≤2As+Sb+Bi+Pb≤25200  (1a)


In the formula (1a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the second aspect, the alloy composition preferably further satisfies the following formula (1b).





275≤2As+Sb+Bi+Pb≤5300  (1b)


In the formula (1b), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the second aspect, the alloy composition preferably further satisfies the following formula (2a).





0.31≤(2As+Sb)/(Bi+Pb)≤10.00  (2a)


In the formula (2a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the second aspect, the solder powder is preferably composed of a solder alloy having an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: more than 0 mass ppm and 10000 mass ppm or less and Pb: more than 0 mass ppm and 5100 mass ppm or less, Sb: more than 0 mass ppm and 3000 mass ppm or less, and a balance of Sn and satisfying the following formula (3) and formula (4).





300≤3As+Sb+Bi+Pb  (3)





0.1≤{(3As+Sb)/(Bi+Pb)}×100≤200  (4)


In the formula (3) and the formula (4), As, Sb, Bi, and Pb each represent a content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the second aspect, the alloy composition preferably further contains Ni: more than 0 mass ppm and 600 mass ppm or less.


In addition, in the solder paste according to the second aspect, the alloy composition preferably contains Fe: more than 0 mass ppm and 100 mass ppm or less.


In addition, in the solder paste according to the second aspect, the alloy composition preferably contains In: more than 0 mass ppm and 1200 mass ppm or less.


In addition, in the solder paste according to the second aspect, the alloy composition preferably further contains at least two of Ni: more than 0 mass ppm and 600 mass ppm or less, Fe: more than 0 mass ppm and 100 mass ppm or less and In: more than 0 mass ppm and 1200 mass ppm or less and satisfies the following formula (6).





0<Ni+Fe≤680  (6)


In the formula (6), Ni and Fe each represent a content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the second aspect, the alloy composition preferably further contains Ni: 0 mass ppm or more and 600 mass ppm or less and Fe: more than 0 mass ppm and 100 mass ppm or less and satisfies the following formula (5) and the following formula (6).





0≤Ni/Fe≤50  (5)





0<Ni+Fe≤680  (6)


In the formula (5) and the formula (6), Ni and Fe each represent a content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the second aspect, the alloy composition preferably further satisfies the following formula (3a).





300≤3As+Sb+Bi+Pb≤18214  (3a)


In the formula (3a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the second aspect, the alloy composition preferably further satisfies the following formula (4a).





0.1≤{(3As+Sb)/(Bi+Pb)}×100≤158.5  (4a)


In the formula (4a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the second aspect, the alloy composition preferably further contains at least one selected from the group consisting of Ag: more than 0% by mass and 4% by mass or less and Cu: more than 0% by mass and 0.9% by mass or less.


In addition, a solder paste according to a third aspect is a solder paste containing a flux and a solder powder, in which the flux contains an organic acid, an acrylic resin, a rosin, a thixotropic agent, and a solvent, but does not contain water, the organic acid contains 1,2,3-propanetricarboxylic acid, a content of the 1,2,3-propanetricarboxylic acid is 0.1% by mass or more and 15% by mass or less with respect to a total amount of the entire flux, a content of the acrylic resin is 5% by mass or more and 45% by mass or less with respect to the total amount of the entire flux, a content of the rosin is 5% by mass or more and 45% by mass or less with respect to the total amount of the entire flux, and the solder powder is composed of a solder alloy having an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: more than 0 mass ppm and 10000 mass ppm or less and Pb: more than 0 mass ppm and 5100 mass ppm or less, Sb: more than 0 mass ppm and 3000 mass ppm or less, and a balance of Sn and satisfying the following formula (3) and formula (4).





300≤3As+Sb+Bi+Pb  (3)





0.1≤{(3As+Sb)/(Bi+Pb)}×100≤200  (4)


In the formula (3) and the formula (4), As, Sb, Bi, and Pb each represent a content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the third aspect, a ratio (mass ratio) of the content of the rosin to the content of the acrylic resin is preferably 1 or more and 9 or less.


In addition, in the solder paste according to the third aspect, a total content of the organic acid is preferably 0.1% by mass or more and 15% by mass or less with respect to the total amount of the entire flux.


In addition, the solder paste according to the third aspect further contains azoles, in which a content of the azoles is preferably 0.1% by mass or more and 10% by mass or less with respect to the total amount of the entire flux.


In addition, in the solder paste according to the third aspect, a ratio (mass ratio) of the total content of the organic acid to the content of the azoles is preferably 0.6 or more and 100 or less.


In addition, the solder paste according to the third aspect further contains a resin other than the acrylic resin and the rosin, in which a content of the resin other than the acrylic resin and the rosin is preferably more than 0% by mass and 10% by mass or less with respect to the total amount of the entire flux.


In addition, the solder paste according to the third aspect further contains a halogen compound, in which a content of the halogen compound is preferably more than 0% by mass and 5% by mass or less with respect to the total amount of the entire flux.


In addition, the solder paste according to the third aspect further contains an antioxidant, in which a content of the antioxidant is preferably more than 0% by mass and 5% by mass or less with respect to the total amount of the entire flux.


In addition, in the solder paste according to the third aspect, the alloy composition preferably further contains Ni: more than 0 mass ppm and 600 mass ppm or less.


In addition, in the solder paste according to the third aspect, the alloy composition preferably further contains Fe: more than 0 mass ppm and 100 mass ppm or less.


In addition, in the solder paste according to the third aspect, the alloy composition preferably further contains In: more than 0 mass ppm and 1200 mass ppm or less.


In addition, in the solder paste according to the third aspect, the alloy composition preferably further contains at least two of Ni: more than 0 mass ppm and 600 mass ppm or less, Fe: more than 0 mass ppm and 100 mass ppm or less and In: more than 0 mass ppm and 1200 mass ppm or less and satisfies the following formula (6).





0<Ni+Fe≤680  (6)


In the formula (6), Ni and Fe each represent a content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the third aspect, the alloy composition preferably further contains Ni: 0 mass ppm or more and 600 mass ppm or less and Fe: more than 0 mass ppm and 100 mass ppm or less and satisfies the following formula (5) and the following formula (6).





0≤Ni/Fe≤50  (5)





0<Ni+Fe≤680  (6)


In the formula (5) and the formula (6), Ni and Fe each represent a content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the third aspect, the alloy composition preferably further satisfies the following formula (3a).





300≤3As+Sb+Bi+Pb≤18214  (3a)


In the formula (3a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the third aspect, the alloy composition preferably further satisfies the following formula (4a).





0.1≤{(3As+Sb)/(Bi+Pb)}×100≤158.5  (4a)


In the formula (4a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In addition, in the solder paste according to the third aspect, the alloy composition preferably further contains at least one of Ag: more than 0% by mass and 4% by mass or less and Cu: more than 0% by mass and 0.9% by mass or less.


Advantageous Effects of Invention

According to the present invention, it is possible to provide a flux capable of enhancing the wettability of solder, having excellent temperature cycle reliability, and capable of suppressing scattering due to heating during reflow and a solder paste using the same.





BRIEF DESCRIPTION OF DRAWING


FIG. 1 is a graph showing a schematic diagram of a reflow profile in evaluation of scattering suppression.





DESCRIPTION OF EMBODIMENTS

<Flux>


A flux of the present embodiment contains an organic acid, an acrylic resin, a rosin, a thixotropic agent, and a solvent, but does not contain water.


The organic acid includes 1,2,3-propanetricarboxylic acid. The content of the 1,2,3-propanetricarboxylic acid is preferably 0.05% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less, and still more preferably 0.5% by mass or more and 15% by mass or less with respect to the total amount of the entire flux.


(Organic Acid)


The flux of the present embodiment contains 1,2,3-propanetricarboxylic acid and is thereby capable of enhancing solder wettability (wetting speed).


The flux of the present embodiment may contain, in addition to the 1,2,3-propanetricarboxylic acid, other organic acids.


Examples of the other organic acids include glutaric acid, adipic acid, azelaic acid, eicosanedioic acid, citric acid, glycolic acid, succinic acid, salicylic acid, diglycolic acid, dipicolinic acid, dibutylaniline diglycolic acid, suberic acid, sebacic acid, thioglycolic acid, terephthalic acid, dodecanedioic acid, parahydroxyphenylacetic acid, picolinic acid, phenylsuccinic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, lauric acid, benzoic acid, tartaric acid, tris(2-carboxyethyl) isocyanurate, glycine, 1,3-cyclohexanedicarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxymethyl)butanoic acid, 2,3-dihydroxybenzoic acid, 2,4-diethylglutaric acid, 2-quinolinecarboxylic acid, 3-hydroxybenzoic acid, malic acid, p-anisic acid, stearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, a dimer acid, a trimer acid, a hydrogenated dimer acid, which is a hydrogenated substance obtained by adding hydrogen to a dimer acid, a hydrogenated trimer acid, which is a hydrogenated substance obtained by adding hydrogen to a trimer acid, and the like.


One organic acid may be used singly or two or more organic acids may be mixed and used.


The other organic acids are preferably one or more selected from the group consisting of sebacic acid, adipic acid, eicosanedioic acid, and a hydrogenated dimer acid.


The total content of the organic acid is preferably 0.1% by mass or more and 20% by mass or less and more preferably 0.1% by mass or more and 15% by mass or less with respect to the total amount of the entire flux.


The content of the 1,2,3-propanetricarboxylic acid is preferably 5% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and most preferably 50% by mass or more and may be 100% by mass with respect to the total content of the organic acid.


(Resin)


The flux of the present embodiment contains an acrylic resin and a rosin as resins.


The flux of the present embodiment may contain a resin other than the acrylic resin and the rosin (other resin).


(Acrylic Resin)


The flux of the present embodiment contains the acrylic resin and is thus capable of enhancing the temperature cycle reliability.


Examples of the acrylic resin include polymers of acrylic acid, polymers of an acrylic acid ester, polymers of acrylic acid and an acrylic acid ester, and the like for which acrylic acid, an acrylic acid ester, which is a reaction product of acrylic acid and an alcohol, methacrylic acid, or a methacrylic acid ester, which is a reaction product of methacrylic acid and an alcohol, is used as a monomer. In addition, examples thereof include polymers of methacrylic acid, polymers of a methacrylic acid ester, polymers of methacrylic acid and a methacrylic acid ester, and the like. Furthermore, examples thereof include polymers of acrylic acid and methacrylic acid, polymers of acrylic acid and a methacrylic acid ester, polymers of methacrylic acid and an acrylic acid ester, polymers of an acrylic acid ester and a methacrylic acid ester, polymers of acrylic acid, methacrylic acid, and an acrylic acid ester, polymers of acrylic acid, methacrylic acid, and a methacrylic acid ester, polymers of acrylic acid, methacrylic acid, an acrylic acid ester, and a methacrylic acid ester, polymers of acrylic acid, an acrylic acid ester, and a methacrylic acid ester, polymers of methacrylic acid, an acrylic acid ester, and a methacrylic acid ester, and the like. Examples of the acrylic acid ester include acrylic acid butyl ester, and examples of the acrylic resin for which the acrylic acid butyl ester is used as a monomer include polymers of acrylic acid butyl ester, polymers of an acrylic acid ester other than acrylic acid butyl ester and acrylic acid butyl ester, polymers of acrylic acid and acrylic acid butyl ester, polymers of acrylic acid, an acrylic acid ester other than acrylic acid butyl ester and acrylic acid butyl ester, and the like. In addition, examples of the methacrylic acid ester include methacrylic acid butyl ester, and examples of the acrylic resin for which the methacrylic acid butyl ester is used as a monomer include polymers of methacrylic acid butyl ester, polymers of a methacrylic acid ester other than methacrylic acid butyl ester and methacrylic acid butyl ester, polymers of methacrylic acid and methacrylic acid butyl ester, polymers of methacrylic acid, a methacrylic acid ester other than methacrylic acid butyl ester and methacrylic acid butyl ester, and the like. Furthermore, examples thereof include polymers of acrylic acid and methacrylic acid butyl ester, polymers of acrylic acid, a methacrylic acid ester other than methacrylic acid butyl ester, and a methacrylic acid butyl ester, polymers of methacrylic acid and acrylic acid butyl ester, polymers of methacrylic acid, an acrylic acid ester other than acrylic acid butyl ester, and acrylic acid butyl ester, polymers of acrylic acid butyl ester and methacrylic acid butyl ester, polymers of acrylic acid ester other than acrylic acid butyl ester and methacrylic acid butyl ester, polymers of acrylic acid butyl ester and a methacrylic acid ester other than methacrylic acid butyl ester, and the like. The polymerization reaction may be random copolymerization, block copolymerization, or the like. In addition, the alcohol is an alcohol in which the carbon chain is linear and the number of carbon atoms is 1 to 24 or an alcohol in which the carbon chain is branched and the number of carbon atoms is 3 to 24, and examples of the alcohol include methanol having 1 carbon atom, ethanol having 2 carbon atoms, 1-propanol having 3 carbon atoms, 2-propanol having 3 carbon atoms, ethylene glycol monomethyl ether having 3 carbon atoms, 1-butanol having 4 carbon atoms, 2-butanol having 4 carbon atoms, isobutanol having 4 carbon atoms, 1-hexanol having 6 carbon atoms, diethylene glycol monoethyl ether having 6 carbon atoms, benzyl alcohol having 7 carbon atoms, 1-octanol having 8 carbon atoms, 2-ethylhexanol having 8 carbon atoms, phenyl glycol having 8 carbon atoms, 1-decanol having 10 carbon atoms, lauryl alcohol having 12 carbon atoms, cetyl alcohol having 16 carbon atoms, stearyl alcohol having 18 carbon atoms, oleyl alcohol having 18 carbon atoms, behenyl alcohol having 22 carbon atoms, and the like.


As the molecular weight of the acrylic resin, the polystyrene-equivalent weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) is preferably 5000 to 30000, and the weight-average molecular weight (Mw) is more preferably 6000 to 15000.


Examples of such an acrylic resin include poly 2-ethylhexyl acrylate (Mw=8300), poly 2-ethylhexyl acrylate having a different molecular weight (Mw=11700), polylauryl methacrylate (Mw=10080), and the like. In addition, the acrylic resin may be a polymer of the acrylic resin and a different resin or may be, for example, a copolymer of each of the above-described acrylic resins and polyethylene. Examples of such an acrylic/polyethylene copolymer resin include poly 2-ethylhexyl acrylate-polyethylene (Mw=12300) and the like.


One acrylic resin may be used singly or two or more acrylic resins may be mixed and used.


The acrylic resin is preferably one or more selected from the group consisting of poly 2-ethylhexyl acrylate (Mw=8300), poly 2-ethylhexyl acrylate (Mw=11700), polylauryl methacrylate (Mw=10080), and poly 2-ethylhexyl acrylate-polyethylene (Mw=12300).


The total content of the acrylic resins is preferably 5% by mass or more and 60% by mass or less and more preferably 5% by mass or more and 45% by mass or less with respect to the total amount of the entire flux.


(Rosin)


Examples of the rosin that is used in the present embodiment include natural rosins, derivatives obtained from the natural rosins, and the like.


Examples of the natural rosins include gum rosin, wood rosin, tall oil rosin, and the like. Examples of the derivatives include purified rosins, modified rosins, and the like. Examples of the modified rosins include hydrogenated rosins, polymerized rosins, disproportionated rosins, acid-modified rosins, rosin esters, phenol-modified rosins, α,β-unsaturated carboxylic acid-modified substances (acrylated rosins, maleated rosins, fumarated rosins, acrylic acid-modified hydrogenated rosins, and the like), the purified substances, hydrides, and disproportionated substances of the polymerized rosin, the purified substances, hydrides, and disproportionated substances of the α,β-unsaturated carboxylic acid-modified substance, and the like.


One rosin may be used singly or two or more rosins may be mixed and used.


The rosin is preferably one or more selected from the group consisting of hydrogenated rosins, acrylic acid-modified hydrogenated rosins, polymerized rosins, and disproportionated rosins.


The total content of the rosins is preferably 5% by mass or more and 60% by mass or less and more preferably 5% by mass or more and 45% by mass or less with respect to the total amount of the entire flux.


The total content of the rosin and the acrylic resin is preferably 30% by mass or more and 60% by mass or less and more preferably 40% by mass or more and 50% by mass or less with respect to the total amount of the entire flux.


In the flux that is used in the present embodiment, the ratio (mass ratio) of the content of the rosin to the content of the acrylic resin is preferably 0.05 or more and 12 or less, more preferably 0.1 or more and 9 or less, and still more preferably 1 or more and 9 or less.


When the ratio of the content of the rosin to the content of the acrylic resin is within the above-described range, it is possible to enhance the temperature cycle reliability of the flux.


The flux that is used in the present embodiment may contain, for example, a polyethylene resin or the like as a resin other than the acrylic resin and the rosin (other resin).


The content of the resin other than the acrylic resin and the rosin is preferably 0% by mass or more and 15% by mass or less, more preferably 0% by mass or more and 10% by mass or less, and still more preferably more than 0% by mass and 10% by mass or less with respect to the total amount of the entire flux.


The total content of the rosin, the acrylic resin, and the other resin is preferably 30% by mass or more and 60% by mass or less and more preferably 40% by mass or more and 50% by mass or less with respect to the total amount of the entire flux.


(Thixotropic Agent)


Examples of the thixotropic agent include an amide compound, an ester compound, a sorbitol-based compound, and the like.


Examples of the amide compound, which is a thixotropic agent, include polyamides, bisamides, monoamides, and the like.


Examples of the monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, saturated fatty acid amides, oleic acid amide, erucic acid amide, unsaturated fatty acid amides, p-toluamide, p-toluenemethane amide, aromatic amides, hexamethylene hydroxystearic acid amide, substituted amides, methylol stearic acid amide, methylol amide, fatty acid ester amides, and the like.


Examples of the bisamides include methylene bis(stearic acid amide), ethylene bis(lauric acid amide), ethylene bis(hydroxy fatty acid (the number of carbon atoms in the fatty acid: C6 to 24) amide), ethylene bis(hydroxystearic acid amide), saturated fatty acid bisamide, methylene bis(oleic acid amide), unsaturated fatty acid bisamide, m-xylylene bis(stearic acid amide), aromatic bisamide, and the like.


Examples of the polyamide include saturated fatty acid polyamides, unsaturated fatty acid polyamides, aromatic polyamides, tris 1,2,3-propanetricarboxylate (2-methylcyclohexylamide), cyclic amide oligomers, acyclic amide oligomers, and the like.


Examples of the cyclic amide oligomers include an amide oligomer in which a dicarboxylic acid and a diamine are polycondensed in a cyclic shape, an amide oligomer in which a tricarboxylic acid and a diamine are polycondensed in a cyclic shape, an amide oligomer in which a dicarboxylic acid and a triamine are polycondensed in a cyclic shape, an amide oligomer in which a tricarboxylic acid and a triamine are polycondensed in a cyclic shape, an amide oligomer in which a dicarboxylic acid, a tricarboxylic acid, and a diamine are polycondensed in a cyclic shape, an amide oligomer in which a dicarboxylic acid, a tricarboxylic acid, and a triamine are polycondensed in a cyclic shape, an amide oligomer in which a dicarboxylic acid, a diamine, and a triamine are polycondensed in a cyclic shape, an amide oligomer in which a tricarboxylic acid, a diamine, and a triamine are polycondensed in a cyclic shape, an amide oligomer in which a dicarboxylic acid, a tricarboxylic acid, a diamine, and a triamine are polycondensed in a cyclic shape, and the like.


In addition, examples of the acyclic amide oligomer include an amide oligomer in which a monocarboxylic acid and a diamine and/or a triamine are polycondensed in an acyclic shape, an amide oligomer in which a dicarboxylic acid and/or a tricarboxylic acid and a monoamine are polycondensed in an acyclic shape, and the like. When the acyclic amide oligomer is an amide oligomer containing a monocarboxylic acid or a monoamine, the monocarboxylic acid or the monoamine functions as a terminal molecule, and the acyclic amide oligomer has a reduced molecular weight. In addition, in a case where the acyclic amide oligomer is an amide compound in which a dicarboxylic acid and/or a tricarboxylic acid and a diamine and/or a triamine are polycondensed in an acyclic shape, the acyclic amide oligomer becomes an acyclic polymer-based amide polymer. Furthermore, examples of the acyclic amide oligomer also include an amide oligomer in which a monocarboxylic acid and a monoamine are condensed in an acyclic shape.


Examples of the ester compound, which is the thixotropic agent, include hydrogenated castor oil and the like.


