WO2020241574A1 - Pâte à braser et flux pour pâte à braser - Google Patents

Pâte à braser et flux pour pâte à braser Download PDF

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Publication number
WO2020241574A1
WO2020241574A1 PCT/JP2020/020549 JP2020020549W WO2020241574A1 WO 2020241574 A1 WO2020241574 A1 WO 2020241574A1 JP 2020020549 W JP2020020549 W JP 2020020549W WO 2020241574 A1 WO2020241574 A1 WO 2020241574A1
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WIPO (PCT)
Prior art keywords
mass
solder
mass ppm
flux
solder paste
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PCT/JP2020/020549
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English (en)
Japanese (ja)
Inventor
浩由 川▲崎▼
正人 白鳥
勇司 川又
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千住金属工業株式会社
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Application filed by 千住金属工業株式会社 filed Critical 千住金属工業株式会社
Priority to JP2020552045A priority Critical patent/JP7104353B2/ja
Publication of WO2020241574A1 publication Critical patent/WO2020241574A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent

Definitions

  • the present invention relates to a solder paste and a flux for solder paste.
  • the present application claims priority based on Japanese Patent Application No. 2019-098936 filed in Japan on May 27, 2019, the contents of which are incorporated herein by reference.
  • Solder paste is generally used to connect an electronic device and a printed circuit board via such fine electrodes.
  • the solder paste is supplied on the electrodes of the printed circuit board by printing or the like.
  • To print the solder paste place a metal mask with an opening on the printed circuit board, move the squeegee while pressing it against the metal mask, and apply the solder paste to the electrodes on the printed circuit board from the opening of the metal mask all at once. Is done by.
  • solder paste if you purchase a solder paste, normally you will not use up the entire amount in one print. As described above, the solder paste must maintain an appropriate viscosity at the time of manufacture so as not to impair the printing performance on the substrate.
  • solder paste is a mixture of solder powder and flux, and if the storage period is long, the viscosity of the solder paste will increase depending on the storage conditions, and the printing performance at the time of purchase cannot be exhibited. Sometimes.
  • Patent Document 1 includes Sn and one or more selected from the group consisting of Ag, Bi, Sb, Zn, In, and Cu in order to suppress the change over time of the solder paste. And, a solder alloy containing a predetermined amount of As is disclosed. The document shows that the viscosity after 2 weeks at 25 ° C. is less than 140% of the initial viscosity.
  • the flux used for soldering has the effect of chemically removing metal oxides existing on the metal surface of the solder and the object to be soldered, and enabling the movement of metal elements at the boundary between the two. have. Therefore, by performing soldering using flux, an intermetallic compound can be formed between the solder and the metal surface of the object to be bonded, and a strong bond can be obtained.
  • thixotropy is imparted by the thixotropic agent contained in the flux.
  • the thixotropic agent builds a network in the flux and imparts thixotropic properties.
  • Patent Document 1 is a solder alloy that can selectively contain 6 kinds of elements in addition to Sn and As. Further, the same document shows that the meltability is inferior when the As content is high.
  • the meltability evaluated in Patent Document 1 is considered to correspond to the wettability of the molten solder.
  • the meltability disclosed in the document is evaluated by observing the appearance of the melt with a microscope and the presence or absence of solder powder that cannot be completely melted. This is because if the wettability of the molten solder is high, it is difficult for solder powder that cannot be completely melted to remain.
  • solder paste is required to maintain stable performance for a long period of time regardless of the usage environment and storage environment, and further higher wettability is also required due to the miniaturization of solder joints.
  • a vicious cycle is unavoidable as described above.
  • solder joint In order to join fine electrodes, it is necessary to improve the mechanical properties of the solder joint. Depending on the element, when the content is increased, the liquidus temperature rises and the liquidus temperature and the solidus temperature spread, and segregation occurs during solidification to form a non-uniform alloy structure. When the solder alloy has such an alloy structure, the solder joint is inferior in mechanical properties such as tensile strength and easily breaks due to external stress. This problem has become remarkable with the recent miniaturization of electrodes.
  • solder paste various methods such as improvement of the wetting speed of the solder, suppression of corrosion of the metal surface (for example, copper plate) of the object to be joined, improvement of printability, suppression of voids, etc. are performed depending on the usage conditions and applications. Characteristics are required.
  • the present invention has been made to solve the above-mentioned problems, and is less likely to cause changes over time such as an increase in viscosity, has excellent wettability, has high mechanical properties, and can further enhance various properties. It is an object of the present invention to provide a solder paste.
  • the present inventors examined a solder powder containing As as a basic composition of Sn, SnCu, and SnAgCu solder alloys conventionally used as solder alloys. Then, paying attention to the reason for suppressing the change with time of the solder paste when this solder powder was used, the As content was examined.
  • the present inventors have expanded the range of As content to a range in which the As content is low and the thickening suppressing effect is not exhibited, and then add an element other than As that exhibits the thickening suppressing effect. I realized that it was necessary to do so, and examined various elements. As a result, by chance, it was found that Sb, Bi and Pb exert the same effect as As. The reason for this is not clear, but it can be inferred as follows.
  • an element having a low ionization tendency can be mentioned as an element having a low reactivity with the flux.
  • the ionization of an alloy is considered in terms of the ionization tendency as the alloy composition, that is, the standard electrode potential.
  • the alloy composition that is, the standard electrode potential.
  • a SnAg alloy containing Ag, which is noble to Sn is less likely to be ionized than Sn. Therefore, an alloy containing an element nobler than Sn is difficult to ionize, and it is presumed that the effect of suppressing thickening of the solder paste is high.
  • Patent Document 1 in addition to Sn, Ag, and Cu, Bi, Sb, Zn, and In are listed as equivalent elements, but in terms of ionization tendency, Zn is the most base of these elements. It is an element that is lower than Sn. That is, Patent Document 1 describes that the thickening suppressing effect can be obtained even if Zn, which is a base element, is added. Therefore, it is considered that the solder alloy containing an element selected according to the ionization tendency can obtain a thickening suppressing effect equal to or higher than that of the solder alloy described in Patent Document 1. Further, as described above, as the As content increases, the wettability deteriorates.
  • the present inventors have examined in detail Bi and Pb that exert an effect of suppressing thickening. Since Bi and Pb lower the liquidus temperature of the solder alloy, the wettability of the solder alloy is improved when the heating temperature of the solder alloy is constant. However, since the solidus temperature is significantly lowered depending on the content, ⁇ T, which is the temperature difference between the liquidus temperature and the solidus temperature, becomes too wide. If ⁇ T becomes too wide, segregation will occur during solidification, leading to deterioration of mechanical properties such as mechanical strength. It was also found that strict control is necessary because the phenomenon that ⁇ T spreads remarkably appears when Bi and Pb are added at the same time.
  • the present inventors reexamined the Bi content and the Pb content in order to improve the wettability of the solder alloy, but as the content of these elements increased, ⁇ T became wider. Therefore, the present inventors have selected Sb as an element having an ionization tendency noble with respect to Sn and improving the wettability of the solder alloy, and have determined the allowable range of the Sb content.
  • the relationship regarding the content of each of As, Bi, Pb and Sb including Sb was examined in detail. As a result, by chance, when the content of these elements satisfies a predetermined relational expression, it is found that there is no practical problem in all of the excellent thickening suppressing effect, wettability, and narrowing of ⁇ T. It was.
  • the wetting speed of the solder is improved and the metal surface (for example, copper plate) of the object to be bonded is corroded. It has been found that various properties such as suppression, improvement of printability, and void suppression can be further enhanced.
  • a solder paste containing a solder powder and a flux wherein the solder powder has As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 0 to 10000 mass ppm, Pb: 0 to 5100.
  • a solder paste comprising a solder alloy having an alloy composition consisting of at least one of mass ppm and Sb: 0 to 3000 mass ppm, and the balance of Sn, and satisfying the following equations (1) and (2).
  • a solder paste containing a solder powder and a flux wherein the solder powder has As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 0 mass ppm or more and 10000 mass ppm or less, Pb: Solder having an alloy composition of more than 0 mass ppm and 5100 mass ppm or less, and Sb: at least one kind of more than 0 mass ppm and 3000 mass ppm or less, and the balance of Sn, and satisfying the following equations (1) and (2). Solder paste containing alloy.
  • the solder powder has As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 50 to 10000 mass ppm, Pb: 0 mass ppm.
  • a solder alloy having an alloy composition of more than 5100 mass ppm or less, Sb: 0 mass ppm or more and 3000 mass ppm or less, and the balance consisting of Sn, and satisfying the following equations (1) and (2). , Solder paste.
  • solder paste containing a solder powder and a flux wherein the solder powder has As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 50 to 10000 mass ppm, Pb: 50 to 5100.
  • a solder paste comprising a solder alloy having an alloy composition consisting of at least one of mass ppm and Sb: 50 to 3000 mass ppm, and the balance of Sn, and satisfying the following equations (1) and (2).
  • solder paste according to any one of [1] to [9] above, wherein the flux contains a resin component, an active component, and a solvent.
  • the flux is a dimer acid which is a reaction product of a monocarboxylic acid and is a dimer acid, a hydrogenated dimer acid which is a hydrogenated dimer acid, a trimer acid which is a trimeric acid which is a reaction product of a monocarboxylic acid, and a trimer acid.
  • the solder paste according to the above [10] which contains at least one organic acid selected from the group consisting of hydrogenated trimeric acid obtained by adding hydrogen to trimeric acid.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • a flux used for a solder paste wherein the solder paste has As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 0 to 10000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0.
  • a flux used for a solder paste in which As: 10 mass ppm or more and less than 40 mass ppm, Bi: 0 mass ppm or more and 10000 mass ppm or less, Pb: 0 mass ppm or more and 5100 mass ppm or more.
  • solder paste and a flux for solder paste which are less likely to change with time such as an increase in viscosity, have excellent wettability, have high mechanical properties, and can further enhance various properties.
  • ppm relating to the solder alloy composition is “mass ppm” unless otherwise specified.
  • % Is “mass%” unless otherwise specified.
  • solder paste of this embodiment contains a specific solder powder and a flux.
  • solder powder used in the solder paste of the present embodiment has As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 0 to 10000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0 to 3000 mass ppm.
  • a solder alloy having an alloy composition of at least one type and the balance of Sn, and satisfying the following equations (1) and (2) is included. 300 ⁇ 3As + Sb + Bi + Pb (1) 0.1 ⁇ ⁇ (3As + Sb) / (Bi + Pb) ⁇ ⁇ 100 ⁇ 200 (2)
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • Alloy composition (1) 10 mass ppm or more and less than 40 mass ppm 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 flux and is a noble element with respect to Sn, so that it can exert an effect of suppressing thickening. If As is less than 10 mass ppm, the thickening suppressing effect cannot be sufficiently exhibited.
  • the lower limit of the As content is 10 mass ppm or more, preferably 14 mass ppm or more. On the other hand, if the amount of As is too large, the wettability of the solder alloy deteriorates depending on the activity of the flux.
  • the upper limit of the As content is less than 40 mass ppm, preferably 38 mass ppm or less, more preferably less than 25 mass ppm, further preferably 24 mass ppm or less, and particularly preferably 18 mass ppm or less. is there.
  • At least one Sb having Bi: 0 to 10000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0 to 3000 mass ppm is an element having low reactivity with flux and exhibiting a thickening suppressing effect. ..
  • the lower limit of the Sb content is 0 mass ppm or more, may exceed 0 mass ppm, or may be 50 mass ppm or more.
  • the Sb content is preferably 82 mass ppm or more, more preferably 123 mass ppm or more, and further preferably 150 mass ppm or more.
  • the upper limit of the Sb content is 3000 mass ppm or less, preferably 1000 mass ppm or less, more preferably 700 mass ppm or less, and further preferably 300 mass ppm or less.
  • Bi and Pb like Sb, are elements that have low reactivity with flux and exhibit an effect of suppressing thickening. Further, Bi and Pb are elements that can suppress deterioration of wettability due to As because the liquidus temperature of the solder alloy is lowered and the viscosity of the molten solder is reduced. If at least one of Sb, Bi and Pb is present, deterioration of wettability due to As can be suppressed.
  • the lower limit of the Bi content is 0 mass ppm or more, may exceed 0 mass ppm, or may be 50 mass ppm or more.
  • the Bi content is preferably 82 mass ppm or more, more preferably 123 mass ppm or more, and further preferably 150 mass ppm or more.
  • the lower limit of the Pb content is 0 mass ppm or more, may exceed 0 mass ppm, or may be 50 mass ppm or more.
  • the Pb content is preferably 82 mass ppm or more, more preferably 123 mass ppm or more, further preferably 150 mass ppm or more, and most preferably 250 mass ppm or more.
  • the upper limit of the Bi content is 10,000 mass ppm or less, preferably 5000 mass ppm or less, and more preferably 1000 mass ppm or less. More preferably, it is 300 mass ppm or less.
  • the upper limit of the Pb content is 5100 mass ppm or less, preferably 5000 mass ppm or less, more preferably 1000 mass ppm or less, and further preferably 500 mass ppm or less. It is less than or equal to, particularly preferably 350 mass ppm or less, and most preferably 300 mass ppm or less.
  • Equation (1) The solder alloy in the present invention must satisfy the following equation (1). 300 ⁇ 3As + Sb + Bi + Pb (1)
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • Sb, Bi and Pb are all elements that have a thickening inhibitory effect.
  • the total of these needs to be 300 mass ppm or more.
  • the As content is tripled when at least one of Sb, Bi and Pb is contained, the As content is less than these contents, and As is Sb or Bi. This is because the thickening suppressing effect is higher than that of Pb and Pb. If the formula (1) is less than 300, the thickening suppressing effect is not sufficiently exhibited.
  • the lower limit of the formula (1) is 300 or more, preferably 318 or more, more preferably 360 or more, further preferably 392 or more, particularly preferably 464 or more, and most preferably 714 or more. ..
  • the upper limit of the formula (1) is not particularly limited from the viewpoint of the thickening suppressing effect, but is preferably 18214 or less, more preferably 15130 or less, from the viewpoint of setting ⁇ T in a suitable range. , More preferably 11030 or less, and particularly preferably 6214 or less.
  • the solder alloy in the present invention contains at least one of Sb, Bi and Pb in a total amount of more than 180 mass ppm.
