(19)
(11)EP 4 108 795 A1

(12)EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC

(43)Date of publication:
28.12.2022 Bulletin 2022/52

(21)Application number: 21756785.8

(22)Date of filing:  17.02.2021
(51)International Patent Classification (IPC): 
C22C 13/00(2006.01)
B23K 35/26(2006.01)
C22C 13/02(2006.01)
B23K 35/363(2006.01)
(52)Cooperative Patent Classification (CPC):
C22C 13/00; C22C 13/02; B23K 35/3601; B23K 35/26
(86)International application number:
PCT/JP2021/005971
(87)International publication number:
WO 2021/166967 (26.08.2021 Gazette  2021/34)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
KH MA MD TN

(30)Priority: 18.02.2020 JP 2020025678

(71)Applicant: Senju Metal Industry Co., Ltd.
Tokyo 120-8555 (JP)

(72)Inventors:
  • KAWASAKI, Hiroyoshi
    Tokyo 120-8555 (JP)
  • SHIRATORI, Masato
    Tokyo 120-8555 (JP)
  • MINEGISHI, Kazuhiro
    Tokyo 120-8555 (JP)
  • KAWAMATA, Yuji
    Tokyo 120-8555 (JP)

(74)Representative: Lavoix 
Bayerstraße 83
80335 München
80335 München (DE)

  


(54)FLUX AND SOLDER PASTE


(57) 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]



[0001] The present invention relates to a flux and a solder paste.

[0002] Priority is claimed on Japanese Patent Application No. 2020-025678, filed in Japan on February 18, 2020, the content of which is incorporated herein by reference.

[Background Art]



[0003] 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.

[0004] 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.

[0005] 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-soiuble flux containing a polyvalent carboxylic acid compound and water and capable of easily washing a residue.

[Citation List]


[Patent Documents]



[0006] 

[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]



[0007] 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.

[0008] 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]



[0009] In order to solve the above-described problems, the present invention adopted the following configurations.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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).





[0022] In the formula (1) and the formula (2), As, Sb, Bi, and Pb each represent a content (mass ppm) in the alloy composition.

[0023] In addition, in the solder paste according to the second aspect, the alloy composition preferably further satisfies the following formula (1a).



[0024] In the formula (1a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

[0025] In addition, in the solder paste according to the second aspect, the alloy composition preferably further satisfies the following formula (1b).



[0026] In the formula (1b), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

[0027] In addition, in the solder paste according to the second aspect, the alloy composition preferably further satisfies the following formula (2a).



[0028] In the formula (2a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

[0029] 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).





[0030] In the formula (3) and the formula (4), As, Sb, Bi, and Pb each represent a content (mass ppm) in the alloy composition.

[0031] 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.

[0032] 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.

[0033] In addition, in the solder paste according to the second aspect, the alloy composition preferably contains In: more than 0 mass ppm and 1 200 mass ppm or less.

[0034] 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).



[0035] In the formula (6), Ni and Fe each represent a content (mass ppm) in the alloy composition.

[0036] 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).





[0037] In the formula (5) and the formula (6), Ni and Fe each represent a content (mass ppm) in the alloy composition.

[0038] In addition, in the solder paste according to the second aspect, the alloy composition preferably further satisfies the following formula (3a).



[0039] In the formula (3a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

[0040] In addition, in the solder paste according to the second aspect, the alloy composition preferably further satisfies the following formula (4a).



[0041] In the formula (4a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

[0042] 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.

[0043]  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).





[0044] In the formula (3) and the formula (4), As, Sb, Bi, and Pb each represent a content (mass ppm) in the alloy composition.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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).



[0056] In the formula (6), Ni and Fe each represent a content (mass ppm) in the alloy composition.

[0057] 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).





[0058] In the formula (5) and the formula (6), Ni and Fe each represent a content (mass ppm) in the alloy composition.

[0059] In addition, in the solder paste according to the third aspect, the alloy composition preferably further satisfies the following formula (3a).



[0060] In the formula (3a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

[0061] In addition, in the solder paste according to the third aspect, the alloy composition preferably further satisfies the following formula (4a).



[0062] In the formula (4a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

[0063] 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]



[0064] 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]



[0065] Fig. 1 is a graph showing a schematic diagram of a reflow profile in evaluation of scattering suppression.

[Description of Embodiments]


<Flux>



[0066] 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.

[0067] 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 1 5% 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)



[0068] The flux of the present embodiment contains 1,2,3-propanetricarboxylic acid and is thereby capable of enhancing solder wettability (wetting speed).

[0069] The flux of the present embodiment may contain, in addition to the 1,2,3-propanetricarboxylic acid, other organic acids.

[0070] 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.

[0071] One organic acid may be used singly or two or more organic acids may be mixed and used.