Examples of the sorbitol-based compound, which is the thixotropic agent, include dibenzylidene sorbitol, bis(4-methylbenzylidene) sorbitol, (D-)sorbitol, monobenzylidene (-D-)sorbitol, mono(4-methylbenzylidene)-(D-)sorbitol, and the like.


One thixotropic agent may be used singly or two or more thixotropic agents may be mixed and used.


The thixotropic agent is preferably one or more selected from the group consisting of an amide compound and an ester compound.


The thixotropic agent is preferably one or more selected from the group consisting of a polyamide, a bisamide, a monoamide, and hydrogenated castor oil.


The polyamide is preferably an aliphatic polyamide. The bisamide is preferably ethylene bis(hydroxystearic acid amide). The monoamide is preferably p-toluamide.


The total content of the thixotropic agents is preferably 2% by mass or more and 12% by mass or less and more preferably 3% by mass or more and 8.5% by mass or less with respect to the total amount of the entire flux.


The total content of the amide compounds is preferably 2% by mass or more and 12% by mass or less and more preferably 3% by mass or more and 8.5% by mass or less with respect to the total amount of the entire flux.


The content of the ester compound is preferably 0% by mass or more and 5% by mass or less and more preferably 0% by mass or more and 3% by mass or less with respect to the total amount of the entire flux.


(Solvent)


The flux of the present embodiment does not contain water. The flux of the present embodiment does not contain water and is thus capable of making the scattering suppression effect sufficient.


Examples of the solvent that is used in the present embodiment include an alcohol-based solvent, a glycol ether-based solvent, terpineols, and the like.


Examples of the alcohol-based solvent include isopropyl alcohol, 1,2-butanediol, isobornyl cyclohexanol, 2,4-diethyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,3-dimethyl-2,3-butanediol, 1,1,1-tris(hydroxymethyl)ethane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 2,2′-oxybis(methylene) bis(2-ethyl-1,3-propanediol), 2,2-bis(hydroxymethyl)-1,3-propanediol, 1,2,6-trihydroxyhexane, bis[2,2,2-tris(hydroxymethyl)ethyl]ether, 1-ethynyl-1-cyclohexanole, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, erythritol, threitol, guaiacol glycerol ether, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and the like.


Examples of the glycol ether-based solvent include aliphatic glycol ether-based solvents such as hexyl glycol, hexyl diglycol, 2-ethyl hexyl glycol, 2-ethyl hexyl diglycol, dimethyl triglycol, dibutyl diglycol, 2-methylpentane-2,4-diol, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and tetraethylene glycol dimethyl ether; aromatic glycol ether-based solvents such as phenyl glycol, phenyl diglycol, benzyl glycol, and benzyl diglycol; and the like.


One solvent or two or more solvents can be used.


(Other Components)


The flux of the present embodiment may contain, for example, an amine, a halogen compound, an antioxidant, and the like as other components.


Examples of the amine include azoles, other amines (excluding azoles), and the like.


The flux of the present embodiment may contain azoles.


The “azoles” mentioned herein means compounds having a 5-membered heterocyclic structure having one or more nitrogen atoms and also include condensed rings of the 5-membered heterocyclic structure and a different ring structure.


When the flux contains the azoles, it is possible to improve the corrosion suppression property of the metallic surface (for example, a copper plate) of an object to be joined.


Examples of the azoles include imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, epoxy-imidazole adduct, 2-methylbenzimidazole, 2-octylbenzimidazole, 2-pentylbenzimidazole, 2-(1-ethylpentyl)benzimidazole, 2-nonylbenzimidazole, 2-(4-thiazolyl)benzimidazole, benzimidazole, 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)benzotriazole, 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol], 1,2,3-benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, carboxybenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, 2,2′-[[(methyl-1H-benzotriazol yl)methyl]imino]bisethanol, 1-(1′,2′-dicarboxyethyl)benzotriazole, 1-(2,3-dicarboxypropyl)benzotriazole, 1-[(2-ethylhexylamino)methyl]benzotriazole, 2,6-bis[(1H-benzotriazol-1-yl)methyl]-4-methylphenol, 5-methylbenzotriazole, 5-phenyltetrazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl phenylimidazolium trimellitate, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-undecylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine isocyanuric acid adduct, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, 6-(2-benzotriazolyl)-4-tert-octyl-6′-tert-butyl-4′-methyl-2,2′-methylenebisphenol, and the like.


One azole may be used singly or two or more azoles may be mixed and used.


The azoles are preferably one or more selected from the group consisting of 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, benzimidazole, and 2-octylbenzimidazole.


In the flux of the present embodiment, the total content of the azoles is preferably 0.1% by mass or more and 15% by mass or less and more preferably 0.1% by mass or more and 10% by mass or less with respect to the total amount of the entire flux.


In the flux of the present embodiment, the ratio (mass ratio) of the total content of the organic acid to the content of the azoles is preferably 0.3 or more and 200 or less and more preferably 0.6 or more and 100 or less.


When the ratio (mass ratio) of the total content of the organic acid to the content of the azoles is within the above-described range, it is possible to make the corrosion suppression effect sufficient.


Examples of the other amines include monoethanolamine, ethylamine, triethylamine, cyclohexylamine, ethylenediamine, triethylenetetramine, 2,4-diamino vinyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, and the like.


The amine is preferably monoethanolamine.


Examples of the halogen compound include an amine hydrohalide and an organic halogen compound.


The amine hydrohalide is a compound obtained by reacting an amine and a hydrogen halide. Examples of the amine in the amine hydrohalide include ethylamine, ethylenediamine, triethylamine, diphenylguanidine, ditolylguanidine, methylimidazole, 2-ethyl-4-methylimidazole, and the like, and examples of the hydrogen halide include hydrides of chlorine, bromine, and iodine.


Examples of the organic halogen compound include trans-2,3-dibromo-2-butene-1,4-diol, triallyl isocyanurate hexabromide, 1-bromo-2-butanol, 1-bromo-2-propanol, 3-bromo-1-propanol, 3-bromo-1,2-propanediol, 1,4-dibromo-2-butanol, 1,3-dibromo-2-propanol, 2,3-dibromo-1-propanol, 2,3-dibromo-1,4-butanediol, 2,3-dibromo-2-butene-1,4-diol, and the like.


The halogen compound is preferably one or more selected from the group consisting of diphenylguanidine/HBr or 2,3-dibromo-1,4-butanediol.


One halogen compound may be used singly or two or more halogen compounds may be mixed and used.


The total content of the halogen compounds is preferably 0% by mass or more and 8% by mass or less, more preferably 0% by mass or more and 5% by mass or less, and still more preferably more than 0% by mass and 5% by mass or less with respect to the total amount of the entire flux.


Examples of the antioxidant include a hindered phenolic antioxidant and the like.


The total content of the antioxidants is preferably 0% by mass or more and 8% by mass or less, more preferably 0% by mass or more and 5% by mass or less, and still more preferably more than 0% by mass and 5% by mass or less with respect to the total amount of the entire flux.


The flux of the present embodiment contains the organic acid, the acrylic resin, the rosin, the thixotropic agent, and the solvent, but does not contain water. The organic acid includes 1,2,3-propanetricarboxylic acid. When the content of the 1,2,3-propanetricarboxylic acid is 0.1% by mass or more and 15% by mass or less with respect to the total amount of the entire flux, it is possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


The flux of the present embodiment further contains the azoles, which makes it possible to make the flux have a sufficient corrosion suppression effect.


Examples of one embodiment of the flux include a flux containing an organic acid, an acrylic resin, a rosin, a thixotropic agent, a solvent, and other organic acids, but not containing water, in which the organic acid includes 1,2,3-propanetricarboxylic acid, the content of the 1,2,3-propanetricarboxylic acid is 0.1% by mass or more and 3% by mass or less with respect to the total amount of the entire flux, and the total content of the organic acid is 3% by mass or more and 15% by mass or less with respect to the total amount of the entire flux.


In addition, examples of one embodiment of the flux include a flux containing an organic acid, an acrylic resin, a rosin, a thixotropic agent, a solvent, and a halogen compound, but not containing water, in which the organic acid includes 1,2,3-propanetricarboxylic acid, the content of the 1,2,3-propanetricarboxylic acid is 0.1% by mass or more and 1% by mass or less with respect to the total amount of the entire flux, and the total content of the organic acid and the halogen compound is 1.1% by mass or more and 2% by mass or less with respect to the total amount of the entire flux.


<Example of Solder Paste of Present Embodiment>


A solder paste of the present embodiment contains the above-described flux and a solder powder.


The solder powder is composed of a powder of pure Sn solder, a Sn—Ag-based alloy, a Sn—Cu-based alloy, a Sn—Ag—Cu-based alloy, a Sn—Bi-based alloy, a Sn—In-based alloy, or a powder of a solder alloy obtained by adding Sb, Bi, In, Cu, Zn, As, Ag, Cd, Fe, Ni, Co, Au, Ge, P, or the like to the above-described alloy.


Content of Flux:


The content of the flux is preferably 5 to 95% by mass and more preferably 5 to 15% by mass with respect to the total mass of the solder paste.


When the content of the flux in the solder paste is within this range, a thickening suppression effect attributed to the solder powder is sufficiently exhibited.


Additionally, favorable wetting and spreading are exhibited even under conditions with a large heat load, and the wetting speed improves.


Solder Alloy (First Embodiment):


The solder alloy preferably has an alloy composition containing As: 25 mass ppm or more and 300 mass ppm or less, at least one of Sb: more than 0 mass ppm and 3000 mass ppm or less, Bi: more than 0 mass ppm and 10000 mass ppm or less, and Pb: more than 0 mass ppm and 5100 mass ppm or less, and a balance (Bal) of Sn. This solder alloy may further contain at least one of Ag: more than 0% by mass and 4% by mass or less and Cu: more than 0% by mass and 0.9% by mass or less.


As is an element capable of suppressing a change in the viscosity of the solder paste over time. It is presumed that As has low reactivity with the flux and is a noble element with respect to Sn and is thus capable of exhibiting a thickening suppression effect. The lower limit of the content of As is, for example, 25 mass ppm or more, preferably 50 mass ppm or more, and more preferably 100 mass ppm or more. On the other hand, when As is too large, the wettability of the solder alloy deteriorates. The upper limit of the content of As is, for example, 300 mass ppm or less, preferably 250 mass ppm or less, and more preferably 200 mass ppm or less.


Sb is an element having low reactivity with the flux and exhibiting a thickening suppression effect. In a case where the solder alloy contains Sb, the lower limit of the content of Sb is, for example, more than 0 mass ppm, preferably 25 mass ppm or more, more preferably 50 mass ppm or more, still more preferably 100 mass ppm or more, and particularly preferably 300 mass ppm or more. On the other hand, when the content of Sb is too large, since the wettability of the solder alloy deteriorates, there is a need for the solder alloy to have an appropriate content of Sb. The upper limit of the content of Sb is, for example, 3000 mass ppm or less, preferably 1150 mass ppm or less, and more preferably 500 mass ppm or less.


Similar to Sb, Bi and Pb are elements having low reactivity with the flux and exhibiting a thickening suppression effect. In addition, Bi and Pb decrease the liquidus temperature of the solder alloy and decrease the viscosity of molten solder and are thus elements capable of suppressing deterioration of the wettability of the solder alloy due to As.


As long as at least one element of Sb, Bi, and Pb is present, it is possible to suppress deterioration of the wettability of the solder alloy due to As. In a case where the solder alloy contains Bi, the lower limit of the content of Bi is, for example, more than 0 mass ppm, preferably 25 mass ppm or more, more preferably 50 mass ppm or more, still more preferably 75 mass ppm or more, particularly preferably 100 mass ppm or more, and most preferably 250 mass ppm or more. In a case where the solder alloy contains Pb, the lower limit of the content of Pb is, for example, more than 0 mass ppm, preferably 25 mass ppm or more, more preferably 50 mass ppm or more, still more preferably 75 mass ppm or more, particularly preferably 100 mass ppm or more, and most preferably 250 mass ppm or more.


On the other hand, when the contents of these elements are too large, since the solidus temperature significantly decreases, ΔT, which is the temperature difference between the liquidus temperature and the solidus temperature, becomes too wide. When ΔT is too wide, since a high-melting point crystal phase having a small content of Bi or Pb is precipitated in a solidification process of the molten solder, the liquid phase Bi or Pb is concentrated. When the temperature of the molten solder further decreases after that, a low-melting point crystal phase having a high concentration of Bi or Pb is segregated. Therefore, the mechanical strength and the like of the solder alloy deteriorate, and the reliability deteriorates. Particularly, since the crystal phase having a high Bi concentration is hard and brittle, segregation of the crystal phase in the solder alloy significantly degrades the reliability.


From such a viewpoint, in a case where the solder alloy contains Bi, the upper limit of the content of Bi is, for example, 10000 mass ppm or less, preferably 1000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 500 mass ppm or less. The upper limit of the content of Pb is, for example, 5100 mass ppm or less, preferably 5000 mass ppm or less, more preferably 1000 mass ppm or less, still more preferably 850 mass ppm or less, and particularly preferably 500 mass ppm or less.


The solder alloy preferably satisfies the following mathematical formula (1).





275≤2As+Sb+Bi+Pb  (1)


In the mathematical formula (1), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


As, Sb, Bi, and Pb are all elements exhibiting a thickening suppression effect. The total of these is preferably 275 mass ppm or more. In the mathematical formula (1), the reason for the content of As to be doubled is that As has a higher thickening suppression effect than Sb, Bi, or Pb.


The lower limit of the mathematical formula (1) is preferably 350 or more and more preferably 1200 or more. On the other hand, the upper limit of the mathematical formula (1) is not particularly limited from the viewpoint of the thickening suppression effect, but is preferably 25200 or less, more preferably 10200 or less, still more preferably 5300 or less, and particularly preferably 3800 or less from the viewpoint of setting ΔT in a suitable range.


The mathematical formula for which the upper limit and the lower limit are appropriately selected from the above-described preferable aspects is the following mathematical formula (1a) and mathematical formula (1b).





275≤2As+Sb+Bi+Pb≤25200  (1a)





275≤2As+Sb+Bi+Pb≤5300  (1b)


In the mathematical formula (1a) and the mathematical formula (1b), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In addition, the solder alloy preferably satisfies the following mathematical formula (2).





0.01≤(2As+Sb)/(Bi+Pb)≤10.00  (2)


In the mathematical formula (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


When the contents of As and Sb are large, the wettability of the solder alloy deteriorates. On the other hand, Bi and Pb suppress the deterioration of the wettability of the solder alloy due to As contained; however, when the contents thereof are too large, ΔT increases. Particularly, in an alloy composition containing Bi and Pb at the same time, ΔT is likely to increase. In consideration of these facts, when an attempt is made to excessively improve the wettability of the solder alloy by increasing the contents of Bi and Pb, ΔT becomes wide. On the other hand, when an attempt is made to improve the thickening suppression effect by increasing the content of As or Sb, the wettability of the solder alloy deteriorates. Therefore, in a case where the components are divided into a group of As and Sb and a group of Bi and Pb, and the total amount of both groups is within a predetermined appropriate range, all of the thickening suppression effect, narrowing of ΔT, and the wettability of the solder alloy are satisfied at the same time.


When the mathematical formula (2) is less than 0.01, since the total of the contents of Bi and Pb becomes relatively large compared with the total of the contents of As and Sb, ΔT becomes wide. The lower limit of the mathematical formula (2) is preferably 0.02 or more, more preferably 0.41 or more, still more preferably 0.90 or more, particularly preferably 1.00 or more, and most preferably 1.40 or more. On the other hand, when the mathematical formula (2) exceeds 10.00, since the total of the contents of As and Sb becomes relatively large compared with the total of the contents of Bi and Pb, the wettability of the solder alloy deteriorates. The upper limit of the mathematical formula (2) is preferably 5.33 or less, more preferably 4.50 or less, still more preferably 2.67 or less, and particularly preferably 2.30 or less.


The denominator of the mathematical formula (2) is “Bi+Pb”, and, when these are not contained, the mathematical formula (2) is not established. Therefore, the solder alloy preferably contains at least one of Bi and Pb. As described above, the alloy composition containing neither Bi nor Pb is poor in the wettability of the solder alloy.


The mathematical formula for which the upper limit and the lower limit are appropriately selected from the above-described preferable aspects is the following mathematical formula (2a).





0.31≤(2As+Sb)/(Bi+Pb)≤10.00  (2a)


In the mathematical formula (2a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


Solder Alloy (Second Embodiment):


In addition, the solder alloy may have an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: 0 to 10000 mass ppm and Pb: 0 to 5100 mass ppm, Sb: more than 0 mass ppm and 3000 mass ppm or less, and a balance of Sn and satisfy the following formula (3) and formula (4). This solder alloy may further contain at least one of Ag: more than 0% by mass and 4% by mass or less and Cu: more than 0% by mass and 0.9% by mass or less.





300≤3As+Sb+Bi+Pb  (3)





0.1≤{(3As+Sb)/(Bi+Pb)}×100≤200  (4)


In the formula (3) and the formula (4), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In a case where such a solder alloy is used, all of the thickening suppression effect, narrowing of ΔT, and the wettability of the solder alloy are satisfied at the same time.


In addition, the solder alloy may have an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: more than 0 mass ppm and 10000 mass ppm or less and Pb: more than 0 mass ppm and 5100 mass ppm or less, Sb: more than 0 mass ppm and 3000 mass ppm or less, and a balance of Sn and satisfy the following formula (3) and formula (4).


In addition, the solder alloy may have an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: 50 to 10000 mass ppm and Pb: more than 0 mass ppm and 5100 mass ppm or less, Sb: more than 0 mass ppm and 3000 mass ppm or less, and a balance of Sn and satisfy the following formula (3) and formula (4).


In addition, the solder alloy may have an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: more than 0 mass ppm and 10000 mass ppm or less and Pb: 50 to 5100 mass ppm, Sb: more than 0 mass ppm and 3000 mass ppm or less, and a balance of Sn and satisfy the following formula (3) and formula (4).


In addition, the solder alloy may have an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: more than 0 mass ppm and 10000 mass ppm or less and Pb: more than 0 mass ppm and 5100 mass ppm or less, Sb: 50 mass ppm to 3000 mass ppm, and a balance of Sn and satisfy the following formula (3) and formula (4).


In addition, the solder alloy may have an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: 50 to 10000 mass ppm and Pb: 50 to 5100 mass ppm, Sb: more than 0 mass ppm and 3000 mass ppm or less, and a balance of Sn and satisfy the formula (3) and the formula (4).


In addition, the solder alloy may have an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: more than 0 mass ppm and 10000 mass ppm or less and Pb: 50 to 5100 mass ppm, Sb: 50 to 3000 mass ppm, and a balance of Sn and satisfy the formula (3) and the formula (4).


In addition, the solder alloy may have an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: 50 to 10000 mass ppm and Pb: more than 0 mass ppm and 5100 mass ppm or less, Sb: 50 to 3000 mass ppm, and a balance of Sn and satisfy the formula (3) and the formula (4).


In addition, the solder alloy may have an alloy composition containing As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: 50 to 10000 mass ppm and Pb: 50 to 5100 mass ppm, Sb: 50 to 3000 mass ppm, and a balance of Sn and satisfy the formula (3) and the formula (4).


In addition, the solder alloy may further contain Ni: more than 0 mass ppm and 600 mass ppm or less.


In addition, the solder alloy may further contain Fe: more than 0 mass ppm and 100 mass ppm or less.


In addition, the solder alloy may further contain In: more than 0 mass ppm and 1200 mass ppm or less.


In addition, the solder alloy may further contain at least two of Ni: more than 0 mass ppm and 600 mass ppm or less, Fe: more than 0 mass ppm and 100 mass ppm or less and In: more than 0 mass ppm and 1200 mass ppm or less and satisfy the following formula (6).





0<Ni+Fe≤680  (6)


In the formula (6), Ni and Fe each represent the content (mass ppm) in the alloy composition.


In addition, the solder alloy may further contain Ni: 0 mass ppm or more and 600 mass ppm or less and Fe: more than 0 mass ppm and 100 mass ppm or less and satisfy the following formula (5) and the following formula (6).





0≤Ni/Fe≤50  (5)





0<Ni+Fe≤680  (6)


In the formula (5) and the formula (6), Ni and Fe each represent the content (mass ppm) in the alloy composition.


In addition, the solder alloy may further satisfy the following formula (3a).