  • the contents of Sb, Bi and Pb are set to be large, and a sufficient thickening suppressing effect is exhibited. If all of Sb, Bi and Pb are not contained, the viscosity of the solder paste will increase immediately.
  • the following formula (1a) is obtained by appropriately selecting the upper limit from the above preferred embodiments. 300 ⁇ 3As + Sb + Bi + Pb ⁇ 18214 (1a)
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • Equation (2) The solder alloy in the present invention must satisfy the following equation (2). 0.1 ⁇ ⁇ (3As + Sb) / (Bi + Pb) ⁇ ⁇ 100 ⁇ 200 (2)
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • the group is divided into As and Sb groups, Bi and Pb groups, and when the total amount of both groups is within an appropriate predetermined range, the thickening suppressing effect, ⁇ T narrowing, and wettability Are all satisfied at the same time.
  • the lower limit of the equation (2) is 0.1 or more, preferably 0.2 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and particularly preferably 0.8 or more. It is most preferably 10.3 or more.
  • the equation (2) exceeds 200, the total content of As and Sb becomes relatively larger than the total content of Bi and Pb, so that the wettability deteriorates.
  • the upper limit of (2) is 200 or less, preferably 192.7 or less, more preferably 158.5 or less, still more preferably 143.9 or less, and even more preferably 102.0 or less. , Especially preferably 96.0 or less.
  • the denominator of Eq. (2) is "Bi + Pb", and if these are not included, Eq. (2) cannot be established. That is, the solder alloy in the present invention always contains at least one of Bi and Pb.
  • the alloy composition containing no Bi and Pb is inferior in wettability as described above.
  • the following formula (2a) is obtained by appropriately selecting the upper limit from the above preferred embodiments. 0.1 ⁇ ⁇ (3As + Sb) / (Bi + Pb) ⁇ ⁇ 100 ⁇ 158.5 (2a)
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • Ni 0 to 600 mass ppm
  • Fe 0 to 100 mass ppm
  • Ni are arbitrary elements that can suppress the growth of intermetallic compounds.
  • Ni is a Cu 6 Sn 5 layer (Cu, Ni) 6 Sn 5 layer formed at the bonding interface when the solder alloy in the present invention joins Cu electrodes or contains Cu as described later. The thickness of the intermetallic compound layer can be reduced.
  • Fe can promote the formation of crystal nuclei during solidification of the molten solder and suppress the growth of intermetallic compound phases such as Cu 6 Sn 5 , Cu 3 Sn, and Ag 3 Sn. When the content of these elements is within a predetermined range, the liquidus temperature does not rise too much, ⁇ T falls within an allowable range, and high mechanical properties can be maintained.
  • the upper limit of the Ni content is preferably 600 mass ppm or less, more preferably 500 mass ppm or less, and further preferably 100 mass ppm or less. Particularly preferably, it is 50 mass ppm or less.
  • the upper limit of the Fe content is preferably 100 mass ppm or less, more preferably 80 mass ppm or less, and further preferably 50 mass ppm or less.
  • the lower limit of the Ni and Fe contents is not particularly limited, but the lower limit of the Ni content is preferably 10 mass ppm or more, more preferably, because the effect of suppressing the growth of the intermetallic compound is sufficiently exhibited. Is 40 mass ppm or more.
  • the lower limit of the Fe content is preferably 10 mass ppm or more, and more preferably 20 mass ppm or more.
  • In is a solid solution-enhanced element of Sn, it is an arbitrary element capable of maintaining high mechanical properties.
  • ⁇ T is within an acceptable range, and high mechanical properties can be maintained.
  • the solder alloy in the present invention contains In, the upper limit of the In content is preferably 1200 mass ppm or less, more preferably 100 mass ppm or less.
  • the lower limit of the In content is not particularly limited, but is preferably 20 mass ppm or more, more preferably 30 mass ppm or more, and further preferably 50 mass ppm or more so that a solid solution can be sufficiently formed. Is.
  • At least two types of Ni: 0 to 600 mass ppm, Fe: 0 to 100 mass ppm, and In: 0 to 1200 mass ppm Ni, Fe, and In are within a predetermined range.
  • ⁇ T easily falls within the permissible range, and high mechanical properties can be maintained.
  • at least two or more of these may be contained within a predetermined range, or three of them may be contained at the same time.
  • the solder alloy in the present invention contains a predetermined amount of Ni and Fe and satisfies the following formula (3). preferable. 0 ⁇ Ni / Fe ⁇ 50 (3)
  • Ni and Fe each represent the content (mass ppm) in the alloy composition.
  • the solder alloy in the present invention preferably contains Ni and Fe in predetermined amounts and then satisfies the equation (3).
  • the lower limit of the formula (3) is preferably 0 or more, more preferably 0.1 or more, further preferably 2 or more, and particularly preferably 7.5 or more. is there.
  • the upper limit of the formula (3) is preferably 50 or less, more preferably 10 or less, and further preferably 8.0 or less.
  • the liquidus temperature does not rise too much, ⁇ T is within the permissible range, and high mechanical properties are maintained, the following equation (4) is further applied. It is preferable to satisfy. 0 ⁇ Ni + Fe ⁇ 680 (4)
  • Ni and Fe each represent the content (mass ppm) in the alloy composition.
  • the lower limit of the formula (4) is preferably 0 or more, more preferably 20 or more, still more preferably 40 or more, and particularly preferably 50 or more. It is most preferably 60 or more.
  • the upper limit of the equation (4) is preferably 680 or less, more preferably 500 or less, still more preferably 200 or less, and particularly preferably 200 or less. It is 150 or less, most preferably 110 or less.
  • At least one kind of Ag: 0 to 4% by mass and Cu: 0 to 0.9% by mass can form Ag 3 Sn at the crystal interface to improve the reliability of the solder alloy. It is an element.
  • Ag is an element whose ionization tendency is noble with respect to Sn, and when it coexists with As, Pb and Bi, it promotes the effect of suppressing thickening.
  • the lower limit of the Ag content is preferably 0% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more.
  • the upper limit of the Ag content is preferably 4% by mass or less, more preferably 3.5% by mass or less, and further preferably 3.0% by mass or less.
  • Cu is an optional element that can improve the joint strength of solder joints.
  • Cu is an element whose ionization tendency is noble with respect to Sn, and when it coexists with As, Pb and Bi, it promotes the effect of suppressing thickening of these elements.
  • the lower limit of the Cu content is preferably 0% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more.
  • the upper limit of the Cu content is preferably 0.9% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.7% by mass or less.
  • Sn The rest of the solder alloy in the present invention is Sn.
  • unavoidable impurities may be contained. Even if it contains unavoidable impurities, it does not affect the above-mentioned effects. Further, as will be described later, even if an element not contained in the present invention is contained as an unavoidable impurity, it does not affect the above-mentioned effect.
  • solder powder in the present invention is used for a solder paste described later, and is preferably a spherical powder.
  • the spherical powder improves the fluidity of the solder alloy.
  • the solder powder in the present invention preferably satisfies a size (particle size distribution) satisfying symbols 1 to 8 in the powder size classification (Table 2) in JIS Z 3284-1: 2014, and more preferably symbols 4 to 8. It is a size satisfying (particle size distribution), and more preferably a size satisfying symbols 5 to 8 (particle size distribution).
  • the sphericity of the solder powder is preferably 0.90 or more, more preferably 0.95 or more, and most preferably 0.99 or more.
  • the sphericity of the spherical powder is measured using a CNC image measuring system (Ultra Quick Vision ULTRA QV350-PRO measuring device manufactured by Mitutoyo Co., Ltd.) using the minimum region centering method (MZC method).
  • the sphericity represents a deviation from the sphere, for example, an arithmetic mean value calculated when the diameter of each of 500 balls is divided by the major axis, and the value is 1.00, which is the upper limit. The closer it is to, the closer it is to a true sphere.
  • Examples of the flux used in the solder paste of the present embodiment include those containing a resin component, an active component, and a solvent.
  • the resin component examples include rosin-based resin, acrylic-based resin, urethane-based resin, polyester-based resin, phenoxy resin, vinyl ether-based resin, terpene resin, and modified terpene resin (for example, aromatic-modified terpene resin and hydrogenated terpene resin).
  • Hydrogenated aromatic modified terpene resin, etc. Hydrogenated aromatic modified terpene resin, etc.
  • terpene phenol resin modified terpene phenol resin (for example, hydrogenated terpene phenol resin, etc.)
  • styrene resin modified styrene resin (for example, styrene acrylic resin, styrene maleine resin, etc.)
  • xylene resin Modified xylene resin (for example, phenol-modified xylene resin, alkylphenol-modified xylene resin, phenol-modified resole-type xylene resin, polyol-modified xylene resin, polyoxyethylene-added xylene resin, etc.) and the like.
  • acrylic resin as used herein refers to a concept that includes a methacrylic resin, an ester thereof, and other derivatives in addition to an acrylic resin.
  • examples of the rosin-based resin include raw material rosins such as gum rosin, wood rosin and tall oil rosin, and derivatives obtained from the raw material rosin.
  • examples of the derivative include purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin and ⁇ , ⁇ unsaturated carboxylic acid modified products (acrylated rosin, maleated rosin, fumarized rosin, etc.), and purification of the polymerized rosin.
  • examples thereof include substances, hydrides and asymmetrics, and purified products of the ⁇ and ⁇ unsaturated carboxylic acid modified products, hydrides and aimitables.
  • Examples of the active ingredient include organic acids, amines, amine hydrohalides, organic halogen compounds, thixo agents, metal inactivating agents, surfactants, antioxidants, silane coupling agents, colorants and the like. Be done.
  • organic acids examples include glutaric acid, adipic acid, azelaic acid, eikosandioic acid, citric acid, glycolic acid, succinic acid, salicylic acid, diglycolic acid, dipicolinic acid, dibutylaniline diglycolic acid, suberic acid, and sebacic acid.
  • Examples thereof include hydrogenated dimeric acid,
  • amines include ethylamine, triethylamine, ethylenediamine, triethylenetetramine, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2 -Phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-Cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 1-
  • Amine hydrohalide is a compound obtained by reacting amine with hydrogen halide.
  • the amine in the amine hydrogen halide include ethylamine, ethylenediamine, triethylamine, diphenylguanidine, ditrilguanidine, methylimidazole, 2-ethyl-4-methylimidazole and the like
  • examples of the hydrogen halide include chlorine, bromine and the like. Examples include hydrides of iodine.
  • organic halogen compound examples include trans-2,3-dibromo-2-butene-1,4-diol, triallyl isocyanurate 6 bromide, 1-bromo-2-butanol, 1-bromo-2-propanol, 3 -Bromo-1-propanol, 3-bromo-1,2-propanediol, 1,4-dibromo-2-butanol, 1,3-dibromo-2-propanol, 2,3-dibromo-1-propanol, 2, Examples thereof include 3-dibromo-1,4-butanediol and 2,3-dibromo-2-butene-1,4-diol.
  • thixotropy examples include wax-based thixotropy, amide-based thixotropy, sorbitol-based thixotropy, and the like.
  • wax-based thixotropy examples include ester compounds, and specific examples thereof include castor oil.
  • amide-based tide agent examples include monoamide-based tide agent, bisamide-based tide agent, and polyamide-based tide agent, and specific examples thereof include lauric acid amide, palmitic acid amide, stearic acid amide, bechenic acid amide, and hydroxysteer.
  • Acid amides saturated fatty acid amides, oleic acid amides, erucic acid amides, unsaturated fatty acid amides, p-toluamides, p-toluenemethaneamides, aromatic amides, hexamethylenehydroxystearic acid amides, substituted amides, methylolstearic acid amides, methylols.
  • Monoamides such as amides and fatty acid ester amides; methylene bisstearic acid amides, ethylene bislauric acid amides, ethylene bishydroxy fatty acid (carbon atoms C6 to 24 of fatty acids) amides, ethylene bishydroxystearic acid amides, saturated fatty acid bisamides, methylene bisolein.
  • Bisamides such as acid amides, unsaturated fatty acid bisamides, m-xylylene bisstearic acid amides, and aromatic bisamides; saturated fatty acid polyamides, unsaturated fatty acid polyamides, aromatic polyamides, tris 1,2,3-propanetricarboxylic acids (2- Examples thereof include polyamides such as methylcyclohexylamide), cyclic amide oligomers, and acyclic amide oligomers.
  • the cyclic amide oligomer includes an amide oligomer in which dicarboxylic acid and diamine are polycondensed cyclically, an amide oligomer in which tricarboxylic acid and diamine are polycondensed cyclically, an amide oligomer in which dicarboxylic acid and triamine are polycondensed cyclically, and tricarboxylic acid.
  • Amido oligomer with cyclic polycondensation of dicarboxylic acid and triamine amide oligomer with cyclic polycondensation of dicarboxylic acid and tricarboxylic acid and diamine, amide oligomer with cyclic polycondensation of dicarboxylic acid and tricarboxylic acid and triamine, dicarboxylic acid and diamine
  • an amide oligomer in which triamine is cyclically polycondensed an amide oligomer in which tricarboxylic acid, diamine and triamine are polycondensed cyclically, and an amide oligomer in which dicarboxylic acid and tricarboxylic acid and diamine and triamine are cyclically polycondensed. ..
  • the acyclic amide oligomer is an amide oligomer in which a monocarboxylic acid and diamine and / or triamine are polycondensed in an acyclic manner
  • the amide in which a dicarboxylic acid and / or the tricarboxylic acid and the monoamine are polycondensed acyclically.
  • examples thereof include the case of an oligomer.
  • the monocarboxylic acid and the monoamine function as terminal molecules (terminal molecules), and become an acyclic amide oligomer having a reduced molecular weight.
  • 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 manner
  • the acyclic amide oligomer is a non-cyclic polymer amide polymer.
  • the acyclic amide oligomer also includes an amide oligomer in which a monocarboxylic acid and a monoamine are acyclically condensed.
  • sorbitol-based thixo agent examples include dibenzylidene-D-sorbitol, bis (4-methylbenzylidene) -D-sorbitol, (D-) sorbitol, monobenzylidene (-D-) sorbitol, and mono (4-methylbenzylidene).
  • -(D-) Sorbitol and the like can be mentioned.
  • metal inactivating agent examples include nitrogen compounds such as hydrazide nitrogen compounds, amide nitrogen compounds, triazole nitrogen compounds, and melamine nitrogen compounds; hindered phenol compounds and the like.
