Solder alloy, solder powder, solder paste and solder joint using these

Abstract

Solder alloy comprising an alloy composition containing at least one of: As: 0.0025 to 0.0300 wt.%, Pb: more than 0 wt.% and 0.5100 wt.% or less, and Sb: more than 0 wt.% and 0.3000 wt.% or less, and furthermore Bi: more than 0 wt.% and 1.0000 wt.% or less, optionally at least one of Ag 0 to 4 wt.% and Cu: 0 to 0.9 wt.%, as well as a residue of Sn and unavoidable impurities, wherein the following expression (1) and expression (2) are satisfied: 0.0275 ≤ 2As + Sn + Bi + Pb 0.01 ≤ (2As + Sb) / (Bi + Pb) ≤ 10.00 where As, Sb, Bi and Pb in expression (1) and expression (2) each have a content (wt.%) in the Represent alloy composition.

Description

technical field

[0001] The present invention relates to a solder alloy, a solder powder, a solder paste which suppresses paste change with time, has excellent wettability and shows a small temperature difference between liquidus temperature and solidus temperature, and relates to a solder joint using the same. State of the art

[0002] In recent years, demands for miniaturization and higher performance in an electronic device with a solder joint such as a B. a CPU (Central Processing Unit) increased. Accordingly, it has become necessary to miniaturize a printed substrate and an electrode of an electronic device. The electronic device is connected to the printed substrate via the electrode. For this reason, a solder joint connecting them must also be downsized in accordance with the miniaturization of the electrode.

[0003] In order to connect an electronic device and a printed substrate via such a fine electrode, solder paste is usually used. The solder paste is applied to the electrode of the printed substrate by printing or the like. Printing of a solder paste is performed in the following manner: a metal mask with an opening provided is placed on a printed substrate; a squeegee is moved while being pressed against the metal mask; this co-deposits the solder paste onto the electrode on the printed substrate through the opening of the metal mask. Then, the electronic component is mounted on the solder paste printed on the printed substrate and held by the solder paste until the soldering is completed.

[0004] For example, if it subsequently takes several hours to insert the electronic component into a reflow oven after mounting it on the printed substrate, the solder paste may not be able to absorb the solder paste due to the change in the solder paste over time retain the shape formed at the time of printing. This can lead to a tilting or lopsided position or a bad connection of the electronic component. Furthermore, in the case of purchased solder paste, the solder paste is not usually completely consumed in one printing operation. For this reason, the solder paste must retain the original proper viscosity at the time of manufacture so as not to affect the printing performance.

[0005] In recent years, as the miniaturization of the electrode has progressed, the printing area of ​​the solder paste has also decreased. As a result, the period of time until the purchased solder paste is used up is also extended. The solder paste is obtained by renting a solder powder and a flux. If the storage time of the solder paste is long, its viscosity may increase depending on the storage conditions. As a result, the solder paste may no longer have the original printing performance at the time of purchase.

[0006] Under these conditions, for example, Patent Document 1 discloses a solder alloy containing Sn and one or two or more selected from the group consisting of Ag, Bi, Sb, Zn, In and Cu and including a predetermined amount of As to suppress a change in solder paste with the lapse of time time to suppress. The patent document discloses the result that the viscosity after two weeks at 25°C is less than 140% compared to the original viscosity at the time of manufacture BibliographyPatent Document

[0007] Patent Document 1: Patent Publication JP-A-2015-98052 SummaryTechnical issue

[0008] As described above, the invention according to Patent Document 1 is a solder alloy that can selectively contain six elements other than Sn and As. Further, the patent document discloses the result that a high As content leads to inferior meltability.

[0009] Here, the meltability evaluated in Patent Document 1 is considered to be equivalent to the wettability of the molten solder. The fusibility disclosed in the patent document is evaluated by the presence or absence of incompletely melted solder powder as determined by observing the external appearance of the melted material with a microscope. This is because the high wettability of the molten solder makes it difficult for incompletely melted solder powder to remain.