300≤3As+Sb+Bi+Pb≤18214  (3a)


In the formula (3a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In addition, the solder alloy may further satisfy the following formula (4a).





0.1≤{(3As+Sb)/(Bi+Pb)}×100≤158.5  (4a)


In the formula (4a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.


In addition, the above-described solder alloy may further contain at least one of Ag: more than 0% by mass and 4% by mass or less and Cu: more than 0% by mass and 0.9% by mass or less.


Ag is an optional element capable of forming Ag3Sn at crystal interfaces to improve the reliability of the solder alloy. In addition, Ag is a nobler element than Sn in terms of the ionization tendency, and, when coexisting with As, Pb and Bi, promotes the thickening suppression effect thereof. The content of Ag is preferably more than 0% by mass and 4% by mass or less, more preferably 0.5% by mass or more and 3.5% by mass or less, and still more preferably 1.0% by mass or more and 3.0% by mass or less.


Cu is an optional element capable of improving the joining strengths of solder joints. In addition, Cu is a nobler element than Sn in terms of the ionization tendency, and, when coexisting with As, Pb and Bi, promotes the thickening suppression effect thereof. The content of Cu is preferably more than 0% by mass and 0.9% by mass or less, more preferably 0.1% by mass or more and 0.8% by mass or less, and still more preferably 0.2% by mass or more and 0.7% by mass or less.


The balance (Bal) of the solder alloy is preferably Sn. The solder alloy may contain unavoidable impurities in addition to the above-described elements. Even in a case where unavoidable impurities are contained, the above-described effects are not affected. When the content of In is too large, since ΔT becomes wide, as long as the content is 1000 mass ppm or less, the above-described effects are not affected.


The solder paste containing the above-described flux and the solder powder is excellent in terms of solder wettability and scattering suppression. Additionally, the viscosity of the solder paste is less likely to increase over time.


EXAMPLES

Hereinafter, the present invention will be described with examples, but the present invention is not limited to the following examples.


Fluxes of examples and comparative examples were prepared according to compositions shown in Tables 1 to 12 below, solder pastes were prepared using these fluxes, and the solder wettability (wetting speed), the temperature cycle reliability of the fluxes, and the scattering suppression of the solder pastes were verified.


Composition fractions in Tables 1 to 12 are “% by mass” in a case where the total amount of the flux is set to 100, and vacant cells means “0% by mass”.


In each table, an acrylic resin A is poly 2-ethylhexyl acrylate (Mw=8300). An acrylic resin B is poly 2-ethylhexyl acrylate having a different molecular weight (Mw=11700). An acrylic resin C is polylauryl methacrylate (Mw=10080). An acrylic resin D is poly 2-ethylhexyl acrylate-polyethylene (Mw=12300).


In each table, an aliphatic polyamide was used as a polyamide, hexamethylene bis(hydroxystearic acid amide) was used as a bisamide, and p-toluamide was used as a monoamide.


The solder pastes contained 11% by mass of the flux and 89% by mass of a solder powder. In addition, the solder powder in the solder paste was a Sn—Ag—Cu-based solder alloy containing 3.0% by mass of Ag, 0.5% by mass of Cu, and a balance of Sn.


In addition, the size of a metal powder in the solder paste is a size (particle size distribution) that satisfies the symbol 5 in the powder size classification (Table 2) in JIS Z 3284-1: 2004.


<Evaluation of Solder Wettability (Wetting Speed)>


(1) Verification Method


The wetting speed of the flux was evaluated as described below based on the method of the meniscograph test by performing an oxidation treatment on a copper plate having a width of 5 mm, a length of 25 mm, and a thickness of 0.5 mm at 150° C. for 1 hour to obtain a copper oxide plate as a test plate using Solder Checker SAT-5200 (manufactured by RHESCA Co., Ltd.) as a testing device and Sn-3Ag-0.5Cu (each numerical value is “mass %”) as solder.


First, the test plate was immersed 5 mm in each of the fluxes of Examples 1 to 54 and Comparative Examples 1 to 4 weighed out into a beaker to apply the flux to the test plate. Subsequently, after the application of the flux, the test plate to which the flux had been applied was rapidly immersed in a solder bath to obtain zero cross time (sec). Subsequently, measurement was performed five times on each of the fluxes of Examples 1 to 54 and Comparative Examples 1 to 4, and the average value of the obtained 5 zero cross times (sec) was calculated. The test conditions were set as described below.


Immersion speed into solder bath: 5 mm/sec (JIS Z 3198-4: 2003)


Immersion depth into solder bath: 2 mm (JIS Z 3198-4: 2003)


Immersion time in solder bath: 10 sec (JIS Z 3198-4: 2003)


Solder bath temperature: 245° C. (JIS C 60068-2-69: 2019)


As the average value of the zero cross times (sec) become shorter, the wetting speed becomes faster, which means that the solder wettability is favorable.


(2) Determination Standards


O: The average value of zero cross times (sec) is 6 seconds or shorter.


X: The average value of zero cross times (sec) exceeds 6 seconds.


<Evaluation of Temperature Cycle Reliability>


(1) Verification Method


In the evaluation of the temperature cycle reliability, each of the fluxes of Examples 1 to 54 and Comparative Examples 1 to 4 was applied onto a copper plate to form a residue on the copper plate. Subsequently, a treatment of holding the copper plate on which the residue was formed for 30 minutes at −30° C. and then at 110° C. was repeated 500 times. Subsequently, the presence or absence of cracks in the residue after the treatment was visually evaluated.


(2) Determination Standards


O: The generation of cracks was not shown in the residue.


X: The generation of cracks was shown in the residue.


<Evaluation of Scattering Suppression>


(1) Verification Method


Each of solder paste compositions of the examples and the comparative examples was printed on a copper-clad laminate (sizes: 105 mm×105 mm, thickness: 1.0 mm) using a metal mask (mask thickness: 0.1 mm, one printing pattern with 6.5 mmφ), and then reflow was performed according to a profile in which scattering as shown in FIG. 1 was likely to occur (temperature rising rate: 1.3° C./s, peak temperature: 250° C.), thereby producing a test substrate. The test substrate was observed, and the number of times of the scattering of the solder paste on the entire test substrate was measured. The test was performed 3 times on each of the solder paste compositions of the examples and the comparative examples, and the average value of the numbers of times of the scattering of the solder paste was calculated.


(2) Determination Standards


O: The number of times of the scattering of the solder pastes is less than 10.


X: The number of times of the scattering of the solder pastes is 10 or more.


<Comprehensive Evaluation>


O: All of the solder wettability (wetting speed), the temperature cycle reliability, and the scattering suppression are O.


X: At least one of the solder wettability (wetting speed), the temperature cycle reliability, and the scattering suppression is X.














TABLE 1





Material
Example 1
Example 2
Example 3
Example 4
Example 5






















Organic acids
Specific
1,2,3-Propanetricarboxylic
3
0.1
0.5
1
5



organic acid
acid



Other organic
Sebacic acid



acids
Adipic acid




Eicosanedioic acid




Hydrogenated dimer acid


Resins
Rosin
Hydrogenated rosin
25
25
25
25
25




Acrylic acid-modified




hydrogenated rosin




Polymerized rosin




Disproportionated rosin



Acrylic resin
Acrylic resin A
25
25
25
25
25




Acrylic resin B




Acrylic resin C




Acrylic resin D



Other resin
Polyethylene resin


Amines
Azoles
2-Phenylimidazole
1
1
1
1
1




2-Phenyl-4-




methylimidazole




2-Heptadecylimidazole




Benzimidazole




2-Octylbenzimidazole



Other amine
Monoethanolamine


Halogens
Amine
Diphenylguanidine/HBr


0.5
0.5



hydrohalide



Organic
2,3-Dibromobutane-1,4-

1
0.5
0.5



halogen
diol



compound













Antioxidant
Hindered phenolic








antioxidant














Thixotropic
Amide
Polyamide
3
3
3
3
3


agents
compound
Bisamide




Monoamide



Ester
Hydrogenated castor oil



compound


Solvents
Water
Water



Other
Tetraethylene glycol
43
44.9
44.5
44
41



solvents
dimethyl ether




Hexyl diglycol

















Total
100
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1
1
1
1
1


Solder wettability (wetting speed)







Temperature cycle reliability







Scattering suppression







Comprehensive evaluation


























TABLE 2





Material
Example 6
Example 7
Example 8
Example 9
Example 10






















Organic acids
Specific
1,2,3-Propanetricarboxylic
7
10
15
3
3



organic acid
acid



Other organic
Sebacic acid



acids
Adipic acid




Eicosanedioic acid




Hydrogenated dimer acid


Resins
Rosin
Hydrogenated rosin
25
25
25
25
25




Acrylic acid-modified




hydrogenated rosin




Polymerized rosin




Disproportionated rosin



Acrylic resin
Acrylic resin A
25
25
25
25
25




Acrylic resin B




Acrylic resin C




Acrylic resin D



Other resin
Polyethylene resin


Amines
Azoles
2-Phenylimidazole
1
1
1
1
1




2-Phenyl-4-




methylimidazole




2-Heptadecylimidazole




Benzimidazole




2-Octylbenzimidazole



Other amine
Monoethanolamine



5


Halogens
Amine
Diphenylguanidine/HBr




3



hydrohalide



Organic
2,3-Dibromobutane-1,4-



halogen
diol



compound













Antioxidant
Hindered phenolic








antioxidant














Thixotropic
Amide
Polyamide
3
3
3
3
3


agents
compound
Bisamide




Monoamide



Ester
Hydrogenated castor oil



compound


Solvents
Water
Water



Other
Tetraethylene glycol
39
36
31
38
40



solvents
dimethyl ether




Hexyl diglycol

















Total
100
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1
1
1
1
1


Solder wettability (wetting speed)







Temperature cycle reliability







Scattering suppression







Comprehensive evaluation


























TABLE 3





Material
Example 11
Example 12
Example 13
Example 14
Example 15






















Organic acids
Specific
1,2,3-Propanetricarboxylic
3
3
3
3
3



organic acid
acid



Other organic
Sebacic acid



acids
Adipic acid




Eicosanedioic acid




Hydrogenated dimer acid


Resins
Rosin
Hydrogenated rosin
25
25
25
25
25




Acrylic acid-modified




hydrogenated rosin




Polymerized rosin




Disproportionated rosin



Acrylic resin
Acrylic resin A
25
25
25
25
25




Acrylic resin B




Acrylic resin C




Acrylic resin D



Other resin
Polyethylene resin


Amines
Azoles
2-Phenylimidazole
1
1
1
1
1




2-Phenyl-4-




methylimidazole




2-Heptadecylimidazole




Benzimidazole




2-Octylbenzimidazole



Other amine
Monoethanolamine


Halogens
Amine
Diphenylguanidine/HBr



1
0.5



hydrohalide



Organic
2,3-Dibromobutane-1,4-
5



0.5



halogen
diol



compound













Antioxidant
Hindered phenolic



3
5



antioxidant














Thixotropic
Amide
Polyamide
3


1
1


agents
compound
Bisamide

3

1
1




Monoamide


3
1
1



Ester
Hydrogenated castor oil




3



compound


Solvents
Water
Water



Other
Tetraethylene glycol
38
43
43
39
34



solvents
dimethyl ether




Hexyl diglycol

















Total
100
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1
1
1
1
1


Solder wettability (wetting speed)







Temperature cycle reliability







Scattering suppression







Comprehensive evaluation


























TABLE 4





Material
Example 16
Example 17
Example 18
Example 19
Example 20






















Organic acids
Specific
1,2,3-Propanetricarboxylic
3
3
3
3
3



organic acid
acid



Other organic
Sebacic acid



acids
Adipic acid




Eicosanedioic acid

10




Hydrogenated dimer acid


10


Resins
Rosin
Hydrogenated rosin
25
5
45
25
25




Acrylic acid-modified




hydrogenated rosin




Polymerized rosin




Disproportionated rosin



Acrylic resin
Acrylic resin A
25
45
5




Acrylic resin B



25




Acrylic resin C




25




Acrylic resin D



Other resin
Polyethylene resin


Amines
Azoles
2-Phenylimidazole
1
1
1
1
1




2-Phenyl-4-




methylimidazole




2-Heptadecylimidazole




Benzimidazole




2-Octylbenzimidazole



Other amine
Monoethanolamine


Halogens
Amine
Diphenylguanidine/HBr



hydrohalide



Organic
2,3-Dibromobutane-1,4-



halogen
diol



compound













Antioxidant
Hindered phenolic








antioxidant














Thixotropic
Amide
Polyamide
1
3
3
3
3


agents
compound
Bisamide
1




Monoamide
1



Ester
Hydrogenated castor oil
3



compound


Solvents
Water
Water



Other
Tetraethylene glycol

33
33
43
43



solvents
dimethyl ether




Hexyl diglycol
40
















Total
100
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1
0.11
9
1
1


Solder wettability (wetting speed)







Temperature cycle reliability







Scattering suppression







Comprehensive evaluation


























TABLE 5





Material
Example 21
Example 22
Example 23
Example 24
Example 25






















Organic acids
Specific
1,2,3-Propanetricarboxylic
3
3
3
3
3



organic acid
acid



Other organic
Sebacic acid



acids
Adipic acid




Eicosanedioic acid




Hydrogenated dimer acid


Resins
Rosin
Hydrogenated rosin
25
25
25
25
25




Acrylic acid-modified




hydrogenated rosin




Polymerized rosin




Disproportionated rosin



Acrylic resin
Acrylic resin A

10




Acrylic resin B

5
15




Acrylic resin C

5

15




Acrylic resin D
25
5


15



Other resin
Polyethylene resin


10
10
10


Amines
Azoles
2-Phenylimidazole
1
1
1
1
1




2-Phenyl-4-




methylimidazole




2-Heptadecylimidazole




Benzimidazole




2-Octylbenzimidazole



Other amine
Monoethanolamine


Halogens
Amine
Diphenylguanidine/HBr



hydrohalide



Organic
2,3-Dibromobutane-1,4-



halogen
diol



compound













Antioxidant
Hindered phenolic








antioxidant














Thixotropic
Amide
Polyamide
3
3
3
3
3


agents
compound
Bisamide




Monoamide



Ester
Hydrogenated castor oil



compound


Solvents
Water
Water



Other
Tetraethylene glycol
43
43
43
43
43



solvents
dimethyl ether




Hexyl diglycol

















Total
100
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1
1
1.67
1.67
1.67


Solder wettability (wetting speed)







Temperature cycle reliability







Scattering suppression







Comprehensive evaluation


























TABLE 6





Material
Example 26
Example 27
Example 28
Example 29
Example 30






















Organic acids
Specific
1,2,3-Propanetricarboxylic
3
3
3
1
1



organic acid
acid



Other organic
Sebacic acid



2



acids
Adipic acid




2




Eicosanedioic acid




Hydrogenated dimer acid


Resins
Rosin
Hydrogenated rosin
25
25
25
25
25




Acrylic acid-modified




hydrogenated rosin




Polymerized rosin




Disproportionated rosin



Acrylic resin
Acrylic resin A
5
25
25
25
25




Acrylic resin B
5




Acrylic resin C
5




Acrylic resin D
5



Other resin
Polyethylene resin
5


Amines
Azoles
2-Phenylimidazole
1
1
1
1
1




2-Phenyl-4-




methylimidazole




2-Heptadecylimidazole




Benzimidazole




2-Octylbenzimidazole



Other amine
Monoethanolamine


Halogens
Amine
Diphenylguanidine/HBr



hydrohalide



Organic
2,3-Dibromobutane-1,4-



halogen
diol



compound













Antioxidant
Hindered phenolic








antioxidant














Thixotropic
Amide
Polyamide
3


3
3


agents
compound
Bisamide




Monoamide

6
8.5



Ester
Hydrogenated castor oil



compound


Solvents
Water
Water



Other
Tetraethylene glycol
43
40
37.5
43
43



solvents
dimethyl ether




Hexyl diglycol

















Total
100
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1.25
1
1
1
1


Solder wettability (wetting speed)







Temperature cycle reliability







Scattering suppression







Comprehensive evaluation


























TABLE 7





Material
Example 31
Example 32
Example 33
Example 34
Example 35






















Organic acids
Specific
1,2,3-Propanetricarboxylic
1
1
1
3
3



organic acid
acid



Other organic
Sebacic acid

0.5

0.5
0.5



acids
Adipic acid

0.5

0.5
0.5




Eicosanedioic acid
2
0.5

0.5
0.5




Hydrogenated dimer acid

0.5
10
0.5
0.5


Resins
Rosin
Hydrogenated rosin
25
25
25
10
10




Acrylic acid-modified



5
5




hydrogenated rosin




Polymerized rosin



5
5




Disproportionated rosin



5
5



Acrylic resin
Acrylic resin A
25
25
25
5
4




Acrylic resin B



5
4




Acrylic resin C



5
4




Acrylic resin D



5
4



Other resin
Polyethylene resin




4


Amines
Azoles
2-Phenylimidazole
1
1
1
1
1




2-Phenyl-4-




1




methylimidazole




2-Heptadecylimidazole




1




Benzimidazole




1




2-Octylbenzimidazole




1



Other amine
Monoethanolamine




1


Halogens
Amine
Diphenylguanidine/HBr



2
1



hydrohalide



Organic
2,3-Dibromobutane-1,4-



1
1



halogen
diol



compound













Antioxidant
Hindered phenolic



2
2



antioxidant














Thixotropic
Amide
Polyamide
3
3
3
1
1


agents
compound
Bisamide



1
1




Monoamide



1
1



Ester
Hydrogenated castor oil



1
1



compound


Solvents
Water
Water



Other
Tetraethylene glycol
43
43
35
20
18



solvents
dimethyl ether




Hexyl diglycol



20
18












Total
100
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1
1
1
1.25
1.56


Solder wettability (wetting speed)







Temperature cycle reliability







Scattering suppression







Comprehensive evaluation


























TABLE 8





Material
Example 36
Example 37
Example 38
Example 39
Example 40






















Organic acids
Specific
1,2,3-Propanetricarboxylic
3
3
0.5
3
3



organic acid
acid



Other organic
Sebacic acid



acids
Adipic acid

5




Eicosanedioic acid

5




Hydrogenated dimer acid


5


Resins
Rosin
Hydrogenated rosin
25
25
25
25
25




Acrylic acid-modified




hydrogenated rosin




Polymerized rosin




Disproportionated rosin



Acrylic resin
Acrylic resin A
25
25
20
25
25




Acrylic resin B




Acrylic resin C




Acrylic resin D



Other resin
Polyethylene resin


Amines
Azoles
2-Phenylimidazole
2
10
0.1




2-Phenyl-4-



2




methylimidazole




2-Heptadecylimidazole




2




Benzimidazole




2-Octylbenzimidazole



Other amine
Monoethanolamine


Halogens
Amine
Diphenylguanidine/HBr


1



hydrohalide



Organic
2,3-Dibromobutane-1,4-



halogen
diol



compound













Antioxidant
Hindered phenolic








antioxidant














Thixotropic
Amide
Polyamide
3
3
3
3
3


agents
compound
Bisamide




Monoamide



Ester
Hydrogenated castor oil



compound


Solvents
Water
Water



Other
Tetraethylene glycol
42
24
45.4
42
42



solvents
dimethyl ether




Hexyl diglycol

















Total
100
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1
1
1.25
1
1


Solder wettability (wetting speed)







Temperature cycle reliability







Scattering suppression







Comprehensive evaluation


























TABLE 9





Material
Example 41
Example 42
Example 43
Example 44
Example 45






















Organic acids
Specific
1,2,3-Propanetricarboxylic
3
3
3
3
3



organic acid
acid



Other organic
Sebacic acid



acids
Adipic acid




Eicosanedioic acid




Hydrogenated dimer acid


Resins
Rosin
Hydrogenated rosin
25
25
25
25
25




Acrylic acid-modified




hydrogenated rosin




Polymerized rosin




Disproportionated rosin



Acrylic resin
Acrylic resin A
25
25
25
25
25




Acrylic resin B




Acrylic resin C




Acrylic resin D



Other resin
Polyethylene resin


Amines
Azoles
2-Phenylimidazole


0.5
5
3




2-Phenyl-4-


0.5




methylimidazole




2-Heptadecylimidazole


0.5




Benzimidazole
2

0.5




2-Octylbenzimidazole

2
0.5



Other amine
Monoethanolamine


0.5


Halogens
Amine
Diphenylguanidine/HBr



hydrohalide



Organic
2,3-Dibromobutane-1,4-



halogen
diol



compound













Antioxidant
Hindered phenolic








antioxidant














Thixotropic
Amide
Polyamide
3
3
3
3
3


agents
compound
Bisamide




Monoamide



Ester
Hydrogenated castor oil



compound


Solvents
Water
Water



Other
Tetraethylene glycol
42
42
41
39
41



solvents
dimethyl ether




Hexyl diglycol

















Total
100
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1
1
1
1
1


Solder wettability (wetting speed)