  • nitrogen compounds such as hydrazide nitrogen compounds, amide nitrogen compounds, triazole nitrogen compounds, and melamine nitrogen compounds; hindered phenol compounds and the like.
  • metal inactivating agent refers to a compound having the ability to prevent the metal from deteriorating due to contact with a certain compound.
  • Nonionic surfactants include polyoxyalkylene acetylene glycols, polyoxyalkylene glyceryl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene esters, polyoxyalkylene alkyl amines, polyoxyalkylene alkyl amides, and aliphatic alcohols polyoxyethylene. Examples thereof include adducts, aromatic alcohol polyoxyethylene adducts, polyhydric alcohol polyoxyethylene adducts and the like.
  • terminal diamine polyethylene glycol terminal diamine polyethylene glycol-polypropylene glycol copolymer, aliphatic amine polyoxyethylene adduct, aromatic amine polyoxyethylene adduct, polyvalent amine polyoxyethylene addition The body etc. can be mentioned.
  • Examples of the solvent include water, alcohol solvents, glycol ether solvents, organic acid ester solvents, terpineols, hydrocarbons and the like.
  • Examples of the alcohol solvent include isopropyl alcohol, 1,2-butanediol, isobornylcyclohexanol, 2,4-diethyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2, 5-Dimethyl-2,5-hexanediol, 2,5-dimethyl-3-hexine-2,5-diol, 2,3-dimethyl-2,3-butanediol, 1,1,1-tris (hydroxymethyl) ) Ethan, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 2,2'-oxybis (methylene) bis (2-ethyl-1,3-propanediol), 2,2-bis (hydroxymethyl) )-1,3-Propanedi
  • glycol ether-based solvent examples include diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, 2-methylpentane-2,4-diol, diethylene glycol monohexyl ether, diethylene glycol dibutyl ether, and triethylene glycol monobutyl ether. ..
  • organic acid ester-based solvent examples include dimethyl adipate, diisopropyl adipate, dibutyl maleate, dimethyl sebacate, diisobutyl adipate, diethyl sebacate, diisopropyl sebacate, dibutyl sebacate, and dioctyl sebacate.
  • hydrocarbons examples include toluene, xylene, n-hexane and the like.
  • the content of the resin component is preferably 20% by mass or more and 70% by mass or less, and more preferably 35% by mass or more and 60% by mass or less with respect to the total mass of the flux. ..
  • the content of the organic acid is preferably more than 0% by mass, preferably 15% by mass or less, and more preferably 0.2% by mass or more and 10% by mass or less with respect to the total mass of the flux.
  • the amine content is preferably 0% by mass or more and 8% by mass or less, and more preferably 1% by mass or more and 6% by mass or less with respect to the total mass of the flux.
  • the content of the amine hydrohalide is preferably 0% by mass or more and 8% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less with respect to the total mass of the flux.
  • the content of the organic halogen compound is preferably 0% by mass or more and 8% by mass or less, and more preferably 0.5% by mass or more and 6% by mass or less with respect to the total mass of the flux.
  • the content of the antioxidant is preferably 0% by mass or more and 8% by mass or less, and more preferably 1% by mass or more and 6% by mass or less with respect to the total mass of the flux.
  • the content of the flux in the solder paste is preferably 5 to 95% by mass, more preferably 5 to 15% by mass, based on the total mass of the solder paste.
  • the content of the flux in the solder paste is in this range, the thickening suppressing effect caused by the solder powder is sufficiently exhibited.
  • the wetting speed of the solder for example, the wetting speed of the solder, the corrosion suppression of the metal surface (for example, copper plate) of the object to be joined, the improvement of printability, and the voids It becomes easy to improve various characteristics such as suppression.
  • the solder paste of this embodiment is produced by a method common in the art.
  • known methods such as a dropping method in which the molten solder material is dropped to obtain particles, a spraying method in which centrifugal spraying is performed, and a method in which the bulk solder material is crushed can be adopted.
  • the dropping method and the spraying method the dropping and spraying are preferably performed in an inert atmosphere or a solvent in order to form particles.
  • each of the above components can be heated and mixed to prepare a flux, and the solder powder can be introduced into the flux, stirred and mixed for production.
  • solder paste of this embodiment a solder powder containing Sn and a solder alloy having an alloy composition in which a specific element (at least one of As and Bi, Pb and Sb) is used in a specific ratio is adopted.
  • a solder paste in which such a solder powder and a flux are combined is less likely to change with time such as an increase in viscosity, has excellent wettability, and exhibits high mechanical properties.
  • solder paste by selecting the components to be blended in the flux, the wetting speed of the solder is improved, the corrosion of the metal surface (for example, copper plate) of the object to be joined is suppressed, the printability is improved, and voids are suppressed. Various characteristics of the above can be further enhanced.
  • the solder paste of the present embodiment contains a specific solder powder and a flux.
  • the specific solder powder the solder powder containing any one of the solder alloy (S1) to the solder alloy (S9) shown below is mentioned as a preferable embodiment.
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • a solder alloy having an alloy composition consisting of Sn and satisfying the following equations (1) and (2). 300 ⁇ 3As + Sb + Bi + Pb (1) 0.1 ⁇ ⁇ (3As + Sb) / (Bi + Pb) ⁇ ⁇ 100 ⁇ 200 (2)
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • a solder alloy having an alloy composition consisting of Sn and satisfying the following equations (1) and (2). 300 ⁇ 3As + Sb + Bi + Pb (1) 0.1 ⁇ ⁇ (3As + Sb) / (Bi + Pb) ⁇ ⁇ 100 ⁇ 200 (2)
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • Solder alloy (S9) An alloy composition consisting of at least one of As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 50 to 10000 mass ppm, Pb: 50 to 5100 mass ppm, and Sb: 50 to 3000 mass ppm, and the balance of Sn.
  • a solder alloy that has and satisfies the following equations (1) and (2). 300 ⁇ 3As + Sb + Bi + Pb (1) 0.1 ⁇ ⁇ (3As + Sb) / (Bi + Pb) ⁇ ⁇ 100 ⁇ 200 (2)
  • As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
  • the flux in the solder paste of the present embodiment is not particularly limited, but for example, a flux containing a resin component, an active component, and a solvent is used.
  • a flux containing a resin component, an active component, and a solvent is used.
  • each composition of flux (F1) to flux (F12) shown below is mentioned as a preferable embodiment.
  • the flux (F1) is a composition containing an acid-modified rosin, and examples thereof include those containing an acid-modified rosin, a thixotropic agent, and a solvent.
  • the acid-modified rosin has heat resistance in the temperature range expected in soldering and functions as an activator during soldering.
  • the acid-modified rosin contained in the flux (F1) is preferably at least one selected from the group consisting of acrylic acid-modified rosin, acrylic acid-modified hydrogenated rosin, maleic acid-modified rosin and maleic acid-modified hydrogenated rosin.
  • the content of the acid-modified rosin is preferably 3.0% by mass or more and 60.0% by mass or less, and 5.0% by mass or more and 50.0% by mass or less, based on the total amount of the flux (F1). It is more preferable that there is 10.0% by mass or more and 50.0% by mass or less.
  • Examples of the thixotropy used in the flux (F1) include amide-based thixotropy, sorbitol-based thixotropy, and wax-based thixotropy (ester compound).
  • the content of the thixotropy is preferably 0.1 to 15.0% by mass, more preferably 0.2% by mass or more and 10.0% by mass or less, based on the total mass of the flux (F1).
  • Examples of the solvent used in the flux (F1) include water, alcohol-based solvents, glycol ether-based solvents, terpineols and the like.
  • the flux (F1) may contain rosins other than acid-modified rosins (other rosins).
  • other rosins include raw material rosins such as gum rosin, wood rosin and tall oil rosin, and derivatives obtained from the raw material rosin.
  • the derivative include purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, phenol-modified rosin, and purified products, hydrides and disproportionated products of the polymerized rosin, and one or two of them. More than seeds can be used.
  • the flux (F1) preferably contains other rosin in an amount of more than 0% by mass and 60.0% by mass or less, and more preferably more than 0% by mass and 45% by mass or less.
  • the flux (F1) preferably contains an acid-modified rosin and other rosins in a total amount of 20% by mass or more and 70% by mass or less, and more preferably 35% by mass or more and 60% by mass or less in total.
  • the flux (F1) may contain an organic acid, an amine, a halogen-based activator, and an antioxidant.
  • the flux (F1) may further contain a surfactant.
  • the flux (F2) is a composition containing an acrylic resin, and examples thereof include those containing an acrylic resin, an organic acid, and a solvent.
  • the acrylic resin has heat resistance in the temperature range expected by soldering, and remains in the flux residue cured after heating, so that the flux residue becomes a soft residue. As a result, cracking of the flux residue is suppressed even if the temperature changes, and the reliability of the temperature cycle is improved.
  • the acrylic resin contained in the flux (F2) is acrylic using acrylic acid, acrylic acid ester which is a reaction product of acrylic acid and alcohol, methacrylic acid, and methacrylic acid ester which is a reaction product of methacrylic acid and alcohol as a monomer.
  • examples thereof include a polymer of acid, a polymer of acrylic acid ester, and a polymer of acrylic acid and acrylic acid ester.
  • examples thereof include a polymer of methacrylic acid, a polymer of methacrylic acid ester, and a polymer of methacrylic acid and methacrylic acid ester.
  • a polymer of acrylic acid and methacrylic acid a polymer of acrylic acid and methacrylic acid ester, a polymer of methacrylic acid and methacrylic acid ester, a polymer of acrylic acid ester and methacrylic acid ester, acrylic acid and methacrylic acid.
  • Examples of the acrylate ester include butyl acrylate, and examples of the acrylate resin using butyl acrylate as a monomer include a polymer of butyl acrylate, an acrylate other than butyl acrylate, and butyl acrylate. , A polymer of acrylate and butyl acrylate, a polymer of acrylate other than acrylate and butyl acrylate and butyl acrylate, and the like.
  • Examples of the methacrylic acid ester include methacrylic acid butyl ester, and examples of the acrylic resin using the methacrylic acid butyl ester as a monomer include a polymer of methacrylic acid butyl ester, a methacrylic acid ester other than the methacrylic acid butyl ester, and methacrylic acid. Examples thereof include a polymer with a butyl ester, a polymer of methacrylic acid and a butyl methacrylic acid ester, and a polymer of a methacrylic acid ester other than the methacrylic acid and the butyl methacrylic acid ester and a butyl methacrylic acid ester.
  • a polymer of acrylic acid and butyl methacrylate ester a polymer of methacrylic acid ester other than acrylic acid and butyl methacrylate ester and butyl methacrylate ester, a polymer of methacrylic acid and butyl acrylate ester, methacrylic acid.
  • the polymerization reaction may be random copolymerization, block copolymerization or the like.
  • the above-mentioned alcohol is an alcohol having a linear carbon chain having 1 to 24 carbon atoms or an alcohol having a branched carbon chain having 3 to 24 carbon atoms.
  • the molecular weight of the acrylic resin is preferably a polystyrene-equivalent weight average molecular weight (Mw) of 5,000 to 30,000 as measured by gel permeation chromatography (GPC), and a weight average molecular weight (Mw) of 6,000 to 15,000. More preferred.
  • the acrylic resin may be a polymer of the above-mentioned acrylic resin and another resin, or may be, for example, a copolymer of each of the above-mentioned acrylic resins and polyethylene.
  • the content of the acrylic resin is preferably 5% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, based on the total mass of the flux (F2). It is more preferably 30% by mass or less.
  • the content of the organic acid used in the flux (F2) is preferably more than 0% by mass, preferably 15% by mass or less, and more preferably 0.2% by mass or more and 13% by mass or less, based on the total mass of the flux (F2).
  • the solvent used in the flux (F2) include water, alcohol-based solvents, glycol ether-based solvents, terpineols and the like.
  • the flux (F2) may contain rosin in an amount of 0% by mass or more and 45.0% by mass or less.
  • the total content of one type of rosin or two or more types of rosin and one type of acrylic resin or two or more types of acrylic resin is 35.0% by mass or more and 60.0% by mass.
  • the following is preferable.
  • the ratio of the total content of one type of rosin or two or more types of rosin to the total content of one type of acrylic resin or two or more types of acrylic resin (total amount of rosin). / Total amount of acrylic resin) is preferably 0.1 or more and 9.0 or less.
  • the flux (F2) may contain a resin other than the acrylic resin and the rosin resin, and contains 0% by mass or more and 10.0% by mass or less of the other resin.
  • the flux (F2) may further contain amines and halogens.
  • Amine is preferably 0% by mass or more and 20.0% by mass or less, more preferably 0% by mass or more and 5.0% by mass or less, and amine halide hydride as a halogen with respect to the total mass of the flux (F2). , 0 mass% or more and 2.0 mass% or less, more preferably 0 mass% or more and 5.0 mass% or less, based on the total mass of the flux (F2).
  • the flux (F2) may contain a thixotropic agent, and preferably contains 0% by mass or more and 10.0% by mass or less of the thixotropic agent with respect to the total mass of the flux (F2).
  • the thixotropy may contain an amide thixotropy, and the amide thixotropy is preferably 0% by mass or more and 10.0% by mass or less, more preferably 0% by mass, based on the total mass of the flux (F2). Includes more than 6.0% by mass or less.
  • the flux (F2) may contain an ester compound as the thixo agent, and the ester compound is preferably 0% by mass or more and 8.0% by mass or less, more preferably, with respect to the total mass of the flux (F2).
  • the flux (F2) may contain a sorbitol-based thixotropy as the thixotropy, and the sorbitol-based thixotropy is preferably 0% by mass or more and 10.0% by mass or less with respect to the total mass of the flux (F2). , More preferably 0% by mass or more and 6.0% by mass or less.
  • the total content of the plurality of thixotropic agents is preferably 10.0% by mass or less with respect to the total mass of the flux (F2).
  • the flux (F2) may further contain an antioxidant, preferably containing 0% by mass or more and 5.0% by mass or less of the total mass of the flux (F2).
  • Flux (F3) is a reaction product of monocarboxylic acid and is a dimer acid, a hydrogenated dimer acid obtained by adding hydrogen to dimer acid, a reaction product of monocarboxylic acid and is a trimer acid, and a trimmer.