[0072] 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.

[0073] 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.

[0074] 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)



[0075] The flux of the present embodiment contains an acrylic resin and a rosin as resins.

[0076] The flux of the present embodiment may contain a resin other than the acrylic resin and the rosin (other resin).

(Acrylic resin)



[0077] The flux of the present embodiment contains the acrylic resin and is thus capable of enhancing the temperature cycle reliability.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] One acrylic resin may be used singly or two or more acrylic resins may be mixed and used.

[0082] 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-polyethylelie (Mw = 12300),

[0083] 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)



[0084] Examples of the rosin that is used in the present embodiment include natural rosins, derivatives obtained from the natural rosins, and the like.

[0085] 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.

[0086] One rosin may be used singly or two or more rosins may be mixed and used.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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).

[0093] 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.

[0094] 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)



[0095] Examples of the thixotropic agent include an amide compound, an ester compound, a sorbitol-based compound, and the like.

[0096]  Examples of the amide compound, which is a thixotropic agent, include polyamides, bisamides, monoamides, and the like.

[0097] 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.

[0098] 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.

[0099] Examples of the polyamide include saturated fatty acid polyainides, unsaturated fatty acid polyamides, aromatic polyamides, tris 1,2,3-propanetricarboxylate (2-niethylcyclohexylamide), cyclic amide oligomers, acyclic amide oligomers, and the like.

[0100] 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.

[0101] 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.

[0102] Examples of the ester compound, which is the thixotropic agent, include hydrogenated castor oil and the like.

[0103] 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-inethylbenzylidene) -(D-)sorbitol, and the like.

[0104] One thixotropic agent may be used singly or two or more thixotropic agents may be mixed and used.

[0105] The thixotropic agent is preferably one or more selected from the group consisting of an amide compound and an ester compound.

[0106] The thixotropic agent is preferably one or more selected from the group consisting of a polyamide, a bisamide, a monoamide, and hydrogenated castor oil.

[0107] The polyamide is preferably an aliphatic polyamide. The bisamide is preferably ethylene bis(hydroxystearic acid amide). The monoamide is preferably p-toluamide.

[0108] 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.

[0109] 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.

[0110] 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)



[0111] 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.

[0112] 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.

[0113] 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(hydroxyimethyl)ethyl]ether, 1-ethynyl-1-cydohexanole, 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.

[0114] 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.

[0115] One solvent or two or more solvents can be used.

(Other components)



[0116] The flux of the present embodiment may contain, for example, an amine, a halogen compound, an antioxidant, and the like as other components.

[0117] Examples of the amine include azoles, other amines (excluding azoles), and the like.

[0118]  The flux of the present embodiment may contain azoles.

[0119] 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.

[0120] 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.

[0121] 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-benxy)-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'-melhylphenyl)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-1-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-2-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.

[0122] One azole may be used singly or two or more azoles may be mixed and used.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] Examples of the other amines include monoethanolamine, ethylamine, triethylamine, cyclohexylamine, ethylenediamine, triethylenetetramine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyelhyl-s-triazine, and the like.

[0128] The amine is preferably monoethanolamine.

[0129] Examples of the halogen compound include an amine hydrohalide and an organic halogen compound.

[0130] 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.

[0131] 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-hromo-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.

[0132] The halogen compound is preferably one or more selected from the group consisting of diphenylguanidine/HBr or 2,3-dibromo-1,4-butanediol.

[0133] One halogen compound may be used singly or two or more halogen compounds may be mixed and used.

[0134] 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.

[0135] Examples of the antioxidant include a hindered phenolic antioxidant and the like.

[0136] 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.

[0137] 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-propanetricatboxylic 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.

[0138] The flux of the present embodiment further contains the azoles, which makes it possible to make the flux have a sufficient corrosion suppression effect.

[0139] 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-propatietricarboxylic 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.

[0140] 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



[0141] A solder paste of the present embodiment contains the above-described flux and a solder powder.

[0142] 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:



[0143] 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.

[0144] 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.

[0145] Additionally, favorable wetting and spreading are exhibited even under conditions with a large heat load, and the wetting speed improves.

Solder alloy (first embodiment):



[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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 1 00 mass ppm or more, and most preferably 250 mass ppm or more.

[0151] 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.

[0152] 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.

[0153] The solder alloy preferably satisfies the following mathematical formula (1).


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

[0154] 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.

[0155] 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.

[0156] 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).




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.

[0157] In addition, the solder alloy preferably satisfies the following mathematical formula (2).


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

[0158]  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.

[0159] 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.

[0160] 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.

[0161] 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).


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

Solder alloy (second embodiment):



[0162] 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 5 100 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.





[0163] In the formula (3) and the formula (4), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

[0164] 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.