Temperature cycle reliability







Scattering suppression







Comprehensive evaluation


























TABLE 10





Material
Example 46
Example 47
Example 48
Example 49
Example 50






















Organic acids
Specific
1,2,3-Propanetricarboxylic
3
3
3
1
1



organic acid
acid



Other organic
Sebacic acid




0.5



acids
Adipic acid




0.5




Eicosanedioic acid




0.5




Hydrogenated dimer acid

2
7
9
0.5


Resins
Rosin
Hydrogenated rosin
25
25
25
25
10




Acrylic acid-modified




5




hydrogenated rosin




Polymerized rosin




5




Disproportionated rosin




5



Acrylic resin
Acrylic resin A
25
25
25
25
5




Acrylic resin B




5




Acrylic resin C




5




Acrylic resin D




5



Other resin
Polyethylene resin


Amines
Azoles
2-Phenylimidazole
1
1
1
0.1
1




2-Phenyl-4-




0.5




methylimidazole




2-Heptadecylimidazole




0.5




Benzimidazole




0.5




2-Octylbenzimidazole




0.5



Other amine
Monoethanolamine


Halogens
Amine
Diphenylguanidine/HBr



1
2



hydrohalide



Organic
2,3-Dibromobutane-1,4-



halogen
diol



compound













Antioxidant
Hindered phenolic








antioxidant














Thixotropic
Amide
Polyamide
3
3
3
3
1


agents
compound
Bisamide




1




Monoamide




1



Ester
Hydrogenated castor oil



compound


Solvents
Water
Water



Other
Tetraethylene glycol
43
41
36
35.9
44



solvents
dimethyl ether




Hexyl diglycol

















Total
100
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1
1
1
1
1.25


Solder wettability (wetting speed)







Temperature cycle reliability







Scattering suppression







Comprehensive evaluation

























TABLE 11





Material
Example 51
Example 52
Example 53
Example 54





















Organic acids
Specific
1,2,3-Propanetricarboxylic
1
1
1
3



organic acid
acid



Other organic
Sebacic acid
0.5
0.5
0.5



acids
Adipic acid
0.5
0.5
0.5




Eicosanedioic acid
0.5
0.5
0.5




Hydrogenated dimer acid
0.5
0.5
0.5


Resins
Rosin
Hydrogenated rosin
10
10
10
21




Acrylic acid-modified
5
5
5




hydrogenated rosin




Polymerized rosin
5
5
5




Disproportionated rosin
5
5
5



Acrylic resin
Acrylic resin A
4
5
4
21




Acrylic resin B
4
5
4




Acrylic resin C
4
5
4




Acrylic resin D
4
5
4



Other resin
Polyethylene resin
4

4


Amines
Azoles
2-Phenylimidazole
1
0.5
0.5




2-Phenyl-4-
0.5
0.5
0.5




methylimidazole




2-Heptadecylimidazole
0.5
0.5
0.5




Benzimidazole
0.5
0.5
0.5




2-Octylbenzimidazole
0.5
0.5
0.5



Other amine
Monoethanolamine

0.5
0.5


Halogens
Amine
Diphenylguanidine/HBr



1



hydrohalide



Organic
2,3-Dibromobutane-1,4-
5



halogen
diol



compound












Antioxidant
Hindered phenolic

3





antioxidant













Thixotropic
Amide
Polyamide
1
1
1
3


agents
compound
Bisamide
1
1
1




Monoamide
1
1
1



Ester
Hydrogenated castor oil
1



compound


Solvents
Water
Water



Other
Tetraethylene glycol
40
43

51



solvents
dimethyl ether




Hexyl diglycol


46












Total
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)
1.56
1.25
1.56
1


Solder wettability (wetting speed)






Temperature cycle reliability






Scattering suppression






Comprehensive evaluation
























TABLE 12






Comparative
Comparative
Comparative
Comparative


Material
Example 1
Example 2
Example 3
Example 4





















Organic acids
Specific
1,2,3-Propanetricarboxylic


3
3



organic acid
acid



Other organic
Sebacic acid



acids
Adipic acid




Eicosanedioic acid
5




Hydrogenated dimer acid

10


Resins
Rosin
Hydrogenated rosin
42
25
42
25




Acrylic acid-modified




hydrogenated rosin




Polymerized rosin




Disproportionated rosin



Acrylic resin
Acrylic resin A

25

25




Acrylic resin B




Acrylic resin C




Acrylic resin D



Other resin
Polyethylene resin


Amines
Azoles
2-Phenylimidazole




2-Phenyl-4-




methylimidazole




2-Heptadecylimidazole




Benzimidazole




2-Octylbenzimidazole



Other amine
Monoethanolamine


Halogens
Amine
Diphenylguanidine/HBr


1



hydrohalide



Organic
2,3-Dibromobutane-1,4-



halogen
diol



compound












Antioxidant
Hindered phenolic







antioxidant













Thixotropic
Amide
Polyamide
3
3
3
3


agents
compound
Bisamide




Monoamide



Ester
Hydrogenated castor oil



compound


Solvents
Water
Water



10



Other
Tetraethylene glycol
50
37
51
34



solvents
dimethyl ether




Hexyl diglycol















Total
100
100
100
100


Rosin total amount/acrylic resin total amount (mass ratio)

1

1


Solder wettability (wetting speed)
X
X




Temperature cycle reliability
X

X



Scattering suppression



X


Comprehensive evaluation
X
X
X
X









In the present invention, as shown in Example 1, when the flux contained 1,2,3-propanetricarboxylic acid as an organic acid, a hydrogenated rosin as a rosin, the acrylic resin A as an acrylic resin, 2-phenylimidazole as an azole, a polyamide as an amide compound, and tetraethylene glycol dimethyl ether as a solvent, the content of the 1,2,3-propanetricarboxylic acid was within the range specified in the present invention, and the flux did not contain water, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 2 to 4, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and a halogen compound was contained, it was possible to make the fluxes have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 5 to 8, even when the content of 1,2,3-propanetricarboxylic acid was changed within the range specified in the present invention, it was possible to make the fluxes have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 9, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and an amine other than the azole (other amine) was contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 10 and 11, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and the content of the halogen compound was changed, it was possible to make the fluxes have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 12 and 13, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and the kind of the amide compound was changed, it was possible to make the fluxes have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 14, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and a halogen compound, an antioxidant, and a plurality of kinds of amide compounds were contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 15, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and a halogen compound, an antioxidant, a plurality of kinds of amide compounds, and an ester compound were contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 16, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and the kind of the solvent was changed, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 17, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, an organic acid other than 1,2,3-propanetricarboxylic acid (other organic acid) was contained, and the content of the acrylic resin was increased by decreasing the content of the rosin, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 18, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, the kind of the other organic acid was changed, and the content of the acrylic resin was decreased by increasing the content of the rosin, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 19 to 21, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and the kind of the acrylic resin was changed, it was possible to make the fluxes have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 22, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and a plurality of kinds of acrylic resins were contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 23 to 25, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and a polyethylene resin other than the rosin and the acrylic resin (other resin) was contained, it was possible to make the fluxes have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 26, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, a plurality of kinds of acrylic resins were contained, and another resin was contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 27 and 28, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, the kind of the amide compound was changed, and the content of the amide compound was increased, it was possible to make the fluxes have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 29 to 31, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and the kind of the other organic acid was changed, it was possible to make the fluxes have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 32, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and a plurality of kinds of other organic acids were contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 33, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and the content of the other organic acid was increased, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 34, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, a plurality of kinds of other organic acids, a plurality of kinds of rosins, a plurality of kinds of acrylic resins, a halogen compound, an antioxidant, a plurality of kinds of amide compounds, an ester compound, and a plurality of kinds of solvents were contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 35, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, a plurality of kinds of other organic acids, a plurality of kinds of rosins, a plurality of kinds of acrylic resins, another resin, a plurality of kinds of azoles, another amine, a halogen compound, an antioxidant, a plurality of kinds of amide compounds, an ester compound, and a plurality of kinds of solvents were contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 36, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and the content of the azole was increased, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 37, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and the contents of the other organic acid and the azole were increased, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 38, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, the content of the other organic acid was increased, the content of the azole was decreased, and a halogen compound was contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 39 to 42, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and the kind of the azole was changed, it was possible to make the fluxes have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 43, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, a plurality of kinds of azoles were contained, and an amine other than the azoles (other amine) was contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 44 to 46, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, and the content of the azole was decreased, it was possible to make the fluxes have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Examples 47 and 48, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, the content of the azole was decreased, and the content of the other organic acid was increased, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 49, even when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, the content of the azole was decreased, the content of the other organic acid was increased, and a halogen compound was contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 50, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, the content of other organic acids was increased, a plurality of kinds of rosins were contained, a plurality of kinds of acrylic resins were contained, a plurality of kinds of azoles were contained, a halogen compound was contained, and a plurality of kinds of amide compounds were contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 51, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, a plurality of kinds of other organic acids were contained, a plurality of kinds of rosins were contained, a plurality of kinds of acrylic resins were contained, another resin was contained, a plurality of kinds of azoles were contained, a halogen compound was contained, a plurality of kinds of amide compounds were contained, and an ester compound was contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 52, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, a plurality of kinds of other organic acids were contained, a plurality of kinds of rosins were contained, a plurality of kinds of acrylic resins were contained, a plurality of kinds of azoles were contained, an antioxidant was contained, and a plurality of kinds of amide compounds were contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 53, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, a plurality of kinds of other organic acids were contained, a plurality of kinds of rosins were contained, a plurality of kinds of acrylic resins were contained, another resin was contained, a plurality of kinds of azoles were contained, and a plurality of kinds of amide compounds were contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


As described in Example 54, when 1,2,3-propanetricarboxylic acid was contained within the range specified in the present invention, a rosin was contained, an acrylic resin was contained, and an amide compound was contained, it was possible to make the flux have sufficient solder wettability, temperature cycle reliability, and scattering suppression effect.


Examples 1 to 54 contained 1,2,3-propanetricarboxylic acid within the range specified in the present invention and had sufficient solder wettability.


In contrast, Comparative Examples 1 and 2 did not contain 1,2,3-propanetricarboxylic acid and had insufficient solder wettability.


From these results, it was clarified that, when 1,2,3-propanetricarboxylic acid is contained within the range specified in the present invention, it is possible to make fluxes have sufficient solder wettability.


Examples 1 to 54 contained an acrylic resin and had sufficient temperature cycle reliability.


In contrast, Comparative Examples 1 and 3 did not contain an acrylic resin and had insufficient temperature cycle reliability.


From these results, it was clarified that, when an acrylic resin is contained, it is possible to make fluxes have sufficient temperature cycle reliability.


In addition, in Examples 1 to 16 and 18 to 54, the ratio (mass ratio) of the content of the rosin to the content of the acrylic resin was 1 or more and 9 or less, and it was possible to make the fluxes have more sufficient temperature cycle reliability.


Examples 1 to 54 did not contain water and had a sufficient scattering suppression effect.


In contrast, Comparative Example 4 contained water and has an insufficient scattering suppression effect.


From these results, it was clarified that, when water was not contained, it is possible to make fluxes have a sufficient scattering suppression effect.


<Evaluation of Copper Plate Corrosion Suppression Capability>


(1) Verification Method


The copper plate corrosion suppression capability was evaluated by the following copper plate corrosion test based on JIS Z 3197: 2012 8.4.1.


Preparation of test copper plate: A 3 mm-deep indent was made with a steel ball having a diameter of 20 mm at the center of a phosphorous-deoxidized copper plate having dimensions of 50 mm×50 mm×0.5 mm to produce a test piece. The test piece was degreased with acetone and then immersed in sulfuric acid at 65° C. for 1 minute to remove an oxide film or the like on the surface. Next, the test piece was immersed in an ammonium persulfate solution at 20° C. for 1 minute, then, washed with purified water, and dried to produce a test copper plate.


The solid contents of the fluxes of Examples 44 to 53 and Comparative Examples 1 to 4 were measured by a method specified in JIS Z 3197: 2012 8.1.3, and the fluxes containing an appropriate amount (0.035 to 0.040 g) of the solid content were added to the indents at the centers of the test copper plates.


Next, the test copper plates were injected into a constant temperature and constant humidity bath set to humidification conditions of a temperature of 40° C. and a relative humidity of 90% and left to stand in the bath for 72 hours. For each flux of each example, two test copper plates were prepared, and one blank was added.


After being left to stand in the bath for 96 hours, the test copper plates were taken out from the constant temperature and constant humidity bath, and corrosion traces were compared with the blanks with a microscope at a magnification of 30 times. The copper plate corrosion suppression capability was evaluated based on determination standards shown below. The evaluation results are shown in Table 13.


(2) Determination Standards


O: There is no discoloration


X: There is discoloration












TABLE 13







Organic acid total amount/




azoles total amount
Corrosion



(mass ratio)
suppression effect


















Example 44
0.6



Example 45
1



Example 46
3



Example 47
5



Example 48
10



Example 49
100



Example 50
1



Example 51
1



Example 52
1.2



Example 53
1.2



Comparative Example 1

x


Comparative Example 2

x


Comparative Example 3

x


Comparative Example 4

x









As shown in Examples 44 to 53, the ratios (mass ratios) of the total content of the organic acid to the content of the azoles were 0.6 or more and 100 or less, and it was possible to make the fluxes have a sufficient corrosion suppression effect.


As shown in Comparative Examples 1 to 4, the ratios (mass ratios) of the total content of the organic acid to the content of the azoles were not 0.6 or more and 100 or less, and the corrosion suppression effects were not sufficient.


From these results, it was clarified that, when the ratio (mass ratios) of the total content of the organic acid to the content of the azoles is set to 0.6 or more and 100 or less, it is possible to make fluxes have a sufficient corrosion suppression effect.


<Evaluation of Thickening Suppression Effect of Solder Paste>


The thickening suppression effects of solder pastes formulated using the above-described flux of each example and a solder alloy having a composition shown in Table 14 below were also verified.


(1) Verification Method


For the obtained solder pastes, the viscosities were continuously measured for 12 hours according to a method specified in “4.2 Viscosity Characteristic Test” of JIS Z 3284-3: 2014 using a spiral viscometer (PCU-205, manufactured by Malcolm Company Limited) at a rotation speed of 10 rpm and a measurement temperature of 25° C. In addition, the initial viscosities (the viscosities after 30 minutes of stirring) and the viscosities after 12 hours were compared, and the thickening suppression effects were evaluated based on the following standards.


(2) Determination Standards


O: Viscosity after 12 hours≤Initial viscosity×1.2 An increase in the viscosity over time is small and favorable.


X: Viscosity after 12 hours>Initial viscosity×1.2 An increase in the viscosity over time is large and poor.














TABLE 14









Alloy composition (Ag, Cu: % by mass, As, Sb, Bi, Pb: mass ppm)
Mathematical
Mathematical
Thickening suppression


















Sn
Ag
Cu
As
Sb
Bi
Pb
formula (1)
formula (2)
effect of solder paste





















Test Example A1
Bal
0
0
100
25
25
25
275
4.50



Test Example A2
Bal
0
0
100
3000
300
300
3800
5.33



Test Example B1
Bal
0
0
0
100
100
100
300
0.50
X


Test Example B2
Bal
0
0
25
25
25
25
125
1.50
X


Test Example A3
Bal
0
0.7
100
25
25
25
275
4.50



Test Example A4
Bal
0
0.7
100
3000
300
300
3800
5.33



Test Example B3
Bal
0
0.7
0
100
100
100
300
0.50
X


Test Example B4
Bal
0
0.7
25
25
25
25
125
1.50
X


Test Example A5
Bal
3
0.5
100
25
25
25
275
4.50



Test Example A6
Bal
3
0.5
100
3000
300
300
3800
5.33



Test Example B5
Bal
3
0.5
0
100
100
100
300
0.50
X


Test Example B6
Bal
3
0.5
25
25
25
25
125
1.50
X









In the solder pastes for which the flux of each example shown in Table 1 to Table 12 and the solder alloy of each of Test Examples A1 to A6 shown in Table 14, which satisfied the following mathematical formula (1) and mathematical formula (2), sufficient effects were obtained in terms of not only solder wettability and scattering suppression but also the thickening suppression effect.





275≤2As+Sb+Bi+Pb  (1)





0.01≤(2As+Sb)/(Bi+Pb)≤10.00  (2)


In the formula (1) and the formula (2), As, Sb, Bi, and Pb each represent a content (mass ppm) in the alloy composition.


In contrast, in the solder pastes for which the flux of each example shown in Table 1 to Table 12 and the solder alloy of each of Test Examples B1 to B6 shown in Table 14, which did not satisfy the mathematical formula (1) and the mathematical formula (2), effects were obtained in terms of the wettability and scattering suppression of the solder pastes, but effects were not obtained in terms of the thickening suppression effect.


Furthermore, in the solder pastes for which the flux of each example shown in Table 1 to Table 12 and the solder alloy of each of Test Examples A1 to A6 that contained at least one of As: 25 to 300 mass ppm, Pb: more than 0 mass ppm and 5100 mass ppm or less, Sb: more than 0 mass ppm and 3000 mass ppm or less and Bi: more than 0% mass ppm and 10000 mass ppm or less, at least one of Ag: 0% by mass or more and 4% by mass or less and Cu: 0% by mass or more and 0.9% by mass or less, and a balance (Bal) of Sn and satisfied the mathematical formula (1) and the mathematical formula (2), solder wettability attributed to the 1,2,3-propanetricarboxylic acid contained, the temperature cycle reliability attributed to the acrylic resin contained, and the scattering suppression effect attributed to water not contained were not impaired, and sufficient effects were obtained in terms of the thickening suppression effect.


In addition, for the solder pastes for which the flux of each example shown in Table 1 to Table 12 and the solder alloy of each test example shown in Table 15 to Table 20 or each test example shown in Table 21 to Table 44 were used, the above-described <evaluation of thickening suppression effect (change over time) of solder paste> and the following <evaluation of solder wettability (wetting speed)> were performed. In addition, the liquidus temperatures and solidus temperatures of the solder powders were measured, and the following <evaluation of ΔT> was performed.


<Evaluation of ΔT>


(1) Verification Method


For the solder powders to be mixed with the flux, DSC measurement was performed using Model No.: EXSTAR DSC7020 manufactured by Seiko Instruments Inc. with a sample amount of approximately 30 mg at a temperature rising rate of 15° C./min, and the solidus temperatures and the liquidus temperatures were obtained. The solidus temperature was subtracted from the obtained liquidus temperature to obtain ΔT.


(2) Determination Standards


O: ΔT is 10° C. or less.


X: ΔT exceeds 10° C.


<Evaluation of Wettability>


(1) Verification Method


Each solder paste immediately after production was printed on a Cu plate, heated from 25° C. to 260° C. at a temperature rising rate of 1° C./s in a N2 atmosphere in a reflow furnace, and then cooled to room temperature. The appearance of solder bumps after cooling was observed with an optical microscope, thereby evaluating wettability.


(2) Determination Standards


O: A case where the solder powder that is not fully melted is not observed.


X: A case where the solder powder that is not fully melted is observed.


<Comprehensive Evaluation>


O: In Tables 15 to 44, the change over time, ΔT, and the wettability are all O in each evaluation.


X: In Tables 15 to 44, at least one of the change over time, ΔT, and wettability is X in each evaluation.