[0010] In general, in order to improve the wettability of a molten solder, it is necessary to use a highly active flux. Regarding the flux described in Patent Document 1, it is considered that deterioration in wettability by As can be suppressed only by using a highly active flux. However, the use of a highly active flux will increase the rate of viscosity increase of the flux. In view of the specification of Patent Document 1, suppressing the increase in a viscosity increase rate requires an increase in As content. In order for the solder paste described in Patent Document 1 to have both a still lower rate of viscosity increase and excellent wettability, it is necessary to further increase the activity of the flux and the As content therein, but this may result in a vicious circle.

[0011] Recently, a solder paste is required to maintain stable performance over long periods of time regardless of the application and storage environment and to have higher wettability due to further miniaturization of solder joint. When trying to meet the recent requirements with the solder paste described in Patent Document 1, a vicious circle is inevitable.

[0012] Furthermore, in order to connect fine electrodes, for example, it is necessary to improve the mechanical properties of the solder joint. Depending on the elements, increasing the content leads to an increase in the liquidus temperature, increasing the difference between the liquidus temperature and the solidus temperature. This leads to segregation upon solidification, leading to the formation of a non-uniform alloy structure. When a brazing alloy has such an alloy structure, mechanical properties such as tensile strength are lowered and the brazing alloy is easily broken by an external stress. This problem has become even more apparent with the recent miniaturization of the electrode

[0013] an object of the present invention is to provide a solder alloy, a solder powder and a solder paste which suppress change of the paste with time, have excellent wettability, have a small temperature difference between the liquidus temperature and the solidus temperature and have high mechanical properties and further to provide a solder joint using these. the solution of the problem

[0014] In order to improve both the suppression of the paste change with time and the excellent wettability, it is necessary to avoid a vicious circle due to the use of a highly active flux and an increase in the As content. The present inventors focused on the alloy composition of a solder powder, and made careful study to achieve a balance between suppression of change of paste with time and excellent wettability regardless of the kind of flux.

[0015] First, the present inventors conducted a study on a solder powder comprising, as a basic composition, an Sn, SnCu, SnAgCu solder alloy which is commonly used as a solder alloy and also contains As. Then, the present inventors investigated the reason of suppression of the change of the solder paste with time and examined a lot of the As content.

[0016] The reason why the viscosity of the solder paste increases with the lapse of time is considered to be that the solder powder and the flux react with each other. A comparison between the results of Example 4 and Comparative Example 2 in Table 1 of Patent Document 1 shows the result that an As content of more than 100 ppm by mass leads to a lower rate of viscosity increase. In view of this connection, the present inventors thought that considering the effect of suppressing the change of the paste with time (hereinafter referred to as “thickening suppression effect” as appropriate), it would be appropriate to further increase the As content. It has been confirmed that as the As content increases, the thickening suppressing effect increases slightly depending on the As content, but if the As content is too high, the wettability of the brazing alloy is deteriorated.

[0017] Under the circumstances, the present inventors recognized the need to add an element showing a thickening suppressing effect in addition to As and searched for various elements. The present inventors found that Sb, Bi and Pb exhibited the same effect as As. Although the reason for this is not clear, it can be assumed as follows.

[0018] The thickening suppressing effect is exhibited by suppressing a reaction with the flux. Accordingly, the element with a low reactivity with the flux is an element with a low ionization tendency. In general, alloy ionization is considered based on the ionization tendency of an alloy composition, i.e. the standard electrode potential. For example, a SnAg alloy containing Ag, which is noble relative to Sn, is less likely to be ionized than Sn. For this reason, the alloy containing an element nobler than Sn is less likely to be ionized and is considered to have a high thickening suppressing effect in the solder paste.

[0019] In Patent Document 1, Bi, Sb, Zn, and In are exemplified as equivalent elements besides Sn, Ag, and Cu. In and Zn are baser elements than Sn in terms of ionization tendency. In other words, Patent Document 1 describes that even if an element less noble than Sn is added, the thickening suppression effect can be obtained. For this reason, it is believed that the solder alloy containing an element selected according to the ionization tendency can provide the thickening suppressing effect equal to or higher than the thickening suppressing effect of the solder alloy described in Patent Document 1. Furthermore, as described above, an increase in the As content leads to a deterioration in wettability.