  • the flux (F3) includes, for example, at least one organic acid selected from the group consisting of the dimer acid, the hydrogenated dimer acid, the trimer acid and the hydrogenated trimer acid, a rosin, a thixo agent, and the like. Examples include those containing a solvent. Dimer acid and trimer acid have heat resistance in the temperature range assumed in soldering and function as an activator at the time of soldering.
  • the dimer acid and trimer acid contained in the flux (F3) are a reaction product of dimer acid, which is a reaction product of oleic acid and linoleic acid, trimer acid, which is a reaction product of oleic acid and linoleic acid, and acrylic acid.
  • Trimmer acid which is a reaction product of methacrylic acid and oleic acid, trimeric acid, which is a reaction product of methacrylic acid and oleic acid, dimer acid, which is a reaction product of methacrylic acid and linoleic acid, and methacrylic acid.
  • Trimmer acid which is a reaction product with linoleic acid, dimer acid, which is a reaction product of methacrylic acid and linolenic acid, trimeric acid, which is a reaction product of methacrylic acid and linolenic acid, and reaction product of oleic acid and linolenic acid.
  • dimer acid which is a reaction product of linoleic acid and linolenic acid
  • trimeric acid which is a reaction product of linoleic acid and linolenic acid
  • dimeric acid, which is a reaction product of oleic acid and linoleic acid is a dimer having 36 carbon atoms.
  • trimeric acid, which is a reaction product of oleic acid and linoleic acid is a trimer having 54 carbon atoms.
  • the flux (F3) contains at least one selected from the group consisting of dimer acid, hydrogenated dimer acid, trimer acid and hydrogenated trimer acid in an amount of 0.5% by mass or more and 20% by mass or less based on the total mass of the flux. It is preferable, and it is more preferable to contain 2% by mass or more and 10% by mass or less. When the content of at least one selected from the group consisting of dimer acid, hydrogenated dimer acid, trimer acid and hydrogenated trimer acid is 0.5% by mass or more, the wettability of the solder and the poor wettability of the solder ( The effect of suppressing dewetting) becomes easier to obtain.
  • the flux (F3) may be added to at least one selected from the group consisting of dimer acid, hydrogenated dimer acid, trimer acid and hydrogenated trimer acid, and organic acids other than these may be used in combination.
  • organic acid other than these at least one selected from the group consisting of succinic acid, glutaric acid and adipic acid is preferable.
  • the content of at least one selected from the group consisting of succinic acid, glutaric acid and adipic acid is preferably 0.1% by mass or more and 5% by mass or less with respect to the total mass of the flux.
  • the total content of at least one selected from the group consisting of dimer acid, hydrogenated dimer acid, trimer acid and hydrogenated trimer acid and organic acids other than these is 0.5 mass by mass with respect to the total mass of the flux. % Or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and further preferably 5% by mass or more and 10% by mass or less.
  • Examples of the rosin used in the flux (F3) include natural rosin and derivatives obtained from the natural rosin.
  • natural rosin examples include gum rosin, wood rosin, tall oil rosin and the like.
  • the derivative examples include purified rosin and modified rosin.
  • Modified rosins include hydrogenated rosin, polymerized rosin, disproportionated rosin, acid-modified rosin, rosin ester, phenol-modified rosin and ⁇ , ⁇ -unsaturated carboxylic acid-modified products (acrylicized rosin, maleated rosin, fumarized rosin, etc.
  • One or more of these can be used.
  • the flux (F3) preferably contains rosin in an amount of 15% by mass or more and 70% by mass or less, and more preferably contains rosin in an amount of 35% by mass or more and 60% by mass or less.
  • thixotropy used in the flux (F3) examples include amide-based thixotropy, sorbitol-based thixotropy, and wax-based thixotropy (ester compound).
  • the content of the thixotropy is preferably 0.1 to 15.0% by mass, more preferably 0.2% by mass or more and 10.0% by mass or less, based on the total mass of the flux (F3).
  • Examples of the solvent used in the flux (F3) include water, alcohol-based solvents, glycol ether-based solvents, terpineols, and the like.
  • the flux (F3) may contain components other than organic acids, rosins, thixo agents and solvents, and examples thereof include amines, halogen-based activators, antioxidants, resin components other than rosin, and surfactants. Be done.
  • the flux (F4) is a composition containing a compound represented by the following general formula (1).
  • Examples of the flux (F4) include those containing a compound represented by the following general formula (1), a rosin, and a solvent.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, a cyclopropyl group, a butyl group and a cyclobutyl group.
  • R 1 , R 2 , R 3 and R 4 are preferably a hydrogen atom, a methyl group, an ethyl group and a cyclopropyl group, more preferably a hydrogen atom and a methyl group, and are hydrogen atoms. Is particularly preferable.
  • R 1 , R 2 , R 3 and R 4 may be the same or different.
  • Examples of the compound represented by the general formula (1) include picolinic acid, 6-methylpicolinic acid, 6-ethylpicolinic acid, 3-cyclopropylpicolinic acid, 4-cyclopropylpicolinic acid, and 6-cyclopropylpicolinic acid. Examples thereof include 5-butylpicolinic acid and 6-cyclobutylpicolinic acid. Of these, picolinic acid is particularly preferred. As the compound represented by the general formula (1), one type may be used alone, or two or more types may be mixed and used.
  • the flux (F4) preferably contains the compound represented by the general formula (1) in an amount of 0.5% by mass or more and 7% by mass or less based on the total mass of the flux (F4), and is represented by the general formula (1). It is more preferable to contain 1.0% by mass or more and 7.0% by mass or less, and more preferably 3.0% by mass or more and 7.0% by mass or less, and 3.0% by mass or more and 5.0% by mass or less. It is particularly preferable to contain% or less.
  • Examples of the rosin used in the flux (F4) include raw material rosins such as gum rosin, wood rosin and tall oil rosin, and derivatives obtained from the raw material rosin.
  • Examples of the derivative include purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, acid-modified rosin, phenol-modified rosin and ⁇ , ⁇ -unsaturated carboxylic acid-modified products (acrylicized rosin, maleated rosin, and fumarized products).
  • the flux (F4) preferably contains rosin in an amount of 30% by mass or more and 60% by mass or less based on the total mass of the flux (F4), and more preferably 35% by mass or more based on the total mass of the flux (F4). Contains 60% by mass or less.
  • Examples of the solvent used in the flux (F4) include water, alcohol-based solvents, glycol ether-based solvents, terpineols, and the like.
  • the flux (F4) may further be used in combination with an organic acid (excluding the compound represented by the general formula (1)).
  • organic acid those exemplified above can be used without particular limitation, and for example, at least one selected from the group consisting of succinic acid, glutaric acid, adipic acid and hydrogenated dimer acid is preferable. ..
  • the compound represented by the general formula (1) when the compound represented by the general formula (1) and the organic acid (excluding the compound represented by the general formula (1)) are not used in combination, the compound represented by the general formula (1) is used. , 1% by mass or more and 7% by mass or less with respect to the total mass of the flux (F4), more preferably 2% by mass or more and 7% by mass or less of the compound represented by the general formula (1), and further.
  • the compound represented by the general formula (1) is contained in an amount of 3% by mass or more and 7% by mass or less, and particularly preferably, the compound represented by the general formula (1) is contained in an amount of 3% by mass or more and 5% by mass or less.
  • the compound represented by the general formula (1) is used. , 0.5% by mass or more and 7% by mass or less with respect to the total mass of the flux (F4), and more preferably 0.5% by mass or more and 5% by mass of the compound represented by the general formula (1). It contains the following, and more preferably contains 1% by mass or more and 5% by mass or less of the compound represented by the general formula (1).
  • the flux (F4) preferably contains an organic acid of 0% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 10% by mass or less, based on the total mass of the flux (F4). It is more preferably contained in an amount of 5.5% by mass or more and 8% by mass or less, and particularly preferably contained in an amount of 1% by mass or more and 6% by mass or less.
  • the compound represented by the general formula (1) and the organic acid are added to the total mass of the flux (F4) by 3% by mass or more in total. It is preferably contained, more preferably 5% by mass or more in total, further preferably 6% by mass or more in total, and particularly preferably 6.5% by mass or more and 15% by mass or less in total.
  • the flux (F4) may further contain an amine, an organic halogen compound, and an amine hydrohalide. Further, the flux (F4) may further contain a thixotropic agent. Examples of the thixotropy used in the flux (F4) include amide thixotropy, sorbitol thixotropy, wax-based thixotropy (ester compound) and the like. The content of the thixotropy is preferably 0.1 to 15.0% by mass, more preferably 0.2% by mass or more and 10.0% by mass or less, based on the total mass of the flux (F4).
  • the flux (F4) may further contain, for example, a resin component other than rosin, a surfactant, an antioxidant and the like.
  • Flux (F5) is a composition containing azoles.
  • the flux (F5) include those containing azoles, organic acids, rosins, and solvents. According to this form, the corrosion inhibitory property of the metal surface (for example, copper plate) of the object to be bonded is improved. Can be done.
  • azoles as used herein means a compound having a complex 5-membered ring structure containing one or more nitrogen atoms, and also includes a fused ring of the complex 5-membered ring structure and another ring structure.
  • azoles examples include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4.
  • the azoles are preferably at least one selected from the group consisting of 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, benzimidazole and 2-octylbenzoimidazole, preferably 2-phenyl. Those containing imidazole are more preferable.
  • the flux (F5) preferably contains azoles in an amount of 0.1% by mass or more and 10% by mass or less with respect to the total mass of the flux (F5), and more preferably 0 with respect to the total mass of the flux (F5). Includes 5.5% by mass or more and 5.0% by mass or less.
  • the content of the organic acid used in the flux (F5) is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 3% by mass or more and 18% by mass or less with respect to the total mass of the flux (F5).
  • the ratio of the organic acid content to the azoles content is preferably 0.5 or more and 10 or less as the mass ratio expressed by the organic acid content / azoles content. More preferably, it is 1 or more and 9 or less. When this mass ratio is within the above-mentioned preferable range, the corrosion inhibitory property of the metal surface (for example, copper plate) of the object to be joined is likely to be enhanced.
  • the total amount of the organic acid content and the azoles content is preferably 3% by mass or more and 25% by mass or less, and 5% by mass or more and 20% by mass with respect to the total mass of the flux (F5). More preferably, it is 5% by mass or more, more preferably 18% by mass or less, and particularly preferably 5% by mass or more and 15% by mass or less.
  • Examples of the rosin used in the flux (F5) include raw material rosins such as gum rosin, wood rosin and tall oil rosin, and derivatives obtained from the raw material rosin.
  • Examples of the derivative include purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, acid-modified rosin, phenol-modified rosin and ⁇ , ⁇ -unsaturated carboxylic acid-modified products (acrylicized rosin, maleated rosin, and fumarized products).
  • the flux (F5) preferably contains rosin in an amount of 30% by mass or more and 60% by mass or less based on the total mass of the flux (F5), and more preferably 35% by mass or more based on the total mass of the flux (F5). Contains 60% by mass or less.
  • Examples of the solvent used in the flux (F5) include water, alcohol-based solvents, glycol ether-based solvents, terpineols, and the like.
  • the flux (F5) may further contain an amine, an organic halogen compound, and an amine hydrohalide. Further, the flux (F5) may further contain a thixotropic agent. Examples of the thixotropy used in the flux (F5) include amide-based thixotropy, sorbitol-based thixotropy, and wax-based thixotropy (ester compound).
  • the content of the thixo agent is preferably 0.1 to 15.0% by mass, more preferably 0.2% by mass or more and 10.0% by mass or less, and 1.0% by mass, based on the total mass of the flux (F5). % Or more and 10.0% by mass or less are more preferable, and 2.0% by mass or more and 8.3% by mass or less are particularly preferable.
  • the flux (F5) may further contain, for example, a resin component other than rosin, a surfactant, an antioxidant and the like.
  • Flux (F6) is a composition containing an aromatic guanidine compound.
  • the flux (F6) include those containing an aromatic guanidine compound, rosin, an organic acid, and a solvent.
  • the aromatic guanidine compound include diphenylguanidine and ditrilguanidine.
  • One type of aromatic guanidine compound may be used alone, or two or more types may be mixed and used.
  • the aromatic guanidine compound is preferably at least one selected from the group consisting of diphenylguanidine and ditrilguanidine, and more preferably contains diphenylguanidine.
  • the flux (F6) preferably contains an aromatic guanidine compound in an amount of 0.2% by mass or more and 15% by mass or less based on the total mass of the flux (F6), and more preferably 0.5% by mass of the aromatic guanidine compound. Includes% or more and 7.0% by mass or less.
  • Examples of the rosin used in the flux (F6) include natural rosin and derivatives obtained from the natural rosin.
  • natural rosin include gum rosin, wood rosin, tall oil rosin and the like.
  • the derivative include purified rosin and modified rosin.
  • Modified rosins include hydrogenated rosin, polymerized rosin, disproportionated rosin, acid-modified rosin, rosin ester, phenol-modified rosin and ⁇ , ⁇ -unsaturated carboxylic acid-modified products (acrylicated rosin, maleated rosin, fumarized rosin, etc.
  • One or more of these can be used.
  • the flux (F6) preferably contains rosin in an amount of 15% by mass or more and 70% by mass or less based on the total mass of the flux (F6), and more preferably 35% by mass or more based on the total mass of the flux (F6). Contains 60% by mass or less.
  • the content of the organic acid used in the flux (F6) is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 0.2% by mass or more and 10% by mass or less with respect to the total mass of the flux (F6). ..
  • the flux (F6) preferably contains an organic acid and an aromatic guanidine compound in a total amount of 2% by mass or more and 18% by mass or less, and 3% by mass or more and 18% by mass or less in total, based on the total mass of the flux (F6). It is more preferable to contain less than mass%.
  • Examples of the solvent used in the flux (F6) include water, alcohol-based solvents, glycol ether-based solvents, terpineols, and the like.
  • the flux (F6) may further contain a thixotropic agent.
  • thixotropy used in the flux (F6) include amide-based thixotropy, sorbitol-based thixotropy, and wax-based thixotropy (ester compound).
  • the content of the thixotropy is preferably 0.1 to 15.0% by mass, more preferably 0.2% by mass or more and 10.0% by mass or less, based on the total mass of the flux (F6).