TABLE 15









Evaluation items















Alloy composition (mass ppm)
Formula
Formula
Change

Wetta-
Comprehensive



















Sn
As
Sb
Bi
Pb
(1)
(2)
over time
ΔT
bility
evaluation






















Test Example C1
Bal
100
 25
 25
 25
 275
4.50






Test Example C2
Bal
100
 50
 25
0
 275
10.00 






Test Example C3
Bal
100
0
 75
0
 275
2.67






Test Example C4
Bal
100
0
0
 75
 275
2.67






Test Example C5
Bal
100
 50
 50
 50
 350
2.50






Test Example C6
Bal
 50
100
100
 50
 350
1.33






Test Example C7
Bal
300
0
300
300
1200
1.00






Test Example C8
Bal
200
300
250
250
1200
1.40






Test Example C9
Bal
100
500
250
250
1200
1.40






Test Example C10
Bal
200
 50
600
850
1900
0.31






Test Example C11
Bal
200
500
500
500
1900
0.90






Test Example C12
Bal
200
500
1000 
0
1900
0.90






Test Example C13
Bal
200
500
 0
1000 
1900
0.90






Test Example C14
Bal
 25
500
350
1000 
1900
0.41






Test Example C15
Bal
100
3000 
300
300
3800
5.33






Test Example C16
Bal
100
0
0
5100 
5300
0.04






Test Example C17
Bal
100
0
10000 
0
10200 
0.02






Test Example C18
Bal
100
0
10000 
5000 
15200 
0.01






Test Example C201
Bal
0
100
100
100
 300
0.50
X


X


Test Example C202
Bal
 25
 25
 25
 25
125
1.50
X


X


Test Example C203
Bal
300
500
 50
 50
1200

11.00



X
X


Test Example C204
Bal

350

1150 
 25
 25
1900

37.00



X
X


Test Example C205
Bal

800

800
100
100
2600

12.00



X
X


Test Example C206
Bal
250

4800

 1
0
5301

5300.00  



X
X


Test Example C207
Bal

800


3500

100
100
5300

25.50



X
X


Test Example C208
Bal
100

10000

 1
0
10201 

10200.00  



X
X


Test Example C209
Bal
100
100

25000


25000

50300 
0.01

X

X


Test Example C210
Bal
100
100

50000

0
50300 
0.01

X

X


Test Example C211
Bal
100
100
 0

50000

50300 
0.01

X

X


Test Example C212
Bal
300
3000 
 0
0
3600





X
X


Test Example C213
Bal
100
0
100

25000

25300 
0.01

X

X





Underlines indicate that the corresponding values are outside the scope of the present invention.

















TABLE 16









Alloy composition (As, Bi, Pb: mass ppm,

Evaluation items















Cu: % by mass)
Formula
Formula
Change

Wetta-
Comprehensive




















Sn
Cu
As
Sb
Bi
Pb
(1)
(2)
over time
ΔT
bility
evaluation























Test Example C19
Bal
0.7
100
 25
 25
 25
 275
4.50






Test Example C20
Bal
0.7
100
 50
 25
0
 275
10.00 






Test Example C21
Bal
0.7
100
0
 75
0
 275
2.67






Test Example C22
Bal
0.7
100
0
0
 75
 275
2.67






Test Example C23
Bal
0.7
100
 50
 50
 50
 350
2.50






Test Example C24
Bal
0.7
 50
100
100
 50
 350
1.33






Test Example C25
Bal
0.7
300
0
300
300
1200
1.00






Test Example C26
Bal
0.7
200
300
250
250
1200
1.40






Test Example C27
Bal
0.7
100
500
250
250
1200
1.40






Test Example C28
Bal
0.7
200
 50
600
850
1900
0.31






Test Example C29
Bal
0.7
200
500
500
500
1900
0.90






Test Example C30
Bal
0.7
200
500
1000 
0
1900
0.90






Test Example C31
Bal
0.7
200
500
 0
1000 
1900
0.90






Test Example C32
Bal
0.7
 25
500
350
1000 
1900
0.41






Test Example C33
Bal
0.7
100
3000 
300
300
3800
5.33






Test Example C34
Bal
0.7
100
0
0
5100 
5300
0.04






Test Example C35
Bal
0.7
100
0
10000 
0
10200 
0.02






Test Example C36
Bal
0.7
100
0
10000 
5000 
15200 
0.01






Test Example C214
Bal
0.7
0
100
100
100
 300
0.50
X


X


Test Example C215
Bal
0.7
 25
 25
 25
 25
125
1.50
X


X


Test Example C216
Bal
0.7
300
500
 50
 50
1200

11.00



X
X


Test Example C217
Bal
0.7

350

1150 
 25
 25
1900

37.00



X
X


Test Example C218
Bal
0.7

800

800
100
100
2600

12.00



X
X


Test Example C219
Bal
0.7
250

4800

 1
0
5301

5300.00  



X
X


Test Example C220
Bal
0.7

800


3500

100
100
5300

25.50



X
X


Test Example C221
Bal
0.7
100

10000

 1
0
10201 

10200.00  



X
X


Test Example C222
Bal
0.7
100
100

25000


25000

50300 
0.01

X

X


Test Example C223
Bal
0.7
100
100

50000

0
50300 
0.01

X

X


Test Example C224
Bal
0.7
100
100
 0

50000

50300 
0.01

X

X


Test Example C225
Bal
0.7
300
3000 
 0
0
3600





X
X


Test Example C226
Bal
0.7
100
0
100

25000

25300 
0.01

X

X





Underlines indicate that the corresponding values are outside the scope of the present invention.

















TABLE 17









Alloy composition (As, Sb, Bi, Pb: mass ppm,

Evaluation items















Ag, Cu: % by mass)
Formula
Formula
Change

Wetta-
Comprehensive





















Sn
Ag
Cu
As
Sb
Bi
Pb
(1)
(2)
over time
ΔT
bility
evaluation
























Test Example C37
Bal
1
0.5
100
 25
 25
 25
 275
4.50






Test Example C38
Bal
1
0.5
100
 50
 25
0
 275
10.00 






Test Example C39
Bal
1
0.5
100
0
 75
0
 275
2.67






Test Example C40
Bal
1
0.5
100
0
0
 75
 275
2.67






Test Example C41
Bal
1
0.5
100
 50
 50
 50
 350
2.50






Test Example C42
Bal
1
0.5
 50
100
100
 50
 350
1.33






Test Example C43
Bal
1
0.5
300
0
300
300
1200
1.00






Test Example C44
Bal
1
0.5
200
300
250
250
1200
1.40






Test Example C45
Bal
1
0.5
100
500
250
250
1200
1.40






Test Example C46
Bal
1
0.5
200
 50
600
850
1900
0.31






Test Example C47
Bal
1
0.5
200
500
500
500
1900
0.90






Test Example C48
Bal
1
0.5
200
500
1000 
0
1900
0.90






Test Example C49
Bal
1
0.5
200
500
 0
1000 
1900
0.90






Test Example C50
Bal
1
0.5
 25
500
350
1000 
1900
0.41






Test Example C51
Bal
1
0.5
100
3000 
300
300
3800
5.33






Test Example C52
Bal
1
0.5
100
0
0
5100 
5300
0.04






Test Example C53
Bal
1
0.5
100
0
10000 
0
10200 
0.02






Test Example C54
Bal
1
0.5
100
0
10000 
5000 
15200 
0.01






Test Example C227
Bal
1
0.5
0
100
100
100
 300
0.50
X


X


Test Example C228
Bal
1
0.5
 25
 25
 25
 25
125
1.50
X


X


Test Example C229
Bal
1
0.5
300
500
 50
 50
1200

11.00



X
X


Test Example C230
Bal
1
0.5

350

1150 
 25
 25
1900

37.00



X
X


Test Example C231
Bal
1
0.5

800

800
100
100
2600

12.00



X
X


Test Example C232
Bal
1
0.5
250

4800

 1
0
5301

5300.00  



X
X


Test Example C233
Bal
1
0.5

800


3500

100
100
5300

25.50



X
X


Test Example C234
Bal
1
0.5
100

10000

 1
0
10201 

10200.00  



X
X


Test Example C235
Bal
1
0.5
100
100

25000


25000

50300 
0.01

X

X


Test Example C236
Bal
1
0.5
100
100

50000

0
50300 
0.01

X

X


Test Example C237
Bal
1
0.5
100
100
 0

50000

50300 
0.01

X

X


Test Example C238
Bal
1
0.5
300
3000 
 0
0
3600





X
X


Test Example C239
Bal
1
0.5
100
0
100

25000

25300 
0.01

X

X





Underlines indicate that the corresponding values are outside the scope of the present invention.

















TABLE 18









Alloy composition (As, Sb, Bi, Pb: mass ppm,

Evaluation items















Ag, Cu: % by mass)
Formula
Formula
Change

Wetta-
Comprehensive





















Sn
Ag
Cu
As
Sb
Bi
Pb
(1)
(2)
over time
ΔT
bility
evaluation
























Test Example C55
Bal
2
0.5
100
 25
 25
 25
 275
4.50






Test Example C56
Bal
2
0.5
100
 50
 25
0
 275
10.00 






Test Example C57
Bal
2
0.5
100
0
 75
0
 275
2.67






Test Example C58
Bal
2
0.5
100
0
0
 75
 275
2.67






Test Example C59
Bal
2
0.5
100
 50
 50
 50
 350
2.50






Test Example C60
Bal
2
0.5
 50
100
100
 50
 350
1.33






Test Example C61
Bal
2
0.5
300
0
300
300
1200
1.00






Test Example C62
Bal
2
0.5
200
300
250
250
1200
1.40






Test Example C63
Bal
2
0.5
100
500
250
250
1200
1.40






Test Example C64
Bal
2
0.5
200
 50
600
850
1900
0.31






Test Example C65
Bal
2
0.5
200
500
500
500
1900
0.90






Test Example C66
Bal
2
0.5
200
500
1000 
0
1900
0.90






Test Example C67
Bal
2
0.5
200
500
 0
1000 
1900
0.90






Test Example C68
Bal
2
0.5
 25
500
350
1000 
1900
0.41






Test Example C69
Bal
2
0.5
100
3000 
300
300
3800
5.33






Test Example C70
Bal
2
0.5
100
0
0
5100 
5300
0.04






Test Example C71
Bal
2
0.5
100
0
10000 
0
10200 
0.02






Test Example C72
Bal
2
0.5
100
0
10000 
5000 
15200 
0.01






Test Example C240
Bal
2
0.5
0
100
100
100
 300
0.50
X


X


Test Example C241
Bal
2
0.5
 25
 25
 25
 25
125
1.50
X


X


Test Example C242
Bal
2
0.5
300
500
 50
 50
1200

11.00



X
X


Test Example C243
Bal
2
0.5

350

1150 
 25
 25
1900

37.00



X
X


Test Example C244
Bal
2
0.5

800

800
100
100
2600

12.00



X
X


Test Example C245
Bal
2
0.5
250

4800

 1
0
5301

5300.00  



X
X


Test Example C246
Bal
2
0.5

800


3500

100
100
5300

25.50



X
X


Test Example C247
Bal
2
0.5
100

10000

 1
0
10201 

10200.00  



X
X


Test Example C248
Bal
2
0.5
100
100

25000


25000

50300 
0.01

X

X


Test Example C249
Bal
2
0.5
100
100

50000

0
50300 
0.01

X

X


Test Example C250
Bal
2
0.5
100
100
 0

50000

50300 
0.01

X

X


Test Example C251
Bal
2
0.5
300
3000 
 0
0
3600





X
X


Test Example C252
Bal
2
0.5
100
0
100

25000

25300 
0.01

X

X





Underlines indicate that the corresponding values are outside the scope of the present invention.

















TABLE 19









Alloy composition (As, Sb, Bi, Pb: mass ppm,

Evaluation items















Ag, Cu: % by mass)
Formula
Formula
Change

Wetta-
Comprehensive





















Sn
Ag
Cu
As
Sb
Bi
Pb
(1)
(2)
over time
ΔT
bility
evaluation
























Test Example C73
Bal
3
0.5
100
 25
 25
 25
 275
4.50






Test Example C74
Bal
3
0.5
100
 50
 25
0
 275
10.00 






Test Example C75
Bal
3
0.5
100
0
 75
0
 275
2.67






Test Example C76
Bal
3
0.5
100
0
0
 75
 275
2.67






Test Example C77
Bal
3
0.5
100
 50
 50
 50
 350
2.50






Test Example C78
Bal
3
0.5
 50
100
100
 50
 350
1.33






Test Example C79
Bal
3
0.5
300
0
300
300
1200
1.00






Test Example C80
Bal
3
0.5
200
300
250
250
1200
1.40






Test Example C81
Bal
3
0.5
100
500
250
250
1200
1.40






Test Example C82
Bal
3
0.5
200
 50
600
850
1900
0.31






Test Example C83
Bal
3
0.5
200
500
500
500
1900
0.90






Test Example C84
Bal
3
0.5
200
500
1000 
0
1900
0.90






Test Example C85
Bal
3
0.5
200
500
 0
1000 
1900
0.90






Test Example C86
Bal
3
0.5
 25
500
350
1000 
1900
0.41






Test Example C87
Bal
3
0.5
100
3000 
300
300
3800
5.33






Test Example C88
Bal
3
0.5
100
0
0
5100 
5300
0.04






Test Example C89
Bal
3
0.5
100
0
10000 
0
10200 
0.02






Test Example C90
Bal
3
0.5
100
0
10000 
5000 
15200 
0.01






Test Example C253
Bal
3
0.5
0
100
100
100
 300
0.50
X


X


Test Example C254
Bal
3
0.5
 25
 25
 25
 25
125
1.50
X


X


Test Example C255
Bal
3
0.5
300
500
 50
 50
1200

11.00



X
X


Test Example C256
Bal
3
0.5

350

1150 
 25
 25
1900

37.00



X
X


Test Example C257
Bal
3
0.5

800

800
100
100
2600

12.00



X
X


Test Example C258
Bal
3
0.5
250

4800

 1
0
5301

5300.00  



X
X


Test Example C259
Bal
3
0.5

800


3500

100
100
5300

25.50



X
X


Test Example C260
Bal
3
0.5
100

10000

 1
0
10201 

10200.00  



X
X


Test Example C261
Bal
3
0.5
100
100

25000


25000

50300 
0.01

X

X


Test Example C262
Bal
3
0.5
100
100

50000

0
50300 
0.01

X

X


Test Example C263
Bal
3
0.5
100
100
 0

50000

50300 
0.01

X

X


Test Example C264
Bal
3
0.5
300
3000 
 0
0
3600





X
X


Test Example C265
Bal
3
0.5
100
0
100

25000

25300 
0.01

X

X





Underlines indicate that the corresponding values are outside the scope of the present invention.

















TABLE 20









Alloy composition (As, Sb, Bi, Pb: mass ppm,

Evaluation items















Ag, Cu: % by mass)
Formula
Formula
Change

Wetta-
Comprehensive





















Sn
Ag
Cu
As
Sb
Bi
Pb
(1)
(2)
over time
ΔT
bility
evaluation
























Test Example C91
Bal
3.5
0.5
100
 25
 25
 25
 275
4.50






Test Example C92
Bal
3.5
0.5
100
 50
 25
0
 275
10.00 






Test Example C93
Bal
3.5
0.5
100
0
 75
0
 275
2.67






Test Example C94
Bal
3.5
0.5
100
0
0
 75
 275
2.67






Test Example C95
Bal
3.5
0.5
100
 50
 50
 50
 350
2.50






Test Example C96
Bal
3.5
0.5
 50
100
100
 50
 350
1.33






Test Example C97
Bal
3.5
0.5
300
0
300
300
1200
1.00






Test Example C98
Bal
3.5
0.5
200
300
250
250
1200
1.40






Test Example C99
Bal
3.5
0.5
100
500
250
250
1200
1.40






Test Example C100
Bal
3.5
0.5
200
 50
600
850
1900
0.31






Test Example C101
Bal
3.5
0.5
200
500
500
500
1900
0.90






Test Example C102
Bal
3.5
0.5
200
500
1000 
0
1900
0.90






Test Example C103
Bal
3.5
0.5
200
500
 0
1000 
1900
0.90






Test Example C104
Bal
3.5
0.5
 25
500
350
1000 
1900
0.41






Test Example C105
Bal
3.5
0.5
100
3000 
300
300
3800
5.33






Test Example C106
Bal
3.5
0.5
100
0
0
5100 
5300
0.04






Test Example C107
Bal
3.5
0.5
100
0
10000 
0
10200 
0.02






Test Example C108
Bal
3.5
0.5
100
0
10000 
5000 
15200 
0.01






Test Example C266
Bal
3.5
0.5
0
100
100
100
 300
0.50
X


X


Test Example C267
Bal
3.5
0.5
 25
 25
 25
 25
125
1.50
X


X


Test Example C268
Bal
3.5
0.5
300
500
 50
 50
1200

11.00



X
X


Test Example C269
Bal
3.5
0.5

350

1150 
 25
 25
1900

37.00



X
X


Test Example C270
Bal
3.5
0.5

800

800
100
100
2600

12.00



X
X


Test Example C271
Bal
3.5
0.5
250

4800

 1
0
5301

5300.00  



X
X


Test Example C272
Bal
3.5
0.5

800


3500

100
100
5300

25.50



X
X


Test Example C273
Bal
3.5
0.5
100

10000

 1
0
10201 

10200.00  



X
X


Test Example C274
Bal
3.5
0.5
100
100

25000


25000

50300 
0.01

X

X


Test Example C275
Bal
3.5
0.5
100
100

50000

0
50300 
0.01

X

X


Test Example C276
Bal
3.5
0.5
100
100
 0

50000

50300 
0.01

X

X


Test Example C277
Bal
3.5
0.5
300
3000 
 0
0
3600





X
X


Test Example C278
Bal
3.5
0.5
100
0
100

25000

25300 
0.01

X

X





Underlines indicate that the corresponding values are outside the scope of the present invention.















TABLE 21









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation


























Test Example
Bal.

18
82
82
 82

300
82.9

0






D1


Test Example
Bal.

18
50
150
150

404
102.0

0






D2


Test Example
Bal.

18
150
300
 50

554
23.1

0






D3


Test Example
Bal.

18
150
50
150

404
102.0

0






D4


Test Example
Bal.

18
123
0
123

300
143.9

0






D5


Test Example
Bal.

18
0
123
123

300
143.9

0






D6


Test Example
Bal.

18
150
300
150

654
45.3

0






D7


Test Example
Bal.

18
300
300
300

954
59.0

0






D8


Test Example
Bal.

18
300
1000
1000 

2354
81.1

0






D9


Test Example
Bal.

18
1000
300
1000 

2354
81.1

0






D10


Test Example
Bal.

18
1000
1000
1000 

3054
52.7

0






D11


Test Example
Bal.

10
10000
5100
3000 

18130
20.1

0






D12


Test Example
Bal.

10
10000
5100
0

15130
0.2

0






D13


Test Example
Bal.

10
10000
0
1000 

11030
10.3

0






D14


Test Example
Bal.

10
0
5100
1000 

6130
20.2

0






D15


Test Example
Bal.

10
150
300
150

630
40.0

0






D16


Test Example
Bal.

14
86
86
 86

300
74.4

0






D17


Test Example
Bal.

14
50
150
150

392
96.0

0






D18


Test Example
Bal.

14
150
300
 50

542
20.4

0






D19


Test Example
Bal.

14
150
50
150

392
96.0

0






D20


Test Example
Bal.

14
200
0
200

442
121.0

0






D21


Test Example
Bal.

14
0
200
200

442
121.0

0






D22


Test Example
Bal.

14
150
300
150

642
42.7

0






D23


Test Example
Bal.

14
300
300
300

942
57.0

0






D24


Test Example
Bal.

14
300
1000
1000 

2342
80.2

0






D25


















TABLE 22









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation


























Test Example
Bal.

14
1000
300
1000

2342
80.2

0






D26


Test Example
Bal.

14
1000
1000
1000

3042
52.1

0






D27


Test Example
Bal.

14
10000
5100
3000

18142
20.1

0






D28


Test Example
Bal.

14
10000
5100
  0

15142
0.3

0






D29


Test Example
Bal.

14
10000
0
1000

11042
10.4

0






D30


Test Example
Bal.

14
0
5100
1000

6142
20.4

0






D31


Test Example
Bal.

14
150
300
 150

642
42.7

0






D32


Test Example
Bal.

24
82
82
 82

318
93.9

0






D33


Test Example
Bal.

24
50
150
 150

422
111.0

0






D34


Test Example
Bal.

24
150
300
 50

572
27.1

0






D35


Test Example
Bal.

24
150
50
 150

422
111.0

0






D36


Test Example
Bal.

24
123
0
 123

318
158.5

0






D37


Test Example
Bal.

24
0
123
 123

318
158.5

0






D38


Test Example
Bal.

24
150
300
 150

672
49.3

0






D39


Test Example
Bal.

24
300
300
 300

972
62.0

0






D40


Test Example
Bal.

24
300
1000
1000

2372
82.5

0






D41


Test Example
Bal.

24
1000
300
1000

2372
82.5

0






D42


Test Example
Bal.

24
1000
1000
1000

3072
53.6

0






D43


Test Example
Bal.