[0020] The present inventors made a detailed study of Bi and Pb to find a thickening suppressing effect. Bi and Pb lower the liquidus temperature of the solder alloy and therefore improve the wettability of the solder alloy when the heating temperature of the solder alloy is constant. However, the solidus temperature drops significantly depending on the content. Because of this, ΔT, the temperature difference between the liquidus temperature and the solidus temperature, becomes too large. Too large ΔT leads to segregation during solidification, resulting in a reduction in mechanical properties such as mechanical strength. The phenomenon in which ΔT increases appears remarkably when Bi and Pb are added at the same time. Accordingly, it was also found that strict control is necessary.

[0021] Further, the present inventors conducted a re-examination of the Bi content and the Pb content in order to improve the wettability of the brazing alloy, and found that an increase in the content of the elements increases ΔT. Therefore, the inventors selected Sb as an element that exhibits a noble ionization tendency relative to Sn and also as an element that improves the wettability of the solder alloy, and defined the allowable range of the Sb content, and then made a detailed study of a relationship between the respective contents of As, Bi, Pb including Sb and the respective Sb contents therein. As a result, the present inventors accidentally found that when the contents of the elements satisfy a prescribed comparative expression, no practical problems are caused in terms of excellent thickening suppressing effect, wettability and reduction of ΔT, thereby completing the present invention.

[0022] The present invention obtained from the findings is as follows: (1) A brazing alloy comprising an alloy composition containing at least one of: As: 25 to 300 ppm by mass, Pb: more than 0 ppm by mass and 5100 ppm by mass or less, and SB: more than 0 ppm by mass and 3000 ppm by mass or less, and further Bi: more than 0 ppm by mass and 10000 ppm by mass or less, and a balance containing Sn, wherein the following expression (1) and expression (2) are satisfied: 275 ≤ 2 As + Sn + Bi + Pb <?page 5=""?> 0,01 ≤ ( 2 As + Sb ) / ( Bi + Pb ) ≤ 10,00 wherein As, Sb, Bi and Pb in the expression (1) and expression (2) each represents a content (ppm by mass) in the alloy composition. (2) The solder alloy according to (1), wherein the alloy composition further satisfies the following expression (1a): 275 ≤ 2 As + Sb + Bi + Pb ≤ 2 5200 where As, Sb, Bi and Pb in the expression (1a) each represents a content (ppm by mass) in the alloy composition. (3) The brazing alloy according to (1), wherein the alloy composition further satisfies the following expression (1a), 275 ≤ 2 As + Sb + Bi + Pb ≤ 5300 where As, Bi and Pb in the expression (1b) each represents a content (ppm by mass) in the alloy composition. (4) The brazing alloy according to any one of (1) to (3), wherein the alloy composition further satisfies the following expression (2a), 0,31 ≤ ( 2 As + Sb ) / ( Bi + Pb ) ≤ 10,00 where As, Sb, Bi and Pb in the expression (2a) each represents a content (ppm by mass) in the alloy composition. (5) The alloy composition according to any one of (1) to (4), wherein the alloy composition further comprises at least one of Ag: 0 to 4% by mass and Cu: 0 to 0.9% by mass. (6) A solder powder includes the solder alloy according to any one of (1) to (5). (7) A solder paste comprising the solder powder according to (6). (8) The solder paste according to (7), further comprising a zirconia powder. (9) The solder paste according to (8), comprising the zirconia powder in an amount of 0.05 to 20.0% by mass based on a total mass of the solder paste. (10) A brazed joint comprising the brazing alloy according to any one of (1) to (5). Description of the embodiments

[0023] The present invention is explained in more detail below. In the present specification, the term "ppm" for the solder alloy composition means "ppm by mass" unless otherwise specified. “%” stands for “mass” unless otherwise noted. Alloy composition As: 25 ppm to 300 ppm

[0024] As is an element capable of suppressing changes in solder paste with the lapse of time. As is an element having a low reactivity with a flux and is noble compared to Sn, and therefore can presumably exhibit the thickening suppressing effect. If the As content is less than 25 ppm, the thickening suppressing effect cannot be exhibited sufficiently. The lower limit of the As content is 25 ppm or more, preferably 50 ppm or more, and more preferably 100 ppm or more. On the other hand, too high an As content leads to a deterioration in the wettability of the solder alloy. The upper limit of the As content is 300 ppm or less, preferably 250 ppm or less, and more preferably 200 ppm or less At least one of Pb: more than 0 ppm by mass and 5100 ppm by mass or less, and Sb: more than 0 ppm by mass and 3000 ppm by mass or less, and Bi: more than 0 ppm by mass and 10000 ppm by mass Or less