  • the flux (F6) may further contain an amine, an organic halogen compound, and an amine hydrohalide. Further, the flux (F6) may further contain, for example, a resin component other than rosin, a surfactant, an antioxidant and the like.
  • Flux (F7) is a composition containing an amide thixotropic agent which is an amide compound.
  • the flux (F7) includes, for example, an amide-based thixo agent which is the above-mentioned amide compound, an organic acid, a resin component which is at least one selected from the group consisting of a rosin-based resin and an acrylic-based resin, a solvent, and the like. Examples include those containing.
  • Examples of the amide thixotropy (amide compound) include polyamide, bisamide, and monoamide.
  • such amide-based thixo agents include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, saturated fatty acid amide, oleic acid amide, erucic acid amide, and unsaturated fatty acid amide.
  • P-toluamide, p-toluenemethaneamide aromatic amide, hexamethylenehydroxystearic acid amide, substituted amide, methylolstearic acid amide, methylolamide, fatty acid esteramide and other monoamides; methylenebisstearic acid amide, ethylenebislauric acid.
  • Amide ethylene bishydroxy fatty acid (carbon number C6-24 of fatty acid) amide, ethylene bishydroxystearic acid amide, saturated fatty acid bisamide, methylene bisoleic acid amide, unsaturated fatty acid bisamide, m-xylylene bisstearic acid amide, aromatic Bisamides such as bisamides; examples thereof include saturated fatty acid polyamides, unsaturated fatty acid polyamides, aromatic polyamides, tris 1,2,3-propanetricarboxylic acids (2-methylcyclohexylamide), cyclic amide oligomers, and polyamides such as acyclic amide oligomers. ..
  • the cyclic amide oligomer includes an amide oligomer in which dicarboxylic acid and diamine are polycondensed cyclically, an amide oligomer in which tricarboxylic acid and diamine are polycondensed cyclically, an amide oligomer in which dicarboxylic acid and triamine are polycondensed cyclically, and tricarboxylic acid.
  • Amido oligomer with cyclic polycondensation of dicarboxylic acid and triamine amide oligomer with cyclic polycondensation of dicarboxylic acid and tricarboxylic acid and diamine, amide oligomer with cyclic polycondensation of dicarboxylic acid and tricarboxylic acid and triamine, dicarboxylic acid and diamine
  • an amide oligomer in which triamine is cyclically polycondensed an amide oligomer in which tricarboxylic acid, diamine and triamine are polycondensed cyclically, and an amide oligomer in which dicarboxylic acid and tricarboxylic acid and diamine and triamine are cyclically polycondensed. ..
  • the acyclic amide oligomer is an amide oligomer in which a monocarboxylic acid and diamine and / or triamine are polycondensed in an acyclic manner
  • the amide in which a dicarboxylic acid and / or the tricarboxylic acid and the monoamine are polycondensed acyclically.
  • examples thereof include the case of an oligomer.
  • the monocarboxylic acid and the monoamine function as terminal molecules (terminal molecules), and become an acyclic amide oligomer having a reduced molecular weight.
  • 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 manner
  • the acyclic amide oligomer is a non-cyclic polymer amide polymer.
  • the acyclic amide oligomer also includes an amide oligomer in which a monocarboxylic acid and a monoamine are acyclically condensed.
  • amide thixotropy (amide compound) contained in the flux (F7) of the present embodiment it is preferable to use one containing at least one selected from the group consisting of polyamide, bisamide and monoamide. Among them, it consists of p-toluamide, ethylenebishydroxy fatty acid (C6-24) amide, hexamethylenehydroxystearic acid amide, tris 1,2,3-propanetricarboxylic acid (2-methylcyclohexylamide), polyamide and cyclic amide oligomer. It is more preferable to use at least one selected from the group.
  • the content of the amide thixotropic agent is preferably more than 0% by mass and 15% by mass or less, preferably 1.5% by mass, based on the total mass of the flux (F7). More preferably, it is% or more and 10.0% by mass or less.
  • thixotropic agents other than amide compounds include wax-based thixotropic agents.
  • wax-based thixotropy include ester compounds, and specific examples thereof include castor oil.
  • the flux of the present embodiment preferably contains the ester compound in an amount of 0% by mass or more and 15% by mass or less, and more than 0% by mass and 12.0% by mass or less, based on the total mass of the flux (F7). preferable.
  • the flux of the present embodiment preferably contains 3.0% by mass or more and 15.0% by mass or less of the total mass of the amide compound which is a thixo agent and the ester compound with respect to the total mass of the flux (F7). It is more preferable to contain 5.0% by mass or more and 10.0% by mass or less.
  • the content of the organic acid used in the flux (F7) is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 0.2% by mass or more and 10% by mass or less with respect to the total mass of the flux (F7). ..
  • the flux (F7) preferably contains at least one resin component selected from the group consisting of rosin-based resins and acrylic-based resins in an amount of 15% by mass or more and 70% by mass or less based on the total mass of the flux (F7). More preferably, it contains 35% by mass or more and 60% by mass or less with respect to the total mass of the flux (F7).
  • Examples of the solvent used in the flux (F7) include water, alcohol-based solvents, glycol ether-based solvents, terpineols, and the like.
  • the flux (F7) may further contain a resin component other than the rosin-based resin and the acrylic-based resin, an amine, a halogen-based activator, a surfactant, and an antioxidant.
  • Flux (F8) is a composition containing a sorbitol-based thixotropy which is a sorbitol compound.
  • the flux (F8) include those containing the above-mentioned sorbitol compound, a sorbitol-based thixotropy, a rosin-based resin, and a solvent.
  • the sorbitol-based thixotropy (sorbitol compound) include dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol and the like.
  • the content of the sorbitol-based thixo agent is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and 0.5% by mass or more and 5.0% by mass with respect to the total mass of the flux (F8).
  • the following is more preferable, and 0.5% by mass or more and 3.5% by mass or less is particularly preferable.
  • a thixotropy other than the above-mentioned sorbitol-based thixotropy may be used in combination.
  • examples of the thixotropy other than the sorbitol-based thixotropy include sorbitol-based additives and other thixotropy agents.
  • the sorbitol-based additive examples include (D-) sorbitol, monobenzylidene (-D-) sorbitol, mono (4-methylbenzylidene)-(D-) sorbitol and the like.
  • the content of this sorbitol-based additive is preferably more than 0% by mass and 0.035% by mass or less, and more preferably 0.00025% by mass or more and 0.035% by mass or less with respect to the total mass of the flux (F8).
  • Examples of the other thixotropy include at least one selected from the group consisting of wax-based thixotropy and amide-based thixotropy (amide compound).
  • Examples of the wax-based thixotropy which is a thixotropy include ester compounds, and specific examples thereof include castor oil.
  • Examples of the amide thixotropy (amide compound) which is a thixotropy include the above-mentioned polyamide, bisamide, and monoamide.
  • the content of the other thixotropy is preferably 0.5 to 15.0% by mass, more preferably 1% by mass or more and 10% by mass or less, based on the total mass of the flux (F8).
  • the flux (F8) of the present embodiment preferably contains a sorbitol-based thixo agent and other thixo agents in a total amount of 2% by mass or more and 15% by mass or less with respect to the total mass of the flux (F8). ), It is more preferable to contain 2.5% by mass or more and 11.5% by mass or less in total.
  • the flux (F8) of the present embodiment preferably contains 2% by mass or more and 15% by mass or less of the total amount of the thixotropic agent with respect to the total mass of the flux (F8). It is more preferable to contain 2.5% by mass or more and 11.5% by mass or less.
  • the thixotropy with respect to the total mass of the flux (F8) of the present embodiment is at least one sorbitol-based thixotropy selected from the group consisting of dibenzylidene sorbitol and bis (4-methylbenzylidene) sorbitol, and other thixotropy. It is preferable to use the agent in combination. As a result, in addition to imparting thixotropic properties, precipitation of crystals and generation of lumps in the flux and the solder paste using the flux can be easily suppressed.
  • the flux (F8) thixotropy of the present embodiment is preferably a combination of the sorbitol-based thixotropy and the sorbitol-based additive.
  • a more preferable thixo agent is at least one selected from the group consisting of the sorbitol-based thixo agent and the group consisting of (D-) sorbitol, monobenzylidene (-D-) sorbitol and mono (4-methylbenzylidene)-(D-) sorbitol.
  • sorbitol-based additives that are.
  • the ratio (mass ratio) of the sorbitol-based additive to the sorbitol-based thixotropy is preferably 0.03 to 1.50, and more preferably 0.05 to 1.00.
  • the thixotropy of the flux (F8) of the present embodiment it is preferable to use the sorbitol-based thixotropy, the sorbitol-based additive, and the other thixotropy in combination.
  • the flux (F8) preferably contains a rosin-based resin in an amount of 15% by mass or more and 70% by mass or less based on the total mass of the flux (F8), and 35% by mass or more and 60% by mass or less based on the total mass of the flux (F8). It is more preferable to contain% or less.
  • Examples of the solvent used in the flux (F8) include water, alcohol-based solvents, glycol ether-based solvents, terpineols, and the like.
  • the flux (F8) may further contain components other than the thixo agent, the rosin-based resin and the solvent, and examples thereof include organic acids, amines, halogen-based activators, surfactants and antioxidants.
  • solder paste which has physical properties and has good fluidity and shape retention.
  • a flux for solder paste which can impart sufficient thixotropy, preferably suppresses the precipitation of crystals, and is less likely to cause lumps.
  • the solder paste is usually supplied to the electrodes of the printed circuit board by dispenser ejection or screen printing.
  • solder paste is required to have printability such as ejection property and plate removal, and further, it is required that the shape of the solder paste is maintained after being supplied.
  • the flow characteristics thixotropic property
  • low viscosity low viscosity
  • shape retention after supply high viscosity
  • the flux (F9) is a composition containing both a glycol solvent and an organic acid ester.
  • Examples of the flux (F9) include those containing a resin component, a solvent, and various active components.
  • Preferred flux (F9) includes those containing a rosin-based resin, an organic acid, and a glycol-based solvent and an organic acid ester as solvents.
  • Examples of the rosin-based resin that can be used in the flux (F9) include natural rosins such as gum rosin and wood rosin, and derivatives thereof (polymerized rosin, hydrogenated rosin, disproportionated rosin, acid-modified rosin, rosin ester, etc.). Can be mentioned.
  • the content of the rosin-based resin in the flux (F9) is not particularly limited, and is preferably in the range of 10 to 80% by mass, preferably in the range of 20 to 70% by mass, based on the total mass of the flux (F9). Is more preferable, and the range of 30 to 60% by mass is further preferable.
  • the content of the organic acid in the flux (F9) is not particularly limited, and is preferably in the range of 1 to 15% by mass, preferably in the range of 3 to 10% by mass, based on the total mass of the flux (F9). More preferred.
  • the flux (F9) of the present embodiment contains at least a glycol-based solvent and an organic acid ester as the solvent.
  • organic acid esters have a boiling point in an appropriate range, and at the joining temperature used in general soldering, they remain in the flux at the initial stage of joining to keep the melt viscosity of the flux low, and decompose gas and the like. Volatilizes to some extent in the late bonding stage, while facilitating the release of the solder.
  • glycol a compound having a structure in which one hydroxyl group is bonded to two different carbon atoms of an aliphatic or alicyclic hydrocarbon
  • the type of glycol-based solvent is not limited, and for example, a flux generally used for soldering flux can be used.
  • glycol-based solvents include diethylene glycol, dipropylene glycol, triethylene glycol, hexylene glycol, phenyl glycol, hexyl diglycol, 2-ethylhexyl diglycol, diethylene glycol monobutyl ether (butyl carbitol), and diethylene glycol monomethyl ether.
  • glycol ethers such as (methylcarbitol), diethylene glycol monohexyl ether (hexylcarbitol), and propylene glycol monophenyl ether.
  • glycol ethers of alcohols having 2 to 24 carbon atoms specifically, monoglycol ethers (carbon atoms: 4 to 26), diglycol ethers (carbon atoms: 6 to 28), oligoglycol ethers (carbon atoms: 6 to 28)).
  • 2 + 2 ⁇ n to 24 + 2 ⁇ n) is preferable
  • alcohol glycol ethers having 4 to 16 carbon atoms are more preferable
  • alcohol glycol ethers having 6 to 8 carbon atoms are particularly preferable.
  • the glycol solvent one kind may be used alone, or two or more kinds may be used in combination.
  • the content of the glycol-based solvent in the flux (F9) (the total content when a plurality of types of glycol-based solvents are used) is not particularly limited, and is, for example, 10 to 60 with respect to the total mass of the flux (F9).
  • the range of mass% is preferable, the range of 15 to 50% by mass is more preferable, and the range of 20 to 45% by mass is further preferable.
  • an organic acid ester is used in combination with the above glycol-based solvent as the solvent.
  • a flux having a low melt viscosity can be realized at the time of soldering.
  • the flux containing the organic acid ester can suppress the reaction between the solder alloy powder and the activator during storage of the solder paste, the activity of the active agent remains even if the activity and the blending amount of the activator are not adjusted. Good wettability at the time of attachment can be ensured, and the generation of voids can be suppressed.
  • organic acid ester examples include dimethyl adipate, diisopropyl adipate, dibutyl maleate, dimethyl sebacate, diisobutyl adipate, diethyl sebacate, diisopropyl sebacate, dibutyl sebacate, dioctyl sebacate and the like. These may be used alone or in admixture of a plurality of types.
  • the content of the organic acid ester in the flux (F9) (the total content when a plurality of types of organic acid esters are used) is not particularly limited, but is 0.5 mass with respect to the total mass of the flux (F9). % Or more is preferable, 1% by mass or more is more preferable, and 5% by mass or more is further preferable. On the other hand, from the viewpoint of eliminating poor drying of flux and solder paste and suppressing stickiness, the content is preferably small, for example, 30% by mass or less, more preferably 25% by mass or less, and further 20% by mass or less. It is preferable, and 15% by mass or less is particularly preferable.
  • the mass ratio of the content of the organic acid ester (mass%) (the total amount when a plurality of types are used) to the content (mass%) of the glycol-based solvent (organic acid ester content / content of the glycol-based solvent). is not particularly limited, but is preferably 0.01 to 1.25, more preferably 0.10 to 1.0, and 0.15 to 0. From the viewpoint of preventing the generation of voids. It is more preferably 75, and particularly preferably 0.15 to 0.50.