24
10000
5100
3000

18172
20.3

0






D44


Test Example
Bal.

24
10000
5100
  0

15172
0.5

0






D45


Test Example
Bal.

24
10000
0
1000

11072
10.7

0






D46


Test Example
Bal.

24
0
5100
1000

6172
21.0

0






D47


Test Example
Bal.

24
150
300
 150

672
49.3

0






D48


Test Example
Bal.


38

82
82
 82

360
119.5

0






D49


Test Example
Bal.


38

50
150
 150

464
132.0

0






D50


















TABLE 23









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation




























Test Example
Bal.


38

150
300
 50



614
36.4

0






D51


Test Example
Bal.


38

150
50
150



464
132.0

0






D52


Test Example
Bal.


38

123
0
123



360
192.7

0






D53


Test Example
Bal.


38

0
123
123



360
192.7

0






D54


Test Example
Bal.


38

150
300
150



714
58.7

0






D55


Test Example
Bal.


38

300
300
300



1014
69.0

0






D56


Test Example
Bal.


38

300
1000
1000 



2414
85.7

0






D57


Test Example
Bal.


38

1000
300
1000 



2414
85.7

0






D58


Test Example
Bal.


38

1000
1000
1000 



3114
55.7

0






D59


Test Example
Bal.


38

10000
5100
3000 



18214
20.6

0






D60


Test Example
Bal.


38

10000
5100
0



15214
0.8

0






D61


Test Example
Bal.


38

10000
0
1000 



11114
11.1

0






D62


Test Example
Bal.


38

0
5100
1000 



6214
21.8

0






D63


Test Example
Bal.


38

150
300
150



714
58.7

0






D64


Test Example
Bal.

18
150
300
150
40


654
45.3

40






D65


Test Example
Bal.

18
150
300
150
100


654
45.3

100






D66


Test Example
Bal.

18
150
300
150
500


654
45.3

500






D67


Test Example
Bal.

18
150
300
150
600


654
45.3

600






D68


Test Example
Bal.

18
150
300
150

20

654
45.3
0
20






D69


Test Example
Bal.

18
150
300
150

100

654
45.3
0
100






D70


Test Example
Bal.

18
150
300
150
40
20

654
45.3
2
60






D71


Test Example
Bal.

18
150
300
150
40
10

654
45.3
4
50






D72


Test Example
Bal.

18
150
300
150
80
10

654
45.3
8
90






D73


Test Example
Bal.

18
150
300
150
500
10

654
45.3
50
510






D74


Test Example
Bal.

18
150
300
150
10
100

654
45.3
0.1
110






D75


















TABLE 24









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation





























Test Exam-
Bal.


18
150
300
150
100
100

654
45.3
1
200






ple D76


Test Exam-
Bal.


18
150
300
150
600
80

654
45.3
7.5
680






ple D77


Test Exam-
Bal.


18
150
300
150


20
654
45.3

0






ple D78


Test Exam-
Bal.


18
150
300
150


100
654
45.3

0






ple D79


Test Exam-
Bal.


18
150
300
150


1200
654
45.3

0






ple D80


Test Exam-
Bal.


18
150
300
150
40
20
20
654
45.3
2
60






ple D81


Test Exam-
Bal.


18
150
300
150
100
50
50
654
45.3
2
150






ple D82


Test Exam-
Bal.


18
150
300
150
500
50
30
654
45.3
10
550






ple D83


Test Exam-
Bal.

0.7
18
82
82
 82



300
82.9

0






ple D84


Test Exam-
Bal.

0.7
18
50
150
150



404
102.0

0






ple D85


Test Exam-
Bal.

0.7
18
150
300
 50



554
23.1

0






ple D86


Test Exam-
Bal.

0.7
18
150
50
150



404
102.0

0






ple D87


Test Exam-
Bal.

0.7
18
123
0
123



300
143.9

0






ple D88


Test Exam-
Bal.

0.7
18
0
123
123



300
143.9

0






ple D89


Test Exam-
Bal.

0.7
18
150
300
150



654
45.3

0






ple D90


Test Exam-
Bal.

0.7
18
300
300
300



954
59.0

0






ple D91


Test Exam-
Bal.

0.7
18
300
1000
1000 



2354
81.1

0






ple D92


Test Exam-
Bal.

0.7
18
1000
300
1000 



2354
81.1

0






ple D93


Test Exam-
Bal.

0.7
18
1000
1000
1000 



3054
52.7

0






ple D94


Test Exam-
Bal.

0.7
10
10000
5100
3000 



18130
20.1

0






ple D95


Test Exam-
Bal.

0.7
10
10000
5100
0



15130
0.2

0






ple D96


Test Exam-
Bal.

0.7
10
10000
0
1000 



11030
10.3

0






ple D97


Test Exam-
Bal.

0.7
10
0
5100
1000 



6130
20.2

0






ple D98


Test Exam-
Bal.

0.7
10
150
300
150



630
40.0

0






ple D99


Test Exam-
Bal.

0.7
14
86
86
 86



300
74.4

0






ple D100


















TABLE 25









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation



























Test Example
Bal.

0.7
14
50
150
150

392
96.0

0






D101


Test Example
Bal.

0.7
14
150
300
 50

542
20.4

0






D102


Test Example
Bal.

0.7
14
150
50
150

392
96.0

0






D103


Test Example
Bal.

0.7
14
200
0
200

442
121.0

0






D104


Test Example
Bal.

0.7
14
0
200
200

442
121.0

0






D105


Test Example
Bal.

0.7
14
150
300
150

642
42.7

0






D106


Test Example
Bal.

0.7
14
300
300
300

942
57.0

0






D107


Test Example
Bal.

0.7
14
300
1000
1000 

2342
80.2

0






D108


Test Example
Bal.

0.7
14
1000
300
1000 

2342
80.2

0






D109


Test Example
Bal.

0.7
14
1000
1000
1000 

3042
52.1

0






D110


Test Example
Bal.

0.7
14
10000
5100
3000 

18142
20.1

0






D111


Test Example
Bal.

0.7
14
10000
5100
0

15142
0.3

0






D112


Test Example
Bal.

0.7
14
10000
0
1000 

11042
10.4

0






D113


Test Example
Bal.

0.7
14
0
5100
1000 

6142
20.4

0






D114


Test Example
Bal.

0.7
14
150
300
150

642
42.7

0






D115


Test Example
Bal.

0.7
24
82
82
 82

318
93.9

0






D116


Test Example
Bal.

0.7
24
50
150
150

422
111.0

0






D117


Test Example
Bal.

0.7
24
150
300
 50

572
27.1

0






D118


Test Example
Bal.

0.7
24
150
50
150

422
111.0

0






D119


Test Example
Bal.

0.7
24
123
0
123

318
158.5

0






D120


Test Example
Bal.

0.7
24
0
123
123

318
158.5

0






D121


Test Example
Bal.

0.7
24
150
300
150

672
49.3

0






D122


Test Example
Bal.

0.7
24
300
300
300

972
62.0

0






D123


Test Example
Bal.

0.7
24
300
1000
1000 

2372
82.5

0






D124


Test Example
Bal.

0.7
24
1000
300
1000 

2372
82.5

0






D125


















TABLE 26









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation





























Test Example
Bal.

0.7
24
1000
1000
1000 



3072
53.6

0






D126


Test Example
Bal.

0.7
24
10000
5100
3000 



18172
20.3

0






D127


Test Example
Bal.

0.7
24
10000
5100
0



15172
0.5

0






D128


Test Example
Bal.

0.7
24
10000
0
1000 



11072
10.7

0






D129


Test Example
Bal.

0.7
24
0
5100
1000 



6172
21.0

0






D130


Test Example
Bal.

0.7
24
150
300
150



672
49.3

0






D131


Test Example
Bal.

0.7

38

82
82
 82



360
119.5

0






D132


Test Example
Bal.

0.7

38

50
150
150



464
132.0

0






D133


Test Example
Bal.

0.7

38

150
300
 50



614
36.4

0






D134


Test Example
Bal.

0.7

38

150
50
150



464
132.0

0






D135


Test Example
Bal.

0.7

38

123
0
123



360
192.7

0






D136


Test Example
Bal.

0.7

38

0
123
123



360
192.7

0






D137


Test Example
Bal.

0.7

38

150
300
150



714
58.7

0






D138


Test Example
Bal.

0.7

38

300
300
300



1014
69.0

0






D139


Test Example
Bal.

0.7

38

300
1000
1000 



2414
85.7

0






D140


Test Example
Bal.

0.7

38

1000
300
1000 



2414
85.7

0






D141


Test Example
Bal.

0.7

38

1000
1000
1000 



3114
55.7

0






D142


Test Example
Bal.

0.7

38

10000
5100
3000 



18214
20.6

0






D143


Test Example
Bal.

0.7

38

10000
5100
0



15214
0.8

0






D144


Test Example
Bal.

0.7

38

10000
0
1000 



11114
11.1

0






D145


Test Example
Bal.

0.7

38

0
5100
1000 



6214
21.8

0






D146


Test Example
Bal.

0.7

38

150
300
150



714
58.7

0






D147


Test Example
Bal.

0.7
18
150
300
150
40


654
45.3

40






D148


Test Example
Bal.

0.7
18
150
300
150
100


654
45.3

100






D149


Test Example
Bal.

0.7
18
150
300
150
500


654
45.3

500






D150


















TABLE 27









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation





























Test Example
Bal.

0.7
18
150
300
150
600


654
45.3

600






D151


Test Example
Bal.

0.7
18
150
300
150

20

654
45.3
0
20






D152


Test Example
Bal.

0.7
18
150
300
150

100

654
45.3
0
100






D153


Test Example
Bal.

0.7
18
150
300
150
40
20

654
45.3
2
60






D154


Test Example
Bal.

0.7
18
150
300
150
40
10

654
45.3
4
50






D155


Test Example
Bal.

0.7
18
150
300
150
80
10

654
45.3
8
90






D156


Test Example
Bal.

0.7
18
150
300
150
500
10

654
45.3
50
510






D157


Test Example
Bal.

0.7
18
150
300
150
10
100

654
45.3
0.1
110






D158


Test Example
Bal.

0.7
18
150
300
150
100
100

654
45.3
1
200






D159


Test Example
Bal.

0.7
18
150
300
150
600
80

654
45.3
7.5
680






D160


Test Example
Bal.

0.7
18
150
300
150


20
654
45.3

0






D161


Test Example
Bal.

0.7
18
150
300
150


100
654
45.3

0






D162


Test Example
Bal.

0.7
18
150
300
150


1200
654
45.3

0






D163


Test Example
Bal.

0.7
18
150
300
150
40
20
20
654
45.3
2
60






D164


Test Example
Bal.

0.7
18
150
300
150
100
50
50
654
45.3
2
150






D165


Test Example
Bal.

0.7
18
150
300
150
500
50
30
654
45.3
10
550






D166


Test Example
Bal.
1
0.5
18
82
82
82



300
82.9

0






D167


Test Example
Bal.
1
0.5
18
50
150
150



404
102.0

0






D168


Test Example
Bal.
1
0.5
18
150
300
50



554
23.1

0






D169


Test Example
Bal.
1
0.5
18
150
50
150



404
102.0

0






D170


Test Example
Bal.
1
0.5
18
123
0
123



300
143.9

0






D171


Test Example
Bal.
1
0.5
18
0
123
123



300
143.9

0






D172


Test Example
Bal.
1
0.5
18
150
300
150



654
45.3

0






D173


Test Example
Bal.
1
0.5
18
300
300
300



954
59.0

0






D174


Test Example
Bal.
1
0.5
18
300
1000
1000



2354
81.1

0






D175


















TABLE 28









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation



























Test Example
Bal.
1
0.5
18
1000
300
1000

2354
81.1

0






D176


Test Example
Bal.
1
0.5
18
1000
1000
1000

3054
52.7

0






D177


Test Example
Bal.
1
0.5
10
10000
5100
3000

18130
20.1

0






D178


Test Example
Bal.
1
0.5
10
10000
5100
  0

15130
0.2

0






D179


Test Example
Bal.
1
0.5
10
10000
0
1000

11030
10.3

0






D180


Test Example
Bal.
1
0.5
10
0
5100
1000

6130
20.2

0






D181


Test Example
Bal.
1
0.5
10
150
300
 150

630
40.0

0






D182


Test Example
Bal.
1
0.5
14
86
86
 86

300
74.4

0






D183


Test Example
Bal.
1
0.5
14
50
150
 150

392
96.0

0






D184


Test Example
Bal.
1
0.5
14
150
300
 50

542
20.4

0






D185


Test Example
Bal.
1
0.5
14
150
50
 150

392
96.0

0






D186


Test Example
Bal.
1
0.5
14
200
0
 200

442
121.0

0






D187


Test Example
Bal.
1
0.5
14
0
200
 200

442
121.0

0






D188


Test Example
Bal.
1
0.5
14
150
300
 150

642
42.7

0






D189


Test Example
Bal.
1
0.5
14
300
300
 300

942
57.0

0






D190


Test Example
Bal.
1
0.5
14
300
1000
1000

2342
80.2

0






D191


Test Example
Bal.
1
0.5
14
1000
300
1000

2342
80.2

0






D192


Test Example
Bal.
1
0.5
14
1000
1000
1000

3042
52.1

0






D193


Test Example
Bal.
1
0.5
14
10000
5100
3000

18142
20.1

0






D194


Test Example
Bal.
1
0.5
14
10000
5100
  0

15142
0.3

0






D195


Test Example
Bal.
1
0.5
14
10000
0
1000

11042
10.4

0






D196


Test Example
Bal.
1
0.5
14
0
5100
1000

6142
20.4

0






D197


Test Example
Bal.
1
0.5
14
150
300
 150

642
42.7

0






D198


Test Example
Bal.
1
0.5
24
82
82
 82

318
93.9

0






D199


Test Example
Bal.
1
0.5
24
50
150
 150

422
111.0

0






D200


















TABLE 29









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation



























Test Example
Bal.
1
0.5
24
150
300
 50

572
27.1

0






D201


Test Example
Bal.
1
0.5
24
150
50
150

422
111.0

0






D202


Test Example
Bal.
1
0.5
24
123
0
123

318
158.5

0






D203


Test Example
Bal.
1
0.5
24
0
123
123

318
158.5

0






D204


Test Example
Bal.
1
0.5
24
150
300
150

672
49.3

0






D205


Test Example
Bal.
1
0.5
24
300
300
300

972
62.0

0






D206


Test Example
Bal.
1
0.5
24
300
1000
1000 

2372
82.5

0






D207


Test Example
Bal.
1
0.5
24
1000
300
1000 

2372
82.5

0






D208


Test Example
Bal.
1
0.5
24
1000
1000
1000 

3072
53.6

0






D209


Test Example
Bal.
1
0.5
24
10000
5100
3000 

18172
20.3

0






D210


Test Example
Bal.
1
0.5
24
10000
5100
0

15172
0.5

0






D211


Test Example
Bal.
1
0.5
24
10000
0
1000 

11072
10.7

0






D212


Test Example
Bal.
1
0.5
24
0
5100
1000 

6172
21.0

0






D213


Test Example
Bal.
1
0.5
24
150
300
150

672
49.3

0






D214


Test Example
Bal.
1
0.5

38

82
82
 82

360
119.5

0






D215


Test Example
Bal.
1
0.5

38

50
150
150

464
132.0

0






D216


Test Example
Bal.
1
0.5

38

150
300
 50

614
36.4

0






D217


Test Example
Bal.
1
0.5

38

150
50
150

464
132.0

0






D218


Test Example
Bal.
1
0.5

38

123
0
123

360
192.7

0






D219


Test Example
Bal.
1
0.5

38

0
123
123

360
192.7

0






D220


Test Example
Bal.
1
0.5

38

150
300
150

714
58.7

0






D221


Test Example
Bal.
1
0.5

38

300
300
300

1014
69.0

0






D222


Test Example
Bal.
1
0.5

38

300
1000
1000 

2414
85.7

0






D223


Test Example
Bal.
1
0.5

38

1000
300
1000 

2414
85.7

0






D224


Test Example
Bal.
1
0.5

38

1000
1000
1000 

3114
55.7

0






D225


















TABLE 30









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation





























Test Exam-
Bal.
1
0.5

38

10000
5100
3000 



18214
20.6

0






ple D226


Test Exam-
Bal.
1
0.5

38

10000
5100
0



15214
0.8

0






ple D227


Test Exam-
Bal.
1
0.5

38

10000
0
1000 



11114
11.1

0






ple D228


Test Exam-
Bal.
1
0.5

38

0
5100
1000 



6214
21.8

0






ple D229


Test Exam-
Bal.
1
0.5

38

150
300
150



714
58.7

0






ple D230


Test Exam-
Bal.
1
0.5
18
150
300
150
40


654
45.3

40






ple D231


Test Exam-
Bal.
1
0.5
18
150
300
150
100


654
45.3

100






ple D232


Test Exam-
Bal.
1
0.5
18
150
300
150
500


654
45.3

500






ple D233


Test Exam-
Bal.
1
0.5
18
150
300
150
600


654
45.3

600






ple D234


Test Exam-
Bal.
1
0.5
18
150
300
150

20

654
45.3
0
20






ple D235


Test Exam-
Bal.
1
0.5
18
150
300
150

100

654
45.3
0
100






ple D236


Test Exam-
Bal.
1
0.5
18
150
300
150
40
20

654
45.3
2
60






ple D237


Test Exam-
Bal.
1
0.5
18
150
300
150
40
10

654
45.3
4
50






ple D238


Test Exam-
Bal.
1
0.5
18
150
300
150
80
10

654
45.3
8
90






ple D239


Test Exam-
Bal.
1
0.5
18
150
300
150
500
10

654
45.3
50
510






ple D240


Test Exam-
Bal.
1
0.5
18
150
300
150
10
100

654
45.3
0.1
110






ple D241


Test Exam-
Bal.
1
0.5
18
150
300
150
100
100

654
45.3
1
200






ple D242


Test Exam-
Bal.
1
0.5
18
150
300
150
600
80

654
45.3
7.5
680






ple D243


Test Exam-
Bal.
1
0.5
18
150
300
150


20
654
45.3

0






ple D244


Test Exam-
Bal.
1
0.5
18
150
300
150


100
654
45.3

0






ple D245


Test Exam-
Bal.
1
0.5
18
150
300
150


1200
654
45.3

0






ple D246


Test Exam-
Bal.
1
0.5
18
150
300
150
40
20
20
654
45.3
2
60






ple D247


Test Exam-
Bal.
1
0.5
18
150
300
150
100
50
50
654
45.3
2
150






ple D248


Test Exam-
Bal.
1
0.5
18
150
300
150
500
50
30
654
45.3
10
550






ple D249


Test Exam-
Bal.
2
0.5
18
82
82
 82



300
82.9

0






ple D250


















TABLE 31









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation



























Test Example D251
Bal.
2
0.5
18
50
150
150

404
102.0

0






Test Example D252
Bal.
2
0.5
18
150
300
 50

554
23.1

0






Test Example D253
Bal.
2
0.5
18
150
50
150

404
102.0

0






Test Example D254
Bal.
2
0.5
18
123
0
123

300
143.9

0






Test Example D255
Bal.
2
0.5
18
0
123
123

300
143.9

0






Test Example D256
Bal.
2
0.5
18
150
300
150

654
45.3

0






Test Example D257
Bal.
2
0.5
18
300
300
300

954
59.0

0






Test Example D258
Bal.
2
0.5
18
300
1000
1000 

2354
81.1

0






Test Example D259
Bal.
2
0.5
18
1000
300
1000 

2354
81.1

0






Test Example D260
Bal.
2
0.5
18
1000
1000
1000 

3054
52.7

0






Test Example D261
Bal.
2
0.5
10
10000
5100
3000 

18130
20.1

0






Test Example D262
Bal.
2
0.5
10
10000
5100
0

15130
0.2

0






Test Example D263
Bal.
2
0.5
10
10000
0
1000 

11030
10.3

0






Test Example D264
Bal.
2
0.5
10
0
5100
1000 

6130
20.2

0






Test Example D265
Bal.
2
0.5
10
150
300
150

630
40.0

0






Test Example D266
Bal.
2
0.5
14
86
86
 86

300
74.4

0






Test Example D267
Bal.
2
0.5
14
50
150
150

392
96.0

0






Test Example D268
Bal.
2
0.5
14
150
300
 50

542
20.4

0






Test Example D269
Bal.
2
0.5
14
150
50
150

392
96.0

0






Test Example D270
Bal.
2
0.5
14
200
0
200

442
121.0

0






Test Example D271
Bal.
2
0.5
14
0
200
200

442
121.0

0






Test Example D272
Bal.
2
0.5
14
150
300
150

642
42.7

0






Test Example D273
Bal.
2
0.5
14
300
300
300

942
57.0

0






Test Example D274
Bal.
2
0.5
14
300
1000
1000 

2342
80.2

0






Test Example D275
Bal.
2
0.5
14
1000
300
1000 

2342
80.2

0






















TABLE 32









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation



























Test Example D276
Bal.
2
0.5
14
1000
1000
1000

3042
52.1

0






Test Example D277
Bal.
2
0.5
14
10000
5100
3000

18142
20.1

0






Test Example D278
Bal.
2
0.5
14
10000
5100
  0

15142
0.3

0






Test Example D279
Bal.
2
0.5
14
10000
0
1000

11042
10.4

0






Test Example D280
Bal.
2
0.5
14
0
5100
1000

6142
20.4

0






Test Example D281
Bal.
2
0.5
14
150
300
 150

642
42.7

0






Test Example D282
Bal.
2
0.5
24
82
82
 82

318
93.9

0






Test Example D283
Bal.
2
0.5
24
50
150
 150

422
111.0

0






Test Example D284
Bal.
2
0.5
24
150
300
 50

572
27.1

0






Test Example D285
Bal.
2
0.5
24
150
50
 150

422
111.0

0






Test Example D286
Bal.
2
0.5
24
123
0
 123

318
158.5

0






Test Example D287
Bal.
2
0.5
24
0
123
 123

318
158.5

0






Test Example D288
Bal.
2
0.5
24
150
300
 150

672
49.3

0






Test Example D289
Bal.
2
0.5
24
300
300
 300

972
62.0

0






Test Example D290
Bal.
2
0.5
24
300
1000
1000

2372
82.5

0






Test Example D291
Bal.
2
0.5
24
1000
300
1000

2372
82.5

0






Test Example D292
Bal.
2
0.5
24
1000
1000
1000

3072
53.6

0






Test Example D293
Bal.
2
0.5
24
10000
5100
3000

18172
20.3

0






Test Example D294
Bal.
2
0.5
24
10000
5100
  0

15172
0.5

0






Test Example D295
Bal.
2
0.5
24
10000
0
1000

11072
10.7

0






Test Example D296
Bal.
2
0.5
24
0
5100
1000

6172
21.0

0






Test Example D297
Bal.
2
0.5
24
150
300
 150

672
49.3

0






Test Example D298
Bal.
2
0.5

38

82
82
 82

360
119.5

0






Test Example D299
Bal.
2
0.5

38

50
150
 150

464
132.0

0






Test Example D300
Bal.
2
0.5

38

150
300
 50

614
36.4

0























TABLE 33








Alloy composition (As, Bi, Pb, Sb: mass ppm,





Ag, Cu: % by mass)
Formula
Formula




















Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)