[0165] 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 5 1 00 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).

[0166] 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).

[0167] 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).

[0168] 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).

[0169] 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).

[0170] 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).

[0171] 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: 50to 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).

[0172] 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).

[0173] In addition, the solder alloy may further contain Ni: more than 0 mass ppm and 600 mass ppm or less.

[0174]  In addition, the solder alloy may further contain Fe: more than 0 mass ppm and 100 mass ppm or less.

[0175] In addition, the solder alloy may further contain In: more than 0 mass ppm and 1200 mass ppm or less.

[0176] 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).



[0177] In the formula (6), Ni and Fe each represent the content (mass ppm) in the alloy composition.

[0178] 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).





[0179] In the formula (5) and the formula (6), Ni and Fe each represent the content (mass ppm) in the alloy composition.

[0180] In addition, the solder alloy may further satisfy the following formula (3a).



[0181] In the formula (3a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

[0182] In addition, the solder alloy may further satisfy the following formula (4a).



[0183] In the formula (4a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

[0184] 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.

[0185] 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.

[0186] 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.

[0187]  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.

[0188] 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]



[0189] Hereinafter, the present invention will be described with examples, but the present invention is not limited to the following examples.

[0190] 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.

[0191] 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".

[0192] 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).

[0193] 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.

[0194] 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.

[0195] 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



[0196] 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.

[0197] 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)



[0198] 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



[0199] 

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



[0200] 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



[0201] 

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



[0202] 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



[0203] 

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>



[0204] 

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.



























[0205] In the present invention, as shown in Example 1 , when the flux contained 1,2,3-propanctricarboxylic 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-propanelricarboxylic 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] 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.

[0214] 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.

[0215] 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.

[0216] As described in Examples 19 to 21, even when 1,2,3-propanetricarboxytic 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.

[0217] 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.

[0218] As described in Examples 23 to 25, when 1,2,3-propanetricarboxyHc 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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] Examples 1 to 54 contained 1,2,3-propanetricarboxylic acid within the range specified in the present invention and had sufficient solder wettability.

[0240] In contrast, Comparative Examples 1 and 2 did not contain 1,2,3-propanetricarboxylic acid and had insufficient solder wettability.

[0241] 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.

[0242] Examples 1 to 54 contained an acrylic resin and had sufficient temperature cycle reliability.

[0243] In contrast, Comparative Examples 1 and 3 did not contain an acrylic resin and had insufficient temperature cycle reliability.

[0244] From these results, it was clarified that, when an acrylic resin is contained, it is possible to make fluxes have sufficient temperature cycle reliability.

[0245] 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.

[0246]  Examples 1 to 54 did not contain water and had a sufficient scattering suppression effect.

[0247] In contrast, Comparative Example 4 contained water and has an insufficient scattering suppression effect.

[0248] 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



[0249] The copper plate corrosion suppression capability was evaluated by the following copper plate corrosion test based on JIS Z 3197: 2012 8.4.1.

[0250] 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.

[0251] 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.

[0252] 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.

[0253] 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



[0254] 

O: There is no discoloration

X: There is discoloration





[0255] 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.

[0256] 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.

[0257] 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>



[0258] 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



[0259] 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



[0260] 

O: Viscosity after 12 hours ≤ Initial viscosity x 1 .2 An increase in the viscosity over time is small and favorable.

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





[0261] 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.





[0262] In the formula (1) and the formula (2), As, Sb, Bi, and Pb each represent a content (mass ppm) in the alloy composition.

[0263] 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.

[0264] 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 A 1 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.

[0265] 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



[0266] 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



[0267] 

O: ΔT is 10°C or less.

X: ΔT exceeds 10°C.


<Evaluation of wettability>


(1) Verification method



[0268] 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



[0269] 

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>



[0270] 

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.































































[0271] In Tables 15 to 44, underlines indicate that the corresponding values are outside the scope of the present invention.

[0272] 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]



[0273] 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, 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.


 
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 or 2,
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 any one of Claims 1 to 3, 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 any one of Claims 1 to 5, 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 any one of Claims 1 to 6, 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 any one of Claims 1 to 7, 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 any one of Claims 1 to 8; and

a 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 and

satisfying the following formula (1) and formula (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),

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 or 11,

wherein the alloy composition further satisfies the following formula (1b),

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


 
13. The solder paste according to any one of Claims 10 to 1 2,

wherein the alloy composition further satisfies the following formula (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),



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),

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),



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 any one of Claims 14 to 19,

wherein the alloy composition further satisfies the following formula (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 any one of Claims 14 to 20,

wherein the alloy composition further satisfies the following formula (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 any one of Claims 10 to 21,
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.
 




Drawing







Search report













Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description