  • solvents such as alcohols such as benzyl alcohol, ethanol, isopropyl alcohol, butanol, 1,5-pentanediol, octanediol, terpineol, ethyl cellosolve, and butyl cellosolve; hydrocarbons such as toluene, xylene, and n-hexane. Examples thereof include hydrogens, and one or more of these can be used.
  • alcohols such as benzyl alcohol, ethanol, isopropyl alcohol, butanol, 1,5-pentanediol, octanediol, terpineol, ethyl cellosolve, and butyl cellosolve
  • hydrocarbons such as toluene, xylene, and n-hexane. Examples thereof include hydrogens, and one or more of these can be used.
  • the total content of the solvent in the flux (F9) of the present embodiment is preferably in the range of 20 to 70% by mass, more preferably in the range of 25 to 60% by mass, based on the total mass of the flux (F9). , 30 to 60% by mass is more preferable.
  • the flux (F9) of the present embodiment may contain a resin component other than the rosin-based resin, a thixotropy, an amine, a halogen-based activator, a surfactant, and an antioxidant.
  • the flux (F10) is a composition containing both a glycol solvent and a monohydric alcohol having 16 to 18 carbon atoms.
  • Examples of the flux (F10) include those containing a resin component, a solvent, and various active components.
  • Preferred flux (F10) includes a rosin-based resin, an organic acid, a glycol-based solvent as a solvent, and a monohydric alcohol having 16 to 18 carbon atoms.
  • Examples of the rosin-based resin that can be used in the flux (F10) include natural rosins such as gum rosin and wood rosin, and derivatives thereof (polymerized rosin, hydrogenated rosin, disproportionated rosin, acid-modified rosin, rosin ester, etc.). Can be mentioned.
  • the content of the rosin-based resin in the flux (F10) is not particularly limited, and is preferably in the range of 10 to 80% by mass, preferably in the range of 20 to 70% by mass, based on the total mass of the flux (F10). Is more preferable, and the range of 30 to 60% by mass is further preferable.
  • the content of the organic acid in the flux (F10) is not particularly limited, and is preferably in the range of 1 to 15% by mass, preferably in the range of 3 to 10% by mass, based on the total mass of the flux (F10). More preferred.
  • the flux (F10) of the present embodiment at least a glycol-based solvent and a monohydric alcohol having 16 to 18 carbon atoms are used together as the solvent.
  • Such monovalent alcohols having a carbon number have a boiling point in an appropriate range, and at the bonding temperature used in general soldering, they remain in the flux at the initial stage of bonding to increase the melt viscosity of the flux. It keeps low and easily releases decomposition gas, etc., and volatilizes to some extent in the latter stage of joining.
  • glycol-based solvent refers to a solvent composed of glycol (a compound having a structure in which one hydroxyl group is bonded to two different carbon atoms of an aliphatic or alicyclic hydrocarbon) or a derivative thereof.
  • the type of glycol-based solvent is not limited, and for example, those generally used for soldering flux can be used.
  • glycol-based solvents include diethylene glycol, dipropylene glycol, triethylene glycol, hexylene glycol, phenyl glycol, hexyl diglycol, 2-ethylhexyl diglycol, diethylene glycol monobutyl ether (butyl carbitol), and diethylene glycol monomethyl ether.
  • glycol ethers such as (methylcarbitol), diethylene glycol monohexyl ether (hexylcarbitol), and propylene glycol monophenyl ether.
  • glycol ethers of alcohols having 2 to 24 carbon atoms specifically, monoglycol ethers (carbon atoms: 4 to 26), diglycol ethers (carbon atoms: 6 to 28), oligoglycol ethers (carbon atoms: 6 to 28)).
  • 2 + 2 ⁇ n to 24 + 2 ⁇ n) is preferable
  • alcohol glycol ethers having 4 to 16 carbon atoms are more preferable
  • alcohol glycol ethers having 6 to 8 carbon atoms are particularly preferable.
  • the glycol solvent one kind may be used alone, or two or more kinds may be used in combination.
  • the content of the glycol-based solvent in the flux (F10) (the total content when a plurality of types of glycol-based solvents are used) is not particularly limited, and is, for example, 10 to 60 with respect to the total mass of the flux (F10).
  • the range of mass% is preferable, the range of 15 to 50% by mass is more preferable, and the range of 20 to 45% by mass is further preferable.
  • a monohydric alcohol having 16 to 18 carbon atoms is used in combination as the solvent in addition to the glycol solvent.
  • a flux having a low melt viscosity can be realized at the time of soldering.
  • monohydric alcohols having 16 to 18 carbon atoms include 1-hexadecanol (16 carbon atoms), 2-hexyldecanol (16 carbon atoms), isohexadecanol (16 carbon atoms), and 1-heptadecanol (carbon carbon atoms).
  • 1-octadecanol (18 carbon atoms), isostearyl alcohol (18 carbon atoms) and the like may be used, and only one type may be used, or two or more types may be used in combination. Among these, those having 16 carbon atoms are preferable, and 2-hexyldecanol (CAS number: 2425-77-6) is particularly preferable because it is less sticky.
  • 2-hexyldecanol for example, Fineoxocol 1600 (manufactured by Nissan Chemical Industries, Ltd., registered trademark) and the like can be used.
  • the content of the monohydric alcohol having 16 to 18 carbon atoms in the flux (F10) is not particularly limited, and it is sufficient that the monohydric alcohol having 16 to 18 carbon atoms is contained in the flux (F10). From the viewpoint of lowering the melt viscosity of the flux or solder paste during soldering, it is preferable that the content of monovalent alcohol having 16 to 18 carbon atoms in the flux (F10) is high, for example, 0.5 mass. % Or more is preferable, 1% by mass or more is more preferable, and 5% by mass or more is further preferable.
  • the content of the monohydric alcohol having 16 to 18 carbon atoms in the flux (F10) is small, for example, 30% by mass or less. Is preferable, 20% by mass or less is more preferable, and 15% by mass or less is further preferable.
  • the monohydric alcohol content / content of the glycol solvent) is not particularly limited, but is preferably 0.01 to 1.25 from the viewpoint of preventing the generation of voids and the balance of drying, and is 0. It is more preferably .15 to 1.25, and even more preferably 0.15 to 0.72.
  • solvents such as alcohols such as benzyl alcohol, ethanol, isopropyl alcohol, butanol, 1,5-pentanediol, octanediol, terpineol, ethyl cellosolve, and butyl cellosolve; carbonization of toluene, xylene, n-hexane and the like.
  • Esters such as isopropyl acetate and butyl benzoate can be mentioned, and one or more of these can be used.
  • the total content of the solvent in the flux (F10) of the present embodiment is preferably in the range of 20 to 70% by mass, more preferably in the range of 25 to 60% by mass, based on the total mass of the flux (F10). , 30 to 55% by mass is more preferable.
  • the flux (F10) of the present embodiment may contain a resin component other than the rosin-based resin, a thixotropy, an amine, a halogen-based activator, a surfactant, and an antioxidant.
  • Flux (F11) is a composition containing a hindered phenolic compound.
  • the flux (F11) include a hindered phenol-based compound, an organic acid, a resin component which is at least one selected from the group consisting of a rosin-based resin and an acrylic-based resin, and a solvent. Be done.
  • Flux (F11) contains a hindered phenolic compound as a metal inactivating agent. Since the flux contains a hindered phenolic compound, it exerts an effect of suppressing thickening in the solder paste.
  • the hindered phenol-based compound refers to a phenol-based compound having a bulky substituent (for example, a branched or cyclic alkyl group such as a t-butyl group) at at least one of the ortho positions of the phenol.
  • the hindered phenol-based compound is not particularly limited, and is, for example, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)], N, N.
  • Z is an optionally substituted alkylene group.
  • R 5 and R 6 are alkyl groups, aralkyl groups, aryl groups, heteroaryl groups, cycloalkyl groups or heterocycloalkyl groups, which may be substituted independently of each other.
  • R 7 and R 8 are alkyl groups that may be substituted independently of each other.
  • the above hindered phenolic compounds are used alone or in combination of two or more.
  • the content of the hindered phenolic compound is preferably 0.5 to 10% by mass with respect to the total mass of the flux (F11).
  • the content is 0.5% by mass or more, the solder paste can further improve the thickening suppressing effect.
  • the content is 10% by mass or less, the solder paste can further improve the solder wettability.
  • the content is more preferably 1.0 to 5.0% by mass with respect to the total mass of the flux (F11), and 2.0 to 4 with respect to the total mass of the flux (F11). It is more preferably 0.0% by mass.
  • the content of the organic acid used in the flux (F11) is preferably 0.1% by mass or more and 15% by mass or less with respect to the total mass of the flux (F11), and is 0.2 with respect to the total mass of the flux (F11). More preferably, it is by mass% or more and 10% by mass or less.
  • the flux (F11) preferably contains at least one resin component selected from the group consisting of rosin-based resins and acrylic-based resins in an amount of 15% by mass or more and 70% by mass or less based on the total mass of the flux (F11). More preferably, it contains 20% by mass or more and 60% by mass or less with respect to the total mass of the flux (F11).
  • Examples of the solvent used in the flux (F11) include water, alcohol-based solvents, glycol ether-based solvents, terpineols, and the like.
  • the flux (F11) may further contain a resin component other than the rosin-based resin and the acrylic-based resin, a thixo agent, an amine, a halogen-based activator, a surfactant, and an antioxidant.
  • Flux (F12) is a composition containing a metal inactivating agent, which is a nitrogen compound.
  • the flux (F12) include a metal inactivating agent which is a nitrogen compound, a resin component which is at least one selected from the group consisting of a rosin resin and an acrylic resin, and a solvent. Be done.
  • Flux (F12) contains a nitrogen compound as a metal inactivating agent. Since the flux contains a metal inactivating agent which is a nitrogen compound, it exerts an effect of suppressing thickening in the solder paste.
  • the nitrogen compound is not particularly limited as long as it contains a nitrogen atom and is used as a metal inactivating agent.
  • the nitrogen compound here is preferably at least one selected from the group consisting of hydrazide-based nitrogen compounds, amide-based nitrogen compounds, triazole-based nitrogen compounds and melamine-based nitrogen compounds from the viewpoint of excellent thickening inhibitory effect, and is preferably hydrazide-based. At least one selected from the group consisting of nitrogen compounds and triazole-based nitrogen compounds is more preferable.
  • the hydrazide-based nitrogen compound may be any nitrogen compound having a hydrazide skeleton, and is bis dodecanoate [N2- (2-hydroxybenzoyl) hydrazide], N, N'-bis [3- (3,5-di-tert).
  • the amide-based nitrogen compound may be a nitrogen compound having an amide skeleton, and N, N'-bis ⁇ 2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyl] ethyl. ⁇ Oxamide and the like can be mentioned.
  • the triazole-based nitrogen compound may be any nitrogen compound having a triazole skeleton, and N- (2H-1,2,4-triazole-5-yl) salicylamide, 3-amino-1,2,4-triazole, Examples thereof include 3- (N-salicyloyl) amino-1,2,4-triazole.
  • the melamine-based nitrogen compound may be any nitrogen compound having a melamine skeleton, and examples thereof include melamine and melamine derivatives. More specifically, for example, trisaminotriazine, alkylated trisaminotriazine, alkoxyalkylated trisaminotriazine, melamine, alkylated melamine, alkoxyalkylated melamine, N2-butyl melamine, N2, N2-diethyl melamine, N, Examples thereof include N, N', N', N'', N''-hexakis (methoxymethyl) melamine and the like.
  • melamine-based nitrogen compound a commercially available product may be used, and examples thereof include ADEKA TAB ZS-27 and ZS-90 manufactured by ADEKA, and ADEKA STAB ZS-27 is more preferable. These specific commercially available products are preferable from the viewpoint that the thickening suppressing effect becomes more remarkable.
  • the above nitrogen compounds may be used alone or in combination of two or more.
  • the content of the nitrogen compound is preferably more than 0% by mass and 10% by mass or less, more preferably 0.05 to 5.0% by mass, and 0, based on the total mass of the flux (F12). .10 to 2.0% by mass is more preferable, and 0.10 to 1.0% by mass is particularly preferable. When the content exceeds 0% by mass, the solder paste is excellent in the thickening suppressing effect.
  • a hindered phenol-based compound may be used in combination with the above-mentioned nitrogen compound as the metal inactivating agent.
  • the solder paste has a more excellent effect of suppressing thickening.
  • the hindered phenolic compound is not particularly limited, and examples thereof include the same hindered phenolic compounds as those exemplified in the above description of the flux (F11).
  • the content of the hindered phenolic compound is, for example, preferably 0 to 10% by mass, more preferably 1 to 10% by mass, still more preferably 2 to 10% by mass, based on the total mass of the flux (F12).
  • the flux (F12) preferably contains at least one resin component selected from the group consisting of rosin-based resins and acrylic-based resins in an amount of 15% by mass or more and 70% by mass or less based on the total mass of the flux (F12). More preferably, it contains 35% by mass or more and 60% by mass or less with respect to the total mass of the flux (F12).
  • the solvent used in the flux (F12) include water, alcohol-based solvents, glycol ether-based solvents, terpineols and the like.
  • the flux (F12) may further contain an organic acid.
  • the content of the organic acid used in the flux (F12) is preferably 0.1% by mass or more and 15% by mass or less with respect to the total mass of the flux (F12), and is 0.2 with respect to the total mass of the flux (F12). It is more preferably 1% by mass or more and 10% by mass or less, and further preferably 1% by mass or more and 8% by mass or less.
  • the flux (F12) may further contain a resin component other than the rosin-based resin and the acrylic-based resin, a thixo agent, an amine, a halogen-based activator, a surfactant, and an antioxidant.
  • solder paste according to the present invention described above is suitable for joining an IC chip and its substrate (interposer) in a semiconductor package, or for joining a semiconductor package and a printed wiring board.
  • the joining method using the solder paste according to the present invention may be carried out according to a conventional method using, for example, a reflow method.
  • the melting temperature of the solder alloy when flow soldering is performed may be about 20 ° C. higher than the liquidus temperature.
  • Other joining conditions can be appropriately adjusted according to the alloy composition of the solder alloy.
  • a low ⁇ -dose alloy can be produced by using a low- ⁇ -dose material as a raw material thereof.