Test Example D301
Bal.
2
0.5

38

150
50
150



464
132.0


Test Example D302
Bal.
2
0.5

38

123
0
123



360
192.7


Test Example D303
Bal.
2
0.5

38

0
123
123



360
192.7


Test Example D304
Bal.
2
0.5

38

150
300
150



714
58.7


Test Example D305
Bal.
2
0.5

38

300
300
300



1014
69.0


Test Example D306
Bal.
2
0.5

38

300
1000
1000 



2414
85.7


Test Example D307
Bal.
2
0.5

38

1000
300
1000 



2414
85.7


Test Example D308
Bal.
2
0.5

38

1000
1000
1000 



3114
55.7


Test Example D309
Bal.
2
0.5

38

10000
5100
3000 



18214
20.6


Test Example D310
Bal.
2
0.5

38

10000
5100
0



15214
0.8


Test Example D311
Bal.
2
0.5

38

10000
0
1000 



11114
11.1


Test Example D312
Bal.
2
0.5

38

0
5100
1000 



6214
21.8


Test Example D313
Bal.
2
0.5

38

150
300
150



714
58.7


Test Example D314
Bal.
2
0.5
18
150
300
150
40


654
45.3


Test Example D315
Bal.
2
0.5
18
150
300
150
100


654
45.3


Test Example D316
Bal.
2
0.5
18
150
300
150
500


654
45.3


Test Example D317
Bal.
2
0.5
18
150
300
150
600


654
45.3


Test Example D318
Bal.
2
0.5
18
150
300
150

20

654
45.3


Test Example D319
Bal.
2
0.5
18
150
300
150

100

654
45.3


Test Example D320
Bal.
2
0.5
18
150
300
150
40
20

654
45.3


Test Example D321
Bal.
2
0.5
18
150
300
150
40
10

654
45.3


Test Example D322
Bal.
2
0.5
18
150
300
150
80
10

654
45.3


Test Example D323
Bal.
2
0.5
18
150
300
150
500
10

654
45.3


Test Example D324
Bal.
2
0.5
18
150
300
150
10
100

654
45.3


Test Example D325
Bal.
2
0.5
18
150
300
150
100
100

654
45.3












Evaluation items
















Formula
Formula
Change


Comprehensive




(5)
(6)
over time
ΔT
Wettability
evaluation







Test Example D301

0







Test Example D302

0







Test Example D303

0







Test Example D304

0







Test Example D305

0







Test Example D306

0







Test Example D307

0







Test Example D308

0







Test Example D309

0







Test Example D310

0







Test Example D311

0







Test Example D312

0







Test Example D313

0







Test Example D314

40







Test Example D315

100







Test Example D316

500







Test Example D317

600







Test Example D318
0
20







Test Example D319
0
100







Test Example D320
2
60







Test Example D321
4
50







Test Example D322
8
90







Test Example D323
50
510







Test Example D324
0.1
110







Test Example D325
1
200
























TABLE 34








Alloy composition (As, Bi, Pb, Sb: mass ppm,





Ag, Cu: % by mass)
Formula
Formula




















Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)





Test Example D326
Bal.
2
0.5
18
150
300
150
600
80

654
45.3


Test Example D327
Bal.
2
0.5
18
150
300
150


20
654
45.3


Test Example D328
Bal.
2
0.5
18
150
300
150


100
654
45.3


Test Example D329
Bal.
2
0.5
18
150
300
150


1200
654
45.3


Test Example D330
Bal.
2
0.5
18
150
300
150
40
20
20
654
45.3


Test Example D331
Bal.
2
0.5
18
150
300
150
100
50
50
654
45.3


Test Example D332
Bal.
2
0.5
18
150
300
150
500
50
30
654
45.3


Test Example D333
Bal.
3
0.5
18
82
82
 82



300
82.9


Test Example D334
Bal.
3
0.5
18
50
150
150



404
102.0


Test Example D335
Bal.
3
0.5
18
150
300
 50



554
23.1


Test Example D336
Bal.
3
0.5
18
150
50
150



404
102.0


Test Example D337
Bal.
3
0.5
18
123
0
123



300
143.9


Test Example D338
Bal.
3
0.5
18
0
123
123



300
143.9


Test Example D339
Bal.
3
0.5
18
150
300
150



654
45.3


Test Example D340
Bal.
3
0.5
18
300
300
300



954
59.0


Test Example D341
Bal.
3
0.5
18
300
1000
1000 



2354
81.1


Test Example D342
Bal.
3
0.5
18
1000
300
1000 



2354
81.1


Test Example D343
Bal.
3
0.5
18
1000
1000
1000 



3054
52.7


Test Example D344
Bal.
3
0.5
10
10000
5100
3000 



18130
20.1


Test Example D345
Bal.
3
0.5
10
10000
5100
0



15130
0.2


Test Example D346
Bal.
3
0.5
10
10000
0
1000 



11030
10.3


Test Example D347
Bal.
3
0.5
10
0
5100
1000 



6130
20.2


Test Example D348
Bal.
3
0.5
10
150
300
150



630
40.0


Test Example D349
Bal.
3
0.5
14
86
86
 86



300
74.4


Test Example D350
Bal.
3
0.5
14
50
150
150



392
96.0












Evaluation items
















Formula
Formula
Change


Comprehensive




(5)
(6)
over time
ΔT
Wettability
evaluation







Test Example D326
7.5
680







Test Example D327

0







Test Example D328

0







Test Example D329

0







Test Example D330
2
60







Test Example D331
2
150







Test Example D332
10
550







Test Example D333

0







Test Example D334

0







Test Example D335

0







Test Example D336

0







Test Example D337

0







Test Example D338

0







Test Example D339

0







Test Example D340

0







Test Example D341

0







Test Example D342

0







Test Example D343

0







Test Example D344

0







Test Example D345

0







Test Example D346

0







Test Example D347

0







Test Example D348

0







Test Example D349

0







Test Example D350

0























TABLE 35









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation



























Test Example D351
Bal.
3
0.5
14
150
300
50

542
20.4

0






Test Example D352
Bal.
3
0.5
14
150
50
150

392
96.0

0






Test Example D353
Bal.
3
0.5
14
200
0
200

442
121.0

0






Test Example D354
Bal.
3
0.5
14
0
200
200

442
121.0

0






Test Example D355
Bal.
3
0.5
14
150
300
150

642
42.7

0






Test Example D356
Bal.
3
0.5
14
300
300
300

942
57.0

0






Test Example D357
Bal.
3
0.5
14
300
1000
1000 

2342
80.2

0






Test Example D358
Bal.
3
0.5
14
1000
300
1000 

2342
80.2

0






Test Example D359
Bal.
3
0.5
14
1000
1000
1000 

3042
52.1

0






Test Example D360
Bal.
3
0.5
14
10000
5100
3000 

18142
20.1

0






Test Example D361
Bal.
3
0.5
14
10000
5100
0

15142
0.3

0






Test Example D362
Bal.
3
0.5
14
10000
0
1000 

11042
10.4

0






Test Example D363
Bal.
3
0.5
14
0
5100
1000 

6142
20.4

0






Test Example D364
Bal.
3
0.5
14
150
300
150

642
42.7

0






Test Example D365
Bal.
3
0.5
24
82
82
 82

318
93.9

0






Test Example D366
Bal.
3
0.5
24
50
150
150

422
111.0

0






Test Example D367
Bal.
3
0.5
24
150
300
 50

572
27.1

0






Test Example D368
Bal.
3
0.5
24
150
50
150

422
111.0

0






Test Example D369
Bal.
3
0.5
24
123
0
123

318
158.5

0






Test Example D370
Bal.
3
0.5
24
0
123
123

318
158.5

0






Test Example D371
Bal.
3
0.5
24
150
300
150

672
49.3

0






Test Example D372
Bal.
3
0.5
24
300
300
300

972
62.0

0






Test Example D373
Bal.
3
0.5
24
300
1000
1000 

2372
82.5

0






Test Example D374
Bal.
3
0.5
24
1000
300
1000 

2372
82.5

0






Test Example D375
Bal.
3
0.5
24
1000
1000
1000 

3072
53.6

0























TABLE 36








Alloy composition (As, Bi, Pb, Sb: mass ppm,





Ag, Cu: % by mass)
Formula
Formula




















Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)





Test Example D376
Bal.
3
0.5
24
10000
5100
3000 



18172
20.3


Test Example D377
Bal.
3
0.5
24
10000
5100
0



15172
0.5


Test Example D378
Bal.
3
0.5
24
10000
0
1000 



11072
10.7


Test Example D379
Bal.
3
0.5
24
0
5100
1000 



6172
21.0


Test Example D380
Bal.
3
0.5
24
150
300
150



672
49.3


Test Example D381
Bal.
3
0.5

38

82
82
 82



360
119.5


Test Example D382
Bal.
3
0.5

38

50
150
150



464
132.0


Test Example D383
Bal.
3
0.5

38

150
300
 50



614
36.4


Test Example D384
Bal.
3
0.5

38

150
50
150



464
132.0


Test Example D385
Bal.
3
0.5

38

123
0
123



360
192.7


Test Example D386
Bal.
3
0.5

38

0
123
123



360
192.7


Test Example D387
Bal.
3
0.5

38

150
300
150



714
58.7


Test Example D388
Bal.
3
0.5

38

300
300
300



1014
69.0


Test Example D389
Bal.
3
0.5

38

300
1000
1000 



2414
85.7


Test Example D390
Bal.
3
0.5

38

1000
300
1000 



2414
85.7


Test Example D391
Bal.
3
0.5

38

1000
1000
1000 



3114
55.7


Test Example D392
Bal.
3
0.5

38

10000
5100
3000 



18214
20.6


Test Example D393
Bal.
3
0.5

38

10000
5100
0



15214
0.8


Test Example D394
Bal.
3
0.5

38

10000
0
1000 



11114
11.1


Test Example D395
Bal.
3
0.5

38

0
5100
1000 



6214
21.8


Test Example D396
Bal.
3
0.5

38

150
300
150



714
58.7


Test Example D397
Bal.
3
0.5
18
150
300
150
40


654
45.3


Test Example D398
Bal.
3
0.5
18
150
300
150
100


654
45.3


Test Example D399
Bal.
3
0.5
18
150
300
150
500


654
45.3


Test Example D400
Bal.
3
0.5
18
150
300
150
600


654
45.3












Evaluation items
















Formula
Formula
Change


Comprehensive




(5)
(6)
over time
ΔT
Wettability
evaluation







Test Example D376

0







Test Example D377

0







Test Example D378

0







Test Example D379

0







Test Example D380

0







Test Example D381

0







Test Example D382

0







Test Example D383

0







Test Example D384

0







Test Example D385

0







Test Example D386

0







Test Example D387

0







Test Example D388

0







Test Example D389

0







Test Example D390

0







Test Example D391

0







Test Example D392

0







Test Example D393

0







Test Example D394

0







Test Example D395

0







Test Example D396

0







Test Example D397

40







Test Example D398

100







Test Example D399

500







Test Example D400

600























TABLE 37









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation





























Test Example D401
Bal.
3
0.5
18
150
300
150

20

654
45.3
0
20






Test Example D402
Bal.
3
0.5
18
150
300
150

100

654
45.3
0
100






Test Example D403
Bal.
3
0.5
18
150
300
150
40
20

654
45.3
2
60






Test Example D404
Bal.
3
0.5
18
150
300
150
40
10

654
45.3
4
50






Test Example D405
Bal.
3
0.5
18
150
300
150
80
10

654
45.3
8
90






Test Example D406
Bal.
3
0.5
18
150
300
150
500
10

654
45.3
50
510






Test Example D407
Bal.
3
0.5
18
150
300
150
10
100

654
45.3
0.1
110






Test Example D408
Bal.
3
0.5
18
150
300
150
100
100

654
45.3
1
200






Test Example D409
Bal.
3
0.5
18
150
300
150
600
80

654
45.3
7.5
680






Test Example D410
Bal.
3
0.5
18
150
300
150


20
654
45.3

0






Test Example D411
Bal.
3
0.5
18
150
300
150


100
654
45.3

0






Test Example D412
Bal.
3
0.5
18
150
300
150


1200
654
45.3

0






Test Example D413
Bal.
3
0.5
18
150
300
150
40
20
20
654
45.3
2
60






Test Example D414
Bal.
3
0.5
18
150
300
150
100
50
50
654
45.3
2
150






Test Example D415
Bal.
3
0.5
18
150
300
150
500
50
30
654
45.3
10
550






Test Example D416
Bal.
3.5
0.5
18
82
82
82



300
82.9

0






Test Example D417
Bal.
3.5
0.5
18
50
150
150



404
102.0

0






Test Example D418
Bal.
3.5
0.5
18
150
300
50



554
23.1

0






Test Example D419
Bal.
3.5
0.5
18
150
50
150



404
102.0

0






Test Example D420
Bal.
3.5
0.5
18
123
0
123



300
143.9

0






Test Example D421
Bal.
3.5
0.5
18
0
123
123



300
143.9

0






Test Example D422
Bal.
3.5
0.5
18
150
300
150



654
45.3

0






Test Example D423
Bal.
3.5
0.5
18
300
300
300



954
59.0

0






Test Example D424
Bal.
3.5
0.5
18
300
1000
1000



2354
81.1

0






Test Example D425
Bal.
3.5
0.5
18
1000
300
1000



2354
81.1

0






















TABLE 38









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation



























Test Example D426
Bal.
3.5
0.5
18
1000
1000
1000

3054
52.7

0






Test Example D427
Bal.
3.5
0.5
10
10000
5100
3000

18130
20.1

0






Test Example D428
Bal.
3.5
0.5
10
10000
5100
  0

15130
0.2

0






Test Example D429
Bal.
3.5
0.5
10
10000
0
1000

11030
10.3

0






Test Example D430
Bal.
3.5
0.5
10
0
5100
1000

6130
20.2

0






Test Example D431
Bal.
3.5
0.5
10
150
300
 150

630
40.0

0






Test Example D432
Bal.
3.5
0.5
14
86
86
 86

300
74.4

0






Test Example D433
Bal.
3.5
0.5
14
50
150
 150

392
96.0

0






Test Example D434
Bal.
3.5
0.5
14
150
300
 50

542
20.4

0






Test Example D435
Bal.
3.5
0.5
14
150
50
 150

392
96.0

0






Test Example D436
Bal.
3.5
0.5
14
200
0
 200

442
121.0

0






Test Example D437
Bal.
3.5
0.5
14
0
200
 200

442
121.0

0






Test Example D438
Bal.
3.5
0.5
14
150
300
 150

642
42.7

0






Test Example D439
Bal.
3.5
0.5
14
300
300
 300

942
57.0

0






Test Example D440
Bal.
3.5
0.5
14
300
1000
1000

2342
80.2

0






Test Example D441
Bal.
3.5
0.5
14
1000
300
1000

2342
80.2

0






Test Example D442
Bal.
3.5
0.5
14
1000
1000
1000

3042
52.1

0






Test Example D443
Bal.
3.5
0.5
14
10000
5100
3000

18142
20.1

0






Test Example D444
Bal.
3.5
0.5
14
10000
5100
  0

15142
0.3

0






Test Example D445
Bal.
3.5
0.5
14
10000
0
1000

11042
10.4

0






Test Example D446
Bal.
3.5
0.5
14
0
5100
1000

6142
20.4

0






Test Example D447
Bal.
3.5
0.5
14
150
300
 150

642
42.7

0






Test Example D448
Bal.
3.5
0.5
24
82
82
 82

318
93.9

0






Test Example D449
Bal.
3.5
0.5
24
50
150
 150

422
111.0

0






Test Example D450
Bal.
3.5
0.5
24
150
300
 50

572
27.1

0






















TABLE 39









Evaluation items

















Alloy composition (As, Bi, Pb, Sb: mass ppm,
For-
For-
For-
For-
Change


Compre-



Ag, Cu: % by mass)
mula
mula
mula
mula
over

Wetta-
hensive


























Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)
(5)
(6)
time
ΔT
bility
evaluation



























Test Example D451
Bal.
3.5
0.5
24
150
50
150

422
111.0

0






Test Example D452
Bal.
3.5
0.5
24
123
0
123

318
158.5

0






Test Example D453
Bal.
3.5
0.5
24
0
123
123

318
158.5

0






Test Example D454
Bal.
3.5
0.5
24
150
300
150

672
49.3

0






Test Example D455
Bal.
3.5
0.5
24
300
300
300

972
62.0

0






Test Example D456
Bal.
3.5
0.5
24
300
1000
1000 

2372
82.5

0






Test Example D457
Bal.
3.5
0.5
24
1000
300
1000 

2372
82.5

0






Test Example D458
Bal.
3.5
0.5
24
1000
1000
1000 

3072
53.6

0






Test Example D459
Bal.
3.5
0.5
24
10000
5100
3000 

18172
20.3

0






Test Example D460
Bal.
3.5
0.5
24
10000
5100
0

15172
0.5

0






Test Example D461
Bal.
3.5
0.5
24
10000
0
1000 

11072
10.7

0






Test Example D462
Bal.
3.5
0.5
24
0
5100
1000 

6172
21.0

0






Test Example D463
Bal.
3.5
0.5
24
150
300
150

672
49.3

0






Test Example D464
Bal.
3.5
0.5

38

82
82
 82

360
119.5

0






Test Example D465
Bal.
3.5
0.5

38

50
150
150

464
132.0

0






Test Example D466
Bal.
3.5
0.5

38

150
300
 50

614
36.4

0






Test Example D467
Bal.
3.5
0.5

38

150
50
150

464
132.0

0






Test Example D468
Bal.
3.5
0.5

38

123
0
123

360
192.7

0






Test Example D469
Bal.
3.5
0.5

38

0
123
123

360
192.7

0






Test Example D470
Bal.
3.5
0.5

38

150
300
150

714
58.7

0






Test Example D471
Bal.
3.5
0.5

38

300
300
300

1014
69.0

0






Test Example D472
Bal.
3.5
0.5

38

300
1000
1000 

2414
85.7

0






Test Example D473
Bal.
3.5
0.5

38

1000
300
1000 

2414
85.7

0






Test Example D474
Bal.
3.5
0.5

38

1000
1000
1000 

3114
55.7

0






Test Example D475
Bal.
3.5
0.5

38

10000
5100
3000 

18214
20.6

0























TABLE 40








Alloy composition (As, Bi, Pb, Sb: mass ppm,





Ag, Cu: % by mass)
Formula
Formula




















Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)