[0025] Sb is an element low in reactivity with a flux and exhibits the thickening suppressing effect. When the solder alloy according to the present invention comprises Sb, the lower limit of the Sb content is more than 0 ppm, preferably 25 ppm or more, more preferably 50 ppm or more, still more preferably 100 ppm or more, and particularly preferably 300 ppm or more. On the other hand, too high a Sb content leads to deterioration in wettability. For this reason, it is necessary to adjust the Sb content to an appropriate level. The upper limit of the Sb content is 3000 ppm or less, preferably 1150 ppm or less, and more preferably 500 ppm or less.

[0026] Bi and Pb are each an element with low reactivity with a flux and exhibit the thickening suppressing effect like Sb. Further, Bi and Pb are each an element that lowers the liquidus temperature of a solder alloy and the viscosity of a molten solder and can therefore cause the deterioration in wettability ace

[0027] When at least one element of Pb, and Sb and Bi is present, deterioration of wettability by As can be suppressed. When the solder alloy according to the present invention comprises Bi, the lower limit of the Bi content is more than 0 ppm, preferably 25 ppm or more, more preferably 50 ppm or more, even more preferably 75 ppm or more, particularly preferably 100 ppm or more and am most preferably 250 ppm or more. The lower limit of the Pb content is more than 0 ppm, preferably 25 ppm or more, more preferably 50 ppm or more, still more preferably 75 ppm or more, particularly preferably 100 ppm or more, and most preferably 250 ppm or more

[0028] On the other hand, too high a content of the elements leads to a significant reduction in the solidus temperature. For this reason, ΔT of the temperature difference between the liquidus temperature and the solidus temperature becomes too large. Too large ΔT leads to the precipitation of a refractory crystal phase with a small content of Bi or Pb during the solidification process of the molten solder. Accordingly, Bi or Pb is concentrated in the liquid phase. Thereafter, when the temperature of the molten solder is further lowered, the low-melting point crystal phase having a high concentration of Bi or Pb segregates. For this reason, the mechanical strength of the brazing alloy or the like deteriorates, resulting in lower reliability. In particular, the crystal phase with a high Bi concentration is hard and brittle. For this reason, when the crystal phase is segregated in the solder alloy, the reliability is remarkably lowered.

[0029] From such a point of view, when the solder alloy according to the present invention contains Bi, the upper limit of the Bi content is 10000 ppm or less, preferably 1000 ppm or less, more preferably 600 ppm or less, and still more preferably 500 ppm or less. The upper limit of the Pb content is 5100 ppm or less, preferably 5000 ppm or less, more preferably 1000 ppm or less, still more preferably 850 ppm or less, and particularly preferably 500 ppm or less. expression (1)

[0030] The solder alloy according to the present invention is required to satisfy the following expression (1). 275 ≤ 2 As + Sn + Bi + Pb

[0031] In the expression (1), As, Sb, Bi and Pb each represents the content (ppm by mass) in the alloy composition.

[0032] As, Sb, Bi and Pb are the elements exhibiting the thickening suppressing effect. Thickening suppression requires a total level of these of 275 ppm or more. The reason why the As content is doubled in expression (1) is that As provides a larger thickening suppressing effect than Sb, Bi or Pb.

[0033] When the expression (1) is less than 275, the thickening suppressing effect is not exerted sufficiently. The lower limit of expression (1) is 275 or more, preferably 350 or more, and more preferably 1200 or more. On the other hand, the upper limit of (1) has no particular limitation from the viewpoint of the thickening suppressing effect, and is preferably 25,200 or less, more preferably 10,200 or less, still more preferably 5,300 or less, and particularly preferably 3,800 or less from the viewpoint of adjusting ΔT within the appropriate range .

[0034] By appropriately selecting the upper limit and the lower limit from the preferred items, the following expressions (1a) and (1b) are obtained. 275 ≤ 2 As + Sn + Bi + Pb ≤ 25200 275 ≤ 2 As + Sn + Bi + Pb ≤ 5300

[0035] In the expressions (1a) and (1b), As, Sb, Bi and Pb each represents the content (ppm by mass) in the alloy composition. expression (2)

[0036] The solder alloy according to the present invention is required to satisfy the following expression (2). 0,01 ≤ ( 2 As + Sb ) / ( Bi + Pb ) ≤ 10,00

[0037] In the expression (2), As, Sb, Bi and Pb each represents the content (ppm by mass) in the alloy composition.

[0038] A high content of As and Sb leads to a deterioration in wettability of a solder alloy. On the other hand, Bi and Pb suppress the deterioration of wettability by inclusion of As. However, too high a content of these leads to an increase in ΔT. For this reason, strict control is necessary. In particular, in the alloy composition containing Bi and Pb simultaneously, ΔT tends to increase. In view of this, if an attempt is made to increase the contents of Bi and Pb in order to excessively improve the wettability, ΔT is increased. On the other hand, if an attempt is made to increase the As or Sb content in order to improve the thickening suppressing effect, the wettability is deteriorated. Therefore, in the present invention, the compositions are classified into a group of As and Sb and a group of Bi and Pb. When the total amount of the two groups is within a certain range, the thickening suppressing effect, the reduction of ΔT and the wettability are satisfied at the same time.

[0039] When the expression (2) is less than 0.01, the total content of Bi and Pb becomes relatively larger than the total content of As and Pb. For this reason, ΔT is increased. The lower limit of expression (2) is 0.01 or more, preferably 0.02 or more, more preferably 0.41 or more, still more preferably 0.90 or more, particularly preferably 1.00 or more, and most preferably 1.40 or more. On the other hand, when expression (2) exceeds 10.00, the total content of As and Sb becomes relatively larger than the total content of Bi and Pb. For this reason, the wettability is deteriorated. The upper limit of (2) is 10.00 or less, preferably 5.33 or less, more preferably 4.50 or less, even more preferably 2.67 or less, even more preferably 4.18 or less, and most preferably 2, 30 or less.

[0040] The denominator of expression (2) is "Bi+Pb" and expression (2) does not apply if these are not included. In particular, it is found that the brazing alloy according to the present invention necessarily contains at least one of Bi and Pb. The alloy composition not containing Bi and Pb is inferior in wettability as described above.

[0041] The one obtained by appropriately selecting the upper and lower limits from the preferred aspects is the following expression (2a). 0,31 ≤ ( 2 As + Sb ) / ( Bi + Pb ) ≤ 10,00

[0042] In the expression (2a), Bi and Pb each represents the content (ppm by mass) in the alloy composition.

[0043] (4) At least one of Ag: 0% to 4% and Cu: 0% to 0.9%

[0044] Ag is a specific element that Ag 3 Sn can form at the crystal interface and improves the reliability of the solder alloy. Further, Ag is an element nobler in ionization tendency than Sn, and coexists with As, Pb, and Bi, thereby promoting their thickening suppressing effect. The Ag content is preferably 0% to 4%, more preferably 0.5% to 3.5%, and still more preferably 1.0% to 3.0%.

[0045] Cu is a specific element that can improve the joint strength of the solder joint. Further, Cu is an element nobler in ionization tendency than Sn, and coexists with As, Pb, and Bi, thereby promoting their thickening suppressing effect. The Cu content is preferably 0% to 0.9%, more preferably 0.1% to 0.8%, and still more preferably 0.2% to 0.7%. Rest: Sn

[0046] The balance of the solder alloy according to the present invention is Sn. Besides these elements, unavoidable impurities may be contained. Even if inevitable impurities are contained, the above effects are not impaired. As will be described later, the introduction of the elements which should not be contained as unavoidable impurities in the present invention does not impair the above effect. When the In content is too high, ΔT is increased. For this reason, In will not affect the above effect as long as the content is 1000ppm or less. solder powder

[0047] The solder powder according to the present invention is used in a solder paste described below.

[0048] The solder powder of the present invention preferably corresponds to the size satisfying characters 1 to 8 (particle size distribution) in the powder size classification (Table 2) in JIS Z 3284-1:2014. Even more preferred is a size that satisfies 4 to 8 characters (particle size distribution), and more preferable is a size that satisfies 5 to 8 characters (particle size distribution). When the particle size satisfies the conditions, the surface area of ​​the powder is not too large, so the increase in viscosity can be suppressed, and the aggregation of a fine powder can be suppressed, which can suppress the increase in viscosity. For this reason, soldering to a finer component becomes possible. solder paste

[0049] The solder paste according to the present invention contains the above solder powder and a flux.

[0050] (1) The flux used in the solder paste of the component of the flux includes any one or a combination of two or more of an organic acid, amine, amine hydrohalic acid salt, organic halogen compound, thixotropic agent, rosin, solvent, surfactant, base agent, high molecular weight compounds, silane coupling agent and dye

[0051] This consists of any one of an organic acid, an amine, an amine hydrohalide salt, an organic halogen compound, a rosin, a solvent, a surfactant, a base agent, a polymer compound, a silane coupling agent and a dye, or a combination of two or more of the above substances.

[0052] As organic acids, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimer acids, propionic acid, 2,2-bis(hydroxymethyl)propionic acid, tartaric acid, maleic acid, glycolic acid, diglycolic acid, thioglycolic acid, dithioglycolic acid, stearic acid, 12-hydroxystearic acid, palmitic acid and oleic acid can be mentioned.

[0053] Amines that can be used are 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 trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6 -[2'-undecylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine-isocyanuric acid adducts, 2-phenylimidazole-isocyanuric acid adducts, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole in, 2-phenylimidazoline, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine-isocyanuric acid adducts, 2,4-diamino-6-methacryloyloxyethyl-s- triazine, epoxy-imidazole adducts, 2-methylbenzimidazole, 2-octylbenzimidazole, 2-pentylbenzimidazole, 2-(1-ethylpentyl)benzimidazole, 2-nonylbenzimidazole, 2-(4-thiazolyl)benzimidazole, benzimidazole, 2-(2'- Hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-Hydroxy-3',5'-di- tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol], 6 -(2-Benzotriazolyl)-4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebisphenol, 1,2,3-benzotriazole, 1-[N,N-bis(2 -ethylhexyl)aminomethyl]benzotriazole, carboxybenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol, 1-(1',2'-dicarboxyethyl)benzotriazole, 1-(2,3-dicarboxypropyl)benzotriazole, 1-[(2-ethylhexyla mino)methyl]benzotriazole, 2,6-bis[(1H-benzotriazol-1-yl)methyl]-4-methylphenol, 5-methylbenzotriazole and 5-phenyltetrazole or the like can be mentioned.

[0054] The amine hydrohalide salt is a compound obtained from a reaction between an amine and a hydrogen halide. As the amine, there can be mentioned ethylamine, ethylenediamine, triethylamine, methylimidazole and 2-ethyl-4-methylimidazole, or the like. As the hydrogen halide, hydrides of chlorine, bromine and iodine can be mentioned.

[0055] As organic halogen compounds, 1-bromo-2-butanol, 1-bromo-2-propanol, 3-bromo-1-propanol, 3-bromo-1,2-propanediol, 1,4-dibromo-2-butanol, 1, 3-dibromo-2-propanol, 2,3-dibromo-1-propanol, 2,3-dibromo-1,4-butanediol and 2,3-dibromo-2-butene-1,4-diol or the like can be mentioned.

[0056] As the thixotropic agent, there can be mentioned a wax type thixotropic agent and an amide type thixotropic agent. Examples of a wax-type thixotropic agent may include, for example, hydrogenated castor oil. As the amide-type thixotropic agent, there can be used amide laurate, amide palmitate, amide stearate, amide behenate, amide hydroxystearate, saturated fatty acid amide, oleic acid amide, erucic acid amide, unsaturated fatty acid amide, p-toluenemethanamide, aromatic amide, methylenebisstearic acid amide, ethylenebislauric acid amide, ethylenebishydroxystearic acid amide, saturated fatty acid bisamide, methylenebisoleic acid amide, unsaturated fatty acid bisamide, m-xylylenebisstearic acid amide, aromatic bisamide, saturated fatty acid polyamide, unsaturated fatty acid polyamide, aromatic polyamide substituted amide, methylol stearic acid amide, methylolamide and fatty acid ester amide or the like.

[0057] As the base, polyethylene glycol and rosin or the like can be mentioned. Examples of the rosin may include, for example, raw rosin such as rosin, wood rosin and tall oil rosin, and derivatives obtained from the raw material rosin. Examples of the derivative may include purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin and α,β-unsaturated carboxylic acid modified products (such as acrylated rosin, maleated rosin and fumarated rosin) and purified products, hydrides and disproportionated products of the polymerized rosin and purified Products, hydrides and disproportionated products of the α,β-unsaturated carboxylic acid modified product include, and two or more of them can be used. Further, in addition to the rosin type resins, at least one or more resins selected from terpene resin, modified terpene resin, terpene phenolic resin, modified terpene phenolic resin, styrene resin, modified styrene resin, xylene resin and modified xylene resin may be contained. As the modified terpene resin, aromatic modified terpene resin, hydrogenated terpene resin, hydrogenated aromatic modified terpene resin or the like can be used. As the modified terpene phenolic resin, hydrogenated terpene phenolic resin or the like can be used. As the modified styrene resin, styrene-acrylic resin, styrene-maleic acid resin or the like can be used. As the modified xylene resin, there can be used phenol-modified xylene resin, alkylphenol-modified xylene resin, resol-type phenol-modified xylene resin, polyol-modified xylene resin, polyoxyethylene-added xylene resin, or the like

[0058] As the solvent, water, alcohol type solvents, glycol ether type solvents, terpineols and the like can be used. As the alcohol type solvent, 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-hexyne-2,5-diol, 2,3-dimethyl-2,3-butanediol, 1,1,1-tris(hydroxymethyl)ethane, 2-ethyl-2-hydroxymethyl-1 ,3-propanediol, 2,2'-oxybis(methylene)bis(2-ethyl-1,3-propanediol), 2,2-bis(hydroxymethyl)-1,3-propanediol, 1,2,6-trihydroxyhexane, Bis[2,2,2-tris(hydroxymethyl)ethyl]ether, 1-ethynyl-1-cyclohexanol, 1,4-cyclohexanediol, 1,4-cyclohexane dimethanol, erythritol, threitol, guaiacol glycerol ether, 3,6-dimethyl-4- octyne-3,6-diol and 2,4,7,9-tetramethyl-5-decyne-4,7-diol and the like can be mentioned. As the glycol ether type solvent, there can be mentioned 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 and the like.

[0059] As the surface active agent, there can be mentioned polyoxyalkylene acetylene glycols, polyoxyalkylene glyceryl ether, polyoxyalkylene alkyl ether, polyoxyalkylene ester, polyoxyalkylene alkylamine and polyoxyalkylene alkylamide and the like. flux content

[0060] The content of the flux is preferably 5% to 95%, more preferably 5% to 15% based on the total mass of the solder paste. When the content is in this range, the thickening suppressing effect by the solder powder is sufficiently exhibited. zirconia powder

[0061] The solder paste according to the present invention preferably contains a zirconia powder. Zirconia can suppress an increase in the viscosity of the paste with the lapse of time. It is believed that by including zirconium oxide, the oxide layer thickness of the solder powder surface can be maintained in the state before it was filled with the flux. Although the details are not known, the following is believed. In general, the active component of the flux has low activity even at normal temperatures. For this reason, the surface oxide layer of the solder powder is reduced in thickness by reduction, resulting in aggregation of the powder. Thus, by adding a zirconia powder to the solder paste, the active component of the flux can preferentially react with the zirconia powder. Accordingly, the oxide film thickness is presumably kept to a level that prevents aggregation of the oxide film on the solder powder surface.

[0062] In order to exhibit such advantageous effects sufficiently, the content of the zirconia powder in the solder paste is preferably 0.05% to 20.0% based on the total mass of the solder paste. When the content is 0.05% or more, the beneficial