  • a low ⁇ -dose alloy is used for forming solder bumps around a memory, soft errors can be suppressed.
  • the solder paste of this embodiment preferably further contains zirconium oxide powder.
  • zirconium oxide By containing zirconium oxide, it is possible to suppress an increase in the viscosity of the paste due to aging. It is presumed that this is because the zirconium oxide is contained so that the oxide film thickness on the surface of the solder powder is maintained in the state before being put into the flux. The details of this are unknown, but it is inferred as follows. Normally, the active component of the flux has a slight activity even at room temperature, so that the surface oxide film of the solder powder becomes thin due to reduction, which causes the powders to aggregate with each other.
  • the active component of the flux reacts preferentially with the zirconium oxide powder, and the oxide film on the surface of the solder powder is maintained to such an extent that it does not aggregate.
  • the content of the zirconium oxide powder in the solder paste is preferably 0.05 to 20.0% by mass with respect to the total mass of the solder paste.
  • the content of the zirconium oxide powder is more preferably 0.05 to 10.0% by mass, and further preferably 0.1 to 3% by mass.
  • the particle size of the zirconium oxide powder in the solder paste is preferably 5 ⁇ m or less. When the particle size is 5 ⁇ m or less, the printability of the paste can be maintained.
  • the lower limit of the particle size is not particularly limited, but may be 0.5 ⁇ m or more.
  • an SEM photograph of the zirconium oxide powder is taken, and the diameter corresponding to the projected circle is obtained by image analysis for each powder of 0.1 ⁇ m or more, and the average value is used.
  • the shape of zirconium oxide is not particularly limited, but if it has a different shape, the contact area with the flux is large and there is an effect of suppressing thickening. When it is spherical, good fluidity can be obtained, so that excellent printability as a paste can be obtained.
  • the shape may be appropriately selected according to the desired characteristics.
  • the flux for solder paste of the present embodiment is used for a solder paste that employs the above-mentioned specific solder powder.
  • the flux preferably contains a resin component, an active component, and a solvent.
  • the flux for solder paste of the present embodiment is a specific solder powder, that is, As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 0 to 10000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0.
  • a flux suitable for solder paste which employs a solder powder containing at least one type of ⁇ 3000 mass ppm and a solder alloy containing a solder alloy satisfying the following equations (1) and (2), having an alloy composition in which the balance is Sn. is there.
  • solder paste flux of the present embodiment is a specific solder powder, that is, As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 0 mass ppm or more and 10000 mass ppm or less, Pb: 0 mass ppm or more 5100.
  • solder paste in which the flux for solder paste of the present embodiment is combined with the above-mentioned specific solder powder is less likely to change with time such as an increase in viscosity, has excellent wettability, and exhibits high mechanical properties. Further, according to the solder paste in which this flux for solder paste is combined with the specific solder powder, by selecting the component to be blended in the flux, the wetting speed of the solder is improved, and the metal surface of the object to be joined (for example,). Various characteristics such as suppression of corrosion of copper plate), improvement of printability, and suppression of voids can be further enhanced.
  • solder powder having the alloy composition shown in Tables 1 to 24 and having a size (particle size distribution) satisfying the symbol 4 in the powder size classification (Table 2) in JIS Z 3284-1: 2014 (Test Examples 1 to 498, Test Examples 501 to 578) were prepared.
  • rosin was used as the resin component.
  • Thixotropy, organic acid, amine and halogen-based activators were used as active ingredients.
  • a glycol solvent was used as the solvent.
  • a flux (F0) is obtained by mixing 42 parts by mass of rosin, 35 parts by mass of a glycol solvent, 8 parts by mass of a thixo agent, 10 parts by mass of an organic acid, 2 parts by mass of an amine, and 3 parts by mass of a halogen-based activator. ) was prepared.
  • the flux (F0) prepared above was mixed with the solder powder having the alloy composition of each example shown in Tables 1 to 24 to prepare a solder paste.
  • the change over time in the viscosity of the solder paste was measured.
  • the liquidus temperature and the solidus temperature of the solder powder were measured.
  • the wettability was evaluated using the solder paste immediately after production. The details are as follows.
  • solder paste containing the solder powder having the alloy composition of Test Examples 1 to 498 and the flux (F0) all the requirements of the present invention are satisfied in any alloy composition. In order to satisfy the requirements, it was confirmed that the thickening inhibitory effect, the narrowing of ⁇ T, and the excellent wettability were exhibited.
  • These solder pastes containing the solder powder having the alloy composition of Test Examples 1 to 498 and the flux (F0) are the solder pastes of the examples to which the present invention is applied.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578 and the flux (F0)
  • the solder paste does not satisfy at least one of the requirements of the present invention in any of the alloy compositions. At least one of the anti-viscous effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • solder wetting speed (solder wetting property)
  • Verification method An evaluation test of the solder wetting speed (solder wettability) was conducted as follows. According to the method of the meniscograph test, a copper plate having a width of 5 mm, a length of 25 mm and a thickness of 0.5 mm was oxidized at 150 ° C. for 1 hour to obtain a copper oxide plate as a test plate, and the Solder Checker SAT-5200 was used as a test apparatus. (Manufactured by RHESCA) was used, and a solder powder having the alloy composition shown in Test Example 1 was used as the solder for evaluation as follows.
  • test plate was immersed in each of the fluxes of Formulation Examples (F1-1) to (F1-55) measured in a beaker by 3 mm, and the flux was applied to the test plate. Subsequently, after the flux was applied, the test plate to which the flux was applied was immediately immersed in a solder bath having an alloy composition shown in Test Example 1 to obtain a zero cross time (sec). Subsequently, the flux of each formulation example was measured 5 times, and the average value of the obtained 5 zero cross times (sec) was calculated.
  • the test conditions were set as follows.
  • an aliphatic polyamide was used as the polyamide
  • hexamethylenebishydroxystearic acid amide was used as the bisamide
  • p-toluamide was used as the monoamide.
  • the fluxes of Formulation Examples (F1-1) to (F1-54) are used for the solder powder having the alloy composition shown in Test Example 1, the flux of Formulation Example (F1-55) is used in each case. It was confirmed that the wetting speed of the solder was higher and the solder wetting property was better than when it was used.
  • the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F1-1) to (F1-54) relates to the embodiment containing the flux (F1). It is a solder paste.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 contains a flux (F1).
  • the solder paste according to the embodiment in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • the composition ratios in Tables 34 to 46 are wt (mass)% when the total amount of flux is 100.
  • an aliphatic polyamide was used as the polyamide, hexamethylenebishydroxystearic acid amide was used as the bisamide, and p-toluamide was used as the monoamide.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 contains a flux (F2).
  • the solder paste according to the embodiment in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • solder paste (flux: solder) when the fluxes of Formulation Examples (F3-1) to (F3-51) shown in Tables 47 to 54 are used for the solder powder having the alloy composition shown in Test Example 1.
  • flux solder
  • the wett spreadability of the solder and the dewet suppression ability of the solder were evaluated.
  • the printed part formed on the mask has a quadrangular opening, and the size is 3.0 mm x 1.5 mm.
  • multiple openings of the same size are lined up at different intervals, and the intervals between the openings are 0.2-0.3-0.4-0.5-0.6-0.7-0.8. It is -0.9-1.0-1.1-1.2 mm.
  • the mask was removed, and before the reflow, it was confirmed that the solder paste was not in contact at the minimum distance of 0.2 mm between the parallel printing parts, and the reflow was performed.
  • the conditions for reflow were that after preheating at 190 ° C. for 120 seconds in an air atmosphere, the temperature was raised from 190 ° C. to 260 ° C. at a heating rate of 1 ° C./sec to perform the main heating.
  • solder dewetting suppression ability (1) Verification method An evaluation test of solder dewetting ability was conducted as follows. Each solder paste was printed on a Cu-OSP land having a length of 0.8 mm and a width of 0.8 mm, and reflow was performed. The printing thickness of the solder paste was 0.12 mm. The conditions for reflow were that after preheating at 190 ° C. for 120 seconds in an air atmosphere, the temperature rising rate was set to 1 ° C./sec, and the temperature was raised from 190 ° C. to 260 ° C. for the main heating.
  • an aliphatic polyamide was used as the polyamide
  • hexamethylenebishydroxystearic acid amide was used as the bisamide
  • p-toluamide was used as the monoamide.
  • the fluxes of Formulation Examples (F3-1) to (F3-50) are used for the solder powder having the alloy composition shown in Test Example 1, the flux of Formulation Example (F3-51) is used in each case. It was confirmed that the wettability of the solder was better and the ability to suppress dewetting was higher than when it was used.
  • the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F3-1) to (F3-50) relates to the embodiment containing the flux (F3). It is a solder paste.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 As a result of such evaluation, it was confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability were exhibited.
  • the solder paste containing each solder powder having the alloy composition of Test Examples 2 to 498 and each flux of Formulation Examples (F3-1) to (F3-50) contains a flux (F3).
  • the solder paste according to the embodiment On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • test plate was immersed 5 mm in each of the fluxes of Formulation Examples (F4-1) to (F4-58) measured in a beaker, and each flux was applied to the test plate. Subsequently, after the flux was applied, the test plate to which the flux was applied was immediately immersed in the solder bath to obtain zero cross time (sec). Subsequently, each flux of Formulation Examples (F4-1) to (F4-58) was measured 5 times, and the average value of the obtained 5 zero cross times (sec) was calculated.
  • the test conditions were set as follows.
  • an aliphatic polyamide was used as the polyamide
  • hexamethylenebishydroxystearic acid amide was used as the bisamide
  • p-toluamide was used as the monoamide.
  • the fluxes of Formulation Examples (F4-1) to (F4-57) are used for the solder powder having the alloy composition shown in Test Example 1, the flux of Formulation Example (F4-58) is used in each case. It was confirmed that the wetting speed of the solder was higher and the solder wetting property was improved as compared with the case of using it.
  • the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F4-1) to (F4-57) relates to the embodiment containing the flux (F4). It is a solder paste.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 contains a flux (F4).
  • the solder paste according to the embodiment in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • test copper plate A hollow with a diameter of 20 mm was made in the center of a phosphorylated copper plate having dimensions of 50 mm ⁇ 50 mm ⁇ 0.5 mm to form a test piece.
  • the test piece was degreased with acetone and then immersed in sulfuric acid at 65 ° C. for 1 minute to remove the oxide film on the surface. Next, it was immersed in an ammonium persulfate solution at 20 ° C. for 1 minute, washed with purified water, and dried to obtain a test copper plate.
  • the solid content of the flux of each example was measured using the method specified in JIS Z 3197: 2012 8.1.3, and an appropriate amount of flux containing 0.035 to 0.040 g as the solid content was obtained. It was added to the hollow in the center of the test copper plate. Next, the test copper plate was placed in a constant temperature and constant humidity bath set to a humidifying condition of a temperature of 40 ° C. and a relative humidity of 90%, and left in the tank for 72 hours. For each flux of each example, two test copper plates were used and one blank was added. After being left in the tank for 96 hours, it was taken out from the constant temperature and humidity chamber, and the traces of corrosion were compared with the blank under a microscope at 30 times. The ability to suppress copper plate corrosion was evaluated based on the criteria shown below.
  • an aliphatic polyamide was used as the polyamide
  • hexamethylenebishydroxystearic acid amide was used as the bisamide
  • p-toluamide was used as the monoamide.
  • the fluxes of Formulation Examples (F5-1) to (F5-61) are used for the solder powder having the alloy composition shown in Test Example 1, the flux of Formulation Example (F5-62) is used in each case. It was confirmed that the copper plate corrosion inhibitory property was enhanced as compared with the case of using it.
  • the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F5-1) to (F5-61) relates to the embodiment containing the flux (F5). It is a solder paste.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 contains a flux (F5).
  • the solder paste according to the embodiment in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • solder wetting speed (solder wettability)
  • Verification method An evaluation test of the solder wetting speed (solder wettability) was conducted as follows. According to the method of the meniscograph test, a copper plate having a width of 5 mm, a length of 25 mm and a thickness of 0.5 mm was oxidized at 150 ° C. for 1 hour to obtain a copper oxide plate as a test plate, and the Solder Checker SAT-5200 was used as a test apparatus. (Manufactured by RHESCA) was used, and a solder powder having an alloy composition shown in Test Example 1 was used as the solder, and the evaluation was performed as follows.
  • test plate was immersed 5 mm in the flux of each example measured in a beaker, and the flux was applied to the test plate. Subsequently, after the flux was applied, the test plate to which the flux was applied was immediately immersed in a solder bath having an alloy composition shown in Test Example 1 to obtain a zero cross time (sec). Subsequently, the flux of each example was measured 5 times, and the average value of the obtained 5 zero cross times (sec) was calculated.
  • the test conditions were set as follows.
  • an aliphatic polyamide was used as the polyamide
  • hexamethylenebishydroxystearic acid amide was used as the bisamide
  • p-toluamide was used as the monoamide.
  • the fluxes of Formulation Examples (F6-1) to (F6-59) are used for the solder powder having the alloy composition shown in Test Example 1, the flux of Formulation Example (F6-60) is used in each case. It was confirmed that the wetting speed of the solder was higher and the solder wetting property was better than when it was used.
  • the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F6-1) to (F6-59) relates to the embodiment containing the flux (F6). It is a solder paste.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 As a result of such evaluation, it was confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability were exhibited.
  • the solder paste containing each solder powder having the alloy composition of Test Examples 2 to 498 and each flux of Formulation Examples (F6-1) to (F6-59) contains a flux (F6).
  • the solder paste according to the embodiment On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • the solder paste was printed on the copper plate using the stainless metal mask on which the solder paste was formed, and after removing the metal mask, it was stored at room temperature of 25 ⁇ 5 ° C. and relative humidity of 50 ⁇ 10% for 10 to 20 minutes for printing. Of each pattern, the minimum interval at which all the printed solder pastes were not integrated was visually confirmed.
  • the thickness of the metal mask is 0.2 mm
  • the solder paste printing portion has a square opening
  • the size is 3.0 ⁇ 1.5 mm.
  • the opening interval L is 0.2-0.3-0.4-0.5-0.6-0.7-. It is 0.8-0.9-1.0-1.1-1.2 mm.
  • aliphatic polyamide was used as the polyamide.
  • cyclic amide oligomer a mixture of compounds represented by the following chemical formula (3) (molecular weight 300 to 1500) was used.
  • m1, m2, m3, and m4 represent the number of repetitions of the methylene group (CH 2 ).
  • p represents the number of repetitions of the unit.
  • the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F7-1) to (F7-52) is in the embodiment containing the flux (F7). This is the solder paste.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 As a result of such evaluation, it was confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability were exhibited.
  • the solder paste containing each solder powder having the alloy composition of Test Examples 2 to 498 and each flux of Formulation Examples (F7-1) to (F7-52) contains a flux (F7).
  • the solder paste according to the embodiment On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • the fluxes of Formulation Examples (F7-1) to (F7-52) were used for each of the solder powders of Test Examples 2 to 498, the fluxes of Formulation Example (F7-53) were all used. Compared with the case of using, the flux property is improved, the printing sagging of the solder paste after printing is suppressed, and the heating sagging of the solder paste due to heating at the time of soldering is suppressed. , Was confirmed. Further, when the fluxes of Formulation Examples (F7-1) to (F7-52) are used for each of the solder powders of Test Examples 2 to 498, the fluxes of Formulation Example (F7-54) are all used. It was confirmed that the heating sagging of the solder paste due to heating during soldering was suppressed as compared with the case of using.
  • thixotropic property was evaluated using a double cylindrical tube type rotational viscometer Malcom Viscometer PCU-205 (manufactured by Malcolm). The viscosity of each solder paste was sequentially measured at the rotation speed (rpm) and the measurement time (min) shown below under the condition of 25 ° C. using the double cylindrical tube type rotational viscometer.
  • solder paste Each solder paste was measured three times using a grind meter GS-2256M (manufactured by Taiyu Kikai Co., Ltd., measuring range: 0 to 100 ⁇ m). Then, the average value of the three measured values was calculated, and this average value was used as the size (grain size) of the agglomerates contained in the solder paste.
  • the surface of the grind meter is provided with a groove whose depth increases by a constant value from 0 at one end to the maximum value at the other end, and the solder paste sample is skied from the maximum depth side with a scraper. Then, linear marks and granular marks remain at the depths corresponding to the size of the agglomerates. The depth of the positions where the linear marks and granular marks are formed can be used to evaluate the precipitation and lumps of crystals in the sample of the solder paste.
  • solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F8-1) to (F8-52) and (F8-54) is the flux (F8).
  • the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F8-1) to (F8-52) and (F8-54) is the flux (F8).
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 As a result of such evaluation, it was confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability were exhibited.
  • the solder paste containing each of the solder powders having the alloy composition of Test Examples 2 to 498 and the fluxes of Formulation Examples (F8-1) to (F8-52) and (F8-54) is a flux.
  • the solder paste according to the embodiment containing (F8) On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • solder pastes when the fluxes of Formulation Examples (F9-1) to (F9-76) were used with respect to the solder powder having the alloy composition shown in Test Example 1 all had the effect of suppressing thickening. , ⁇ T stenosis, and excellent wettability were confirmed.
  • solder paste flux: solder
  • fluxes of Formulation Examples (F9-1) to (F9-76) shown in Tables 105 to 119 are used for the solder powder having the alloy composition shown in Test Example 1.
  • the powder 11:89 mass ratio
  • the void generation and the solder wetting rate (solder wettability) were evaluated.
  • solder wettability The solder wettability of the flux was evaluated according to JIS Z 3198-4: 2003. Specifically, the flux of each compounding example is applied to the portion of the surface of a copper plate having a width of 5 mm, a length of 25 mm, and a thickness of 0.5 mm, which is fired at 150 ° C. for 1 hour, from the lower end to 3 mm in the length direction with a needle tip. , It was immersed in a solder bath under the following conditions, and the zero cross time was measured.
  • Solder wettability was evaluated according to the following criteria. A: Zero cross time is 5.5 seconds or less B: Zero cross time is more than 5.5 seconds
  • an aliphatic polyamide was used as the polyamide
  • hexamethylenebishydroxystearic acid amide was used as the bisamide
  • p-toluamide was used as the monoamide.
  • the fluxes of Formulation Examples (F9-1) to (F9-74) are used for the solder powder having the alloy composition shown in Test Example 1, the flux of Formulation Example (F9-75) is used in each case. It was confirmed that the solder wettability was better than when it was used. Further, when each of the fluxes of Formulation Examples (F9-1) to (F9-74) is used for the solder powder having the alloy composition shown in Test Example 1, all of them are described in Formulation Example (F9-76). It was confirmed that the generation of voids was suppressed as compared with the case of using flux. Among these, the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F9-1) to (F9-74) is in the embodiment containing the flux (F9). This is the solder paste.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 contains a flux (F9).
  • the solder paste according to the embodiment in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • solder paste (flux: solder) when the fluxes of Formulation Examples (F10-1) to (F10-30) shown in Tables 120 to 125 are used for the solder powder having the alloy composition shown in Test Example 1.
  • the dryness, void generation, and solder wetting rate (solder wettability) were evaluated for the powder (mass ratio of 11:89).
  • solder wettability The solder wettability of the flux was evaluated according to JIS Z 3198-4: 2003. Specifically, the flux of each compounding example is applied with a needle tip to the portion of the surface of a copper plate having a width of 5 mm, a length of 25 mm, and a thickness of 0.5 mm, which is fired at 150 ° C. for 1 hour, from the lower end to 3 mm in the length direction. , It was immersed in a solder bath under the following conditions, and the zero cross time was measured.
  • Solder wettability was evaluated according to the following criteria. A: Zero cross time is 5.5 seconds or less B: Zero cross time is more than 5.5 seconds
  • the flux of Formulation Example (F10-29) is used in each case. It was confirmed that it had good drying property and better solder wettability as compared with the case of using it. Further, when each of the fluxes of Formulation Examples (F10-1) to (F10-28) is used for the solder powder having the alloy composition shown in Test Example 1, all of them are described in Formulation Example (F10-30). It was confirmed that the generation of voids was more suppressed than when the flux was used. Among these, the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F10-1) to (F10-28) is in the embodiment containing the flux (F10). This is the solder paste.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 As a result of such evaluation, it was confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability were exhibited.
  • the solder paste containing each solder powder having the alloy composition of Test Examples 2 to 498 and each flux of Formulation Examples (F10-1) to (F10-28) contains a flux (F10).
  • the solder paste according to the embodiment On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • solder paste (flux: solder) when the fluxes of Formulation Examples (F11-1) to (F11-18) shown in Tables 126 to 128 are used for the solder powder having the alloy composition shown in Test Example 1.
  • powder 11:89 mass ratio
  • thickening suppression evaluation and wettability evaluation were performed, respectively.
  • each flux of Formulation Examples (F11-1) to (F11-18) is placed on a Cu plate with an opening diameter of 6.5 mm, a numerical aperture of 4, and a mask thickness of 0. printed using a metal mask of 2 mm, in a reflow furnace, after heating under N 2, from 25 ° C. at a heating rate of 1 ° C. / sec to 260 ° C., then cooled to room temperature (25 ° C.), 4 pieces of solder A bump was formed. The appearance of the obtained solder bumps was observed using an optical microscope (magnification: 100 times), and evaluation was performed based on the following criteria. No solder particles that could not be completely melted were observed in all four solder bumps: Good solder wettability (A) Solder particles that could not be completely melted were observed in one or more of the four solder bumps: poor solder wettability (B).
  • Metal inactivating agents A to H were used as the hindered phenolic metal inactivating agents.
  • Metal inactivating agent A Reagent name: Bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [Ethylene bis (oxyethylene)]; CAS No. 36443-68-2.
  • Metal inactivating agent B Reagent name: N, N'-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide]; CAS No. 23128-74-7.
  • Metal inactivating agent C Reagent name: 1,6-Hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; CAS No. 35074-77-2.
  • Metal inactivating agent D Reagent name: 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol]; CAS No. 77-62-3.
  • Metal inactivating agent E Reagent name: 2,2'-methylenebis (6-tert-butyl-p-cresol); CAS No. 119-47-1.
  • Metal inactivating agent F Reagent name: 2,2'-methylenebis (6-tert-butyl-4-ethylphenol); CAS No. 88-24-4.
  • Metal inactivating agent G Reagent name: N- (2H-1,2,4-triazole-5-yl) salicylamide; CAS No. 36411-52-6.
  • Methodal inactivating agent H Reagent name: N, N'-bis [2- [2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethylcarbonyloxy] ethyl] oxamide; CAS No. 70331-94-1.
  • the fluxes of Formulation Examples (F11-1) to (F11-17) are used for the solder powder having the alloy composition shown in Test Example 1, the flux of Formulation Example (F11-18) is used in each case. It was confirmed that the effect of suppressing thickening was enhanced as compared with the case of using it.
  • the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F11-1) to (F11-17) relates to the embodiment containing the flux (F11). It is a solder paste.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 As a result of such evaluation, it was confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability were exhibited.
  • the solder paste containing each solder powder having the alloy composition of Test Examples 2 to 498 and each flux of Formulation Examples (F11-1) to (F11-17) contains a flux (F11).
  • the solder paste according to the embodiment On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • each flux of Formulation Examples (F12-1) to (F12-8) is placed on a Cu plate with an opening diameter of 6.5 mm, a numerical aperture of 4, and a mask thickness of 0. printed using a metal mask of 2 mm, in a reflow furnace, after heating under N 2, from 25 ° C. at a heating rate of 1 ° C. / sec to 260 ° C., then cooled to room temperature (25 ° C.), 4 pieces of solder A bump was formed. The appearance of the obtained solder bumps was observed using an optical microscope (magnification: 100 times), and evaluation was performed based on the following criteria. No solder particles that could not be completely melted were observed in all four solder bumps: Good solder wettability (A) Solder particles that could not be completely melted were observed in one or more of the four solder bumps: poor solder wettability (B).
  • Metal inactivating agents A to E were used as the nitrogen-containing compound-based metal inactivating agents.
  • Metal inactivating agent A Reagent name: N- (2H-1,2,4-triazole-5-yl) salicylamide; CAS No. 36411-52-6
  • Metal inactivating agent B Reagent name: Bis dodecanedioate [N2- (2-hydroxybenzoyl) hydrazide]; CAS No.
  • Metal inactivating agent F Reagent name: Bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [Ethylene bis (oxyethylene)]; CAS No. 36443-68-2
  • the fluxes of Formulation Examples (F12-1) to (F12-7) are used for the solder powder having the alloy composition shown in Test Example 1, the flux of Formulation Example (F12-8) is used in each case. It was confirmed that the effect of suppressing thickening was enhanced as compared with the case of using it.
  • the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of Formulation Examples (F12-1) to (F12-7) relates to the embodiment containing the flux (F12). It is a solder paste.
  • the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498 contains a flux (F12).
  • the solder paste according to the embodiment in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, at least one of the thickening suppressing effect, the narrowing of ⁇ T, and the excellent wettability was inferior.
  • solder paste which is less likely to change with time such as an increase in viscosity, has excellent wettability, has high mechanical properties, and can further enhance various properties.
  • the wetting speed of the solder is improved, the corrosion of the metal surface (for example, a copper plate) of the object to be joined is suppressed, and the printability is improved.
  • a flux for solder paste which can further enhance various characteristics such as void suppression.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

La présente invention utilise une pâte à braser qui contient une poudre de brasage tendre spécifique et un flux spécifique. Cette poudre de brasage tendre contient un alliage de brasage tendre qui a une composition d'alliage comprenant 10 ppm en masse ou plus et moins de 40 ppm en masse d'As et 0 à 10 000 ppm en masse de Bi, 0 à 5100 ppm en masse de Pb et/ou 0 à 3 000 ppm en masse de Sb, le reste comprenant du Sn, et l'alliage de brasage tendre répondant à la formule (1) et à la formule (2). Formule (1) : 300 ≤ 3As + Sb + Bi + Pb Formule (2) : 0,1 ≤ {(3As + Sb)/(Bi + Pb)}×100 ≤ 200. Dans la formule (1) et la formule (2), As, Sb, Bi et Pb représentent les valeurs de teneur, en ppm en masse, de ces constituants dans la composition de l'alliage.
PCT/JP2020/020549 2019-05-27 2020-05-25 Pâte à braser et flux pour pâte à braser WO2020241574A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11114691A (ja) * 1997-10-07 1999-04-27 Uchihashi Estec Co Ltd はんだ合金
JP2006016681A (ja) * 2004-07-05 2006-01-19 Nosaku:Kk 金属製器ならびに該金属製器に用いる金属からなる金属製品およびその製造方法
JP2006181637A (ja) * 2004-12-03 2006-07-13 Tamura Seisakusho Co Ltd フラックス及びこれを用いたはんだ付方法
JP2013214704A (ja) * 2012-03-06 2013-10-17 Mitsubishi Materials Corp はんだバンプの製造方法
JP2015098052A (ja) * 2013-10-16 2015-05-28 三井金属鉱業株式会社 半田合金及び半田粉

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101305801B1 (ko) * 2012-05-10 2013-09-06 센주긴조쿠고교 가부시키가이샤 음향용 땜납 합금
SG11201401482UA (en) * 2012-10-09 2014-06-27 Alpha Metals Lead-free and antimony-free tin solder reliable at high temperatures
EP3103565B1 (fr) * 2014-02-04 2018-10-24 Senju Metal Industry Co., Ltd BILLE DE Cu, BILLE À NOYAU EN Cu, JOINT À BRASURE, PÂTE À BRASER ET MOUSSE DE BRASURE
JP6047214B1 (ja) * 2015-11-02 2016-12-21 田中電子工業株式会社 ボールボンディング用貴金属被覆銅ワイヤ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11114691A (ja) * 1997-10-07 1999-04-27 Uchihashi Estec Co Ltd はんだ合金
JP2006016681A (ja) * 2004-07-05 2006-01-19 Nosaku:Kk 金属製器ならびに該金属製器に用いる金属からなる金属製品およびその製造方法
JP2006181637A (ja) * 2004-12-03 2006-07-13 Tamura Seisakusho Co Ltd フラックス及びこれを用いたはんだ付方法
JP2013214704A (ja) * 2012-03-06 2013-10-17 Mitsubishi Materials Corp はんだバンプの製造方法
JP2015098052A (ja) * 2013-10-16 2015-05-28 三井金属鉱業株式会社 半田合金及び半田粉

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