Test Example D476
Bal.
3.5
0.5

38

10000
5100
0



15214
0.8


Test Example D477
Bal.
3.5
0.5

38

10000
0
1000 



11114
11.1


Test Example D478
Bal.
3.5
0.5

38

0
5100
1000 



6214
21.8


Test Example D479
Bal.
3.5
0.5

38

150
300
150



714
58.7


Test Example D480
Bal.
3.5
0.5
18
150
300
150
40


654
45.3


Test Example D481
Bal.
3.5
0.5
18
150
300
150
100


654
45.3


Test Example D482
Bal.
3.5
0.5
18
150
300
150
500


654
45.3


Test Example D483
Bal.
3.5
0.5
18
150
300
150
600


654
45.3


Test Example D484
Bal.
3.5
0.5
18
150
300
150

20

654
45.3


Test Example D485
Bal.
3.5
0.5
18
150
300
150

100

654
45.3


Test Example D486
Bal.
3.5
0.5
18
150
300
150
40
20

654
45.3


Test Example D487
Bal.
3.5
0.5
18
150
300
150
40
10

654
45.3


Test Example D488
Bal.
3.5
0.5
18
150
300
150
80
10

654
45.3


Test Example D489
Bal.
3.5
0.5
18
150
300
150
500
10

654
45.3


Test Example D490
Bal.
3.5
0.5
18
150
300
150
10
100

654
45.3


Test Example D491
Bal.
3.5
0.5
18
150
300
150
100
100

654
45.3


Test Example D492
Bal.
3.5
0.5
18
150
300
150
600
80

654
45.3


Test Example D493
Bal.
3.5
0.5
18
150
300
150


20
654
45.3


Test Example D494
Bal.
3.5
0.5
18
150
300
150


100
654
45.3


Test Example D495
Bal.
3.5
0.5
18
150
300
150


1200
654
45.3


Test Example D496
Bal.
3.5
0.5
18
150
300
150
40
20
20
654
45.3


Test Example D497
Bal.
3.5
0.5
18
150
300
150
100
50
50
654
45.3


Test Example D498
Bal.
3.5
0.5
18
150
300
150
500
50
30
654
45.3












Evaluation items
















Formula
Formula
Change


Comprehensive




(5)
(6)
over time
ΔT
Wettability
evaluation







Test Example D476

0







Test Example D477

0







Test Example D478

0







Test Example D479

0







Test Example D480

40







Test Example D481

100







Test Example D482

500







Test Example D483

600







Test Example D484
0
20







Test Example D485
0
100







Test Example D486
2
60







Test Example D487
4
50







Test Example D488
8
90







Test Example D489
50
510







Test Example D490
0.1
110







Test Example D491
1
200







Test Example D492
7.5
680







Test Example D493

0







Test Example D494

0







Test Example D495

0







Test Example D496
2
60







Test Example D497
2
150







Test Example D498
10
550
























TABLE 41








Alloy composition (As, Bi, Pb, Sb: mass ppm,





Ag, Cu: % by mass)
Formula
Formula




















Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)





Test Example D501
Bal.


0
100
100 
100



 300
 50.0


Test Example D502
Bal.


 18
 25
25 
 25



129
 158.0


Test Example D503
Bal.



300

 50
50 
500



1500

1400.0



Test Example D504
Bal.



350

 25
25 
1150 



2250

4400.0



Test Example D505
Bal.



800

100
100 
800



3400

1600.0



Test Example D506
Bal.



250

 1
0

4800




5551

555000.0



Test Example D507
Bal.



800

100
100 

3500




6100

2950.0



Test Example D508
Bal.


 18
 1
0

10000




10055 

1005400.0  



Test Example D509
Bal.


 18

25000


25000  

100



50154 
  0.3


Test Example D510
Bal.


 18

50000

0
100



50154 
  0.3


Test Example D511
Bal.


 18
 0

50000  

100



50154 
  0.3


Test Example D512
Bal.



300

0

0

3000 



3900





Test Example D513
Bal.



100

100

25000  

0



25400 
  1.2


Test Example D514
Bal.

0.7
0
100
100 
100



 300
 50.0


Test Example D515
Bal.

0.7
 18
 25
25 
 25



129
 158.0


Test Example D516
Bal.

0.7

300

 50
50 
500



1500

1400.0



Test Example D517
Bal.

0.7

350

 25
25 
1150 



2250

4400.0



Test Example D518
Bal.

0.7

800

100
100 
800



3400

1600.0



Test Example D519
Bal.

0.7

250

 1
0

4800




5551

555000.0



Test Example D520
Bal.

0.7

800

100
100 

3500




6100

2950.0



Test Example D521
Bal.

0.7
 18
 1
0

10000




10055 

1005400.0  



Test Example D522
Bal.

0.7
 18

25000


25000  

100



50154 
  0.3


Test Example D523
Bal.

0.7
 18

50000

0
100



50154 
  0.3


Test Example D524
Bal.

0.7
 18
 0

50000  

100



50154 
  0.3


Test Example D525
Bal.

0.7

300

0

0

3000 



3900















Evaluation items
















Formula
Formula
Change


Comprehensive




(5)
(6)
over time
ΔT
Wettability
evaluation







Test Example D501

0
X


X



Test Example D502

0
X


X



Test Example D503

0


X
X



Test Example D504

0


X
X



Test Example D505

0


X
X



Test Example D506

0


X
X



Test Example D507

0


X
X



Test Example D508

0


X
X



Test Example D509

0

X

X



Test Example D510

0

X

X



Test Example D511

0

X

X



Test Example D512

0


X
X



Test Example D513

0

X

X



Test Example D514

0
X


X



Test Example D515

0
X


X



Test Example D516

0


X
X



Test Example D517

0


X
X



Test Example D518

0


X
X



Test Example D519

0


X
X



Test Example D520

0


X
X



Test Example D521

0


X
X



Test Example D522

0

X

X



Test Example D523

0

X

X



Test Example D524

0

X

X



Test Example D525

0


X
X




















TABLE 42








Alloy composition (As, Bi, Pb, Sb: mass ppm,





Ag, Cu: % by mass)
Formula
Formula




















Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)





Test Example D526
Bal.

0.7

100

100

25000  

0



25400 
  1.2


Test Example D527
Bal.
1
0.5
0
100
100 
100



 300
 50.0


Test Example D528
Bal.
1
0.5
 18
 25
25 
 25



129
 158.0


Test Example D529
Bal.
1
0.5

300

 50
50 
500



1500

1400.0



Test Example D530
Bal.
1
0.5

350

 25
25 
1150 



2250

4400.0



Test Example D531
Bal.
1
0.5

800

100
100 
800



3400

1600.0



Test Example D532
Bal.
1
0.5

250

 1
0

4800




5551

555000.0



Test Example D533
Bal.
1
0.5

800

100
100 

3500




6100

2950.0



Test Example D534
Bal.
1
0.5
 18
 1
0

10000




10055 

1005400.0  



Test Example D535
Bal.
1
0.5
 18

25000


25000  

100



50154 
  0.3


Test Example D536
Bal.
1
0.5
 18

50000

0
100



50154 
  0.3


Test Example D537
Bal.
1
0.5
 18
 0

50000  

100



50154 
  0.3


Test Example D538
Bal.
1
0.5

300

0

0

3000 



3900





Test Example D539
Bal.
1
0.5

100

100

25000  

0



25400 
  1.2


Test Example D540
Bal.
2
0.5
 0
100
100 
100



 300
 50.0


Test Example D541
Bal.
2
0.5
 18
 25
25 
 25



129
 158.0


Test Example D542
Bal.
2
0.5

300

 50
50 
500



1500

1400.0



Test Example D543
Bal.
2
0.5

350

 25
25 
1150 



2250

4400.0



Test Example D544
Bal.
2
0.5

800

100
100 
800



3400

1600.0



Test Example D545
Bal.
2
0.5

250

 1
0

4800




5551

555000.0



Test Example D546
Bal.
2
0.5

800

100
100 

3500




6100

2950.0



Test Example D547
Bal.
2
0.5
 18
 1
0

10000




10055 

1005400.0  



Test Example D548
Bal.
2
0.5
 18

25000


25000  

100



50154 
  0.3


Test Example D549
Bal.
2
0.5
 18

50000

0
100



50154 
  0.3


Test Example D550
Bal.
2
0.5
 18
 0

50000  

100



50154 
  0.3












Evaluation items
















Formula
Formula
Change


Comprehensive




(5)
(6)
over time
ΔT
Wettability
evaluation







Test Example D526

0

X

X



Test Example D527

0
X


X



Test Example D528

0
X


X



Test Example D529

0


X
X



Test Example D530

0


X
X



Test Example D531

0


X
X



Test Example D532

0


X
X



Test Example D533

0


X
X



Test Example D534

0


X
X



Test Example D535

0

X

X



Test Example D536

0

X

X



Test Example D537

0

X

X



Test Example D538

0


X
X



Test Example D539

0

X

X



Test Example D540

0
X


X



Test Example D541

0
X


X



Test Example D542

0


X
X



Test Example D543

0


X
X



Test Example D544

0


X
X



Test Example D545

0


X
X



Test Example D546

0


X
X



Test Example D547

0


X
X



Test Example D548

0

X

X



Test Example D549

0

X

X



Test Example D550

0

X

X




















TABLE 43








Alloy composition (As, Bi, Pb, Sb: mass ppm,





Ag, Cu: % by mass)
Formula
Formula




















Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)





Test Example D551
Bal.
2
0.5

300

0
0
3000 



3900



Test Example D552
Bal.
2
0.5

100

100

25000  

0



25400 
  1.2


Test Example D553
Bal.
3
0.5
0
100
100 
100



 300
 50.0


Test Example D554
Bal.
3
0.5
 18
 25
25
 25



129
 158.0


Test Example D555
Bal.
3
0.5

300

 50
50
500



1500

1400.0



Test Example D556
Bal.
3
0.5

350

 25
25
1150 



2250

4400.0



Test Example D557
Bal.
3
0.5

800

100
100 
800



3400

1600.0



Test Example D558
Bal.
3
0.5

250

 1
 0

4800




5551

555000.0



Test Example D559
Bal.
3
0.5

800

100
100 

3500




6100

2950.0



Test Example D560
Bal.
3
0.5
 18
 1
 0

10000




10055 

1005400.0  



Test Example D561
Bal.
3
0.5
 18

25000


25000  

100



50154 
  0.3


Test Example D562
Bal.
3
0.5
 18

50000

 0
100



50154 
  0.3


Test Example D563
Bal.
3
0.5
 18
 0

50000  

100



50154 
  0.3


Test Example D564
Bal.
3
0.5

300

 0
 0
3000 



3900





Test Example D565
Bal.
3
0.5

100

100

25000  

0



25400 
  1.2


Test Example D566
Bal.
3.5
0.5
 0
100
100 
100



 300
 50.0


Test Example D567
Bal.
3.5
0.5
 18
 25
25
 25



129
 158.0


Test Example D568
Bal.
3.5
0.5

300

 50
50
500



1500

1400.0



Test Example D569
Bal.
3.5
0.5

350

 25
25
1150 



2250

4400.0



Test Example D570
Bal.
3.5
0.5

800

100
100 
800



3400

1600.0













Evaluation items
















Formula
Formula
Change


Comprehensive




(5)
(6)
over time
ΔT
Wettability
evaluation







Test Example D551



0


X
X



Test Example D552

0

X

X



Test Example D553

0
X


X



Test Example D554

0
X


X



Test Example D555

0


X
X



Test Example D556

0


X
X



Test Example D557

0


X
X



Test Example D558

0


X
X



Test Example D559

0


X
X



Test Example D560

0


X
X



Test Example D561

0

X

X



Test Example D562

0

X

X



Test Example D563

0

X

X



Test Example D564

0


X
X



Test Example D565

0

X

X



Test Example D566

0
X


X



Test Example D567

0
X


X



Test Example D568

0


X
X



Test Example D569

0


X
X



Test Example D570

0


X
X




















TABLE 44








Alloy composition (As, Bi, Pb, Sb: mass ppm,





Ag, Cu: % by mass)
Formula
Formula




















Sn
Ag
Cu
As
Bi
Pb
Sb
Ni
Fe
In
(3)
(4)





Test Example D571
Bal.
3.5
0.5

250

1
0

4800




5551

555000.0   



Test Example D572
Bal.
3.5
0.5

800

100 
100 

3500




6100

2950.0  



Test Example D573
Bal.
3.5
0.5
 18
1
0

10000




10055

1005400.0   



Test Example D574
Bal.
3.5
0.5
 18

25000  


25000  

100



50154
0.3


Test Example D575
Bal.
3.5
0.5
 18

50000  

0
100



50154
0.3


Test Example D576
Bal.
3.5
0.5
 18
0

50000  

100



50154
0.3


Test Example D577
Bal.
3.5
0.5

300


0


0

3000 



3900





Test Example D578
Bal.
3.5
0.5

100

100 

25000  

0



25400
1.2












Evaluation items
















Formula
Formula
Change


Comprehensive




(5)
(6)
over time
ΔT
Wettability
evaluation







Test Example D571

0


X
X



Test Example D572

0


X
X



Test Example D573

0


X
X



Test Example D574

0

X

X



Test Example D575

0

X

X



Test Example D576

0

X

X



Test Example D577

0


X
X



Test Example D578

0

X

X










In Tables 15 to 44, underlines indicate that the corresponding values are outside the scope of the present invention.


As a result, for the solder pastes for which the flux of each example shown in Table 1 to Table 12 and the solder alloy of each test example shown in Table 15 to Table 20 and each test example within the scope of the present invention shown in Table 21 to Table 44 were used, sufficient effects were obtained in terms of the thickening suppression effects (changes over time) of the solder pastes> and the solder wettability (wetting speed). In addition, in the solder alloy of each test example shown in Table 15 to Table 20 and each test example within the scope of the present invention shown in Table 21 to Table 44, narrowing of ΔT was shown.


INDUSTRIAL APPLICABILITY

According to the present invention, it is possible to provide a flux capable of enhancing the wettability of solder, having excellent temperature cycle reliability, and capable of suppressing scattering due to heating during reflow and a solder paste using the same.

Claims
  • 1. A flux comprising: an organic acid, an acrylic resin, a rosin a thixotropic agent, and a solvent,wherein the flux does not contain water,the organic acid includes 1,2,3-propanetricarboxylic acid, anda content of the 1,2,3-propanetricarboxylic acid is 0.1% by mass or more and 15% by mass or less with respect to a total amount of the entire flux.
  • 2. The flux according to claim 1, wherein a ratio (mass ratio) of a content of the rosin to a content of the acrylic resin is 1 or more and 9 or less.
  • 3. The flux according to claim 1, wherein a total content of the organic acid is 0.1% by mass or more and 15% by mass or less with respect to the total amount of the entire flux.
  • 4. The flux according to claim 1, further comprising: azoles,wherein a content of the azoles is 0.1% by mass or more and 10% by mass or less with respect to the total amount of the entire flux.
  • 5. The flux according to claim 4, wherein a ratio (mass ratio) of a total content of the organic acid to the content of the azoles is 0.6 or more and 100 or less.
  • 6. The flux according to claim 1, further comprising: a resin other than the acrylic resin and the rosin,wherein a content of the resin other than the acrylic resin and the rosin is more than 0% by mass and 10% by mass or less with respect to the total amount of the entire flux.
  • 7. The flux according to claim 1, further comprising: a halogen compound,wherein a content of the halogen compound is more than 0% by mass and 5% by mass or less with respect to the total amount of the entire flux.
  • 8. The flux according to claim 1, further comprising: an antioxidant,wherein a content of the antioxidant is more than 0% by mass and 5% by mass or less with respect to the total amount of the entire flux.
  • 9. A solder paste comprising: the flux according to claim 1; anda solder powder.
  • 10. The solder paste according to claim 9, wherein the solder powder comprises a solder alloy having an alloy composition comprising As: 25 to 300 mass ppm, Pb: more than 0 mass ppm and 5100 mass ppm or less, at least one of Sb: more than 0 mass ppm and 3000 mass ppm or less and Bi: more than 0 mass ppm and 10000 mass ppm or less, and a balance of Sn andsatisfying the following formula (1) and formula (2), 275≤2As+Sb+Bi+Pb  (1)0.01≤(2As+Sb)/(Bi+Pb)≤10.00  (2)in the formula (1) and the formula (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.
  • 11. The solder paste according to claim 10, wherein the alloy composition further satisfies the following formula (1a), 275≤2As+Sb+Bi+Pb≤25200  (1a)in the formula (1a), As, Sb, Bi, and Pb each represent a content (mass ppm) in the alloy composition.
  • 12. The solder paste according to claim 10, wherein the alloy composition further satisfies the following formula (1b), 275≤2As+Sb+Bi+Pb≤5300  (1b)in the formula (1b), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.
  • 13. The solder paste according to claim 10, wherein the alloy composition further satisfies the following formula (2a), 0.31≤(2As+Sb)/(Bi+Pb)≤10.00  (2a)in the formula (2a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.
  • 14. The solder paste according to claim 9, wherein the solder powder comprises a solder alloy having an alloy composition comprising As: 10 mass ppm or more and less than 25 mass ppm, at least one of Bi: more than 0 mass ppm and 10000 mass ppm or less and Pb: more than 0 mass ppm and 5100 mass ppm or less, Sb: more than 0 mass ppm and 3000 mass ppm or less, and a balance of Sn and satisfying the following formula (3) and formula (4), 300≤3As+Sb+Bi+Pb  (3)0.1≤{(3As+Sb)/(Bi+Pb)}×100≤200  (4)in the formula (3) and the formula (4), As, Sb, Bi, and Pb each represent a content (mass ppm) in the alloy composition.
  • 15. The solder paste according to claim 14, wherein the alloy composition further contains Ni: more than 0 mass ppm and 600 mass ppm or less.
  • 16. The solder paste according to claim 14, wherein the alloy composition further contains Fe: more than 0 mass ppm and 100 mass ppm or less.
  • 17. The solder paste according to claim 14, wherein the alloy composition further contains In: more than 0 mass ppm and 1200 mass ppm or less.
  • 18. The solder paste according to claim 14, wherein the alloy composition further contains at least two of Ni: more than 0 mass ppm and 600 mass ppm or less, Fe: more than 0 mass ppm and 100 mass ppm or less and In: more than 0 mass ppm and 1200 mass ppm or less and satisfies the following formula (6), 0<Ni+Fe≤680  (6)in the formula (6), Ni and Fe each represent a content (mass ppm) in the alloy composition.
  • 19. The solder paste according to claim 14, wherein the alloy composition further contains Ni: 0 mass ppm or more and 600 mass ppm or less and Fe: more than 0 mass ppm and 100 mass ppm or less and satisfies the following formula (5) and the following formula (6), 0≤Ni/Fe≤50  (5)0<Ni+Fe≤680  (6)in the formula (5) and the formula (6), Ni and Fe each represent a content (mass ppm) in the alloy composition.
  • 20. The solder paste according to claim 14, wherein the alloy composition further satisfies the following formula (3a), 300≤3As+Sb+Bi+Pb≤18214  (3a)in the formula (3a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.
  • 21. The solder paste according to claim 14, wherein the alloy composition further satisfies the following formula (4a), 0.1≤{(3As+Sb)/(Bi+Pb)}×100≤158.5  (4a)in the formula (4a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.
  • 22. The solder paste according to claim 14, wherein the alloy composition further contains at least one of Ag: more than 0% by mass and 4% by mass or less and Cu: more than 0% by mass and 0.9% by mass or less.
Priority Claims (1)
Number Date Country Kind
2020-025678 Feb 2020 JP national
PCT Information
Filing Document Filing Date Country Kind
PCT/JP2021/005971 2/17/2021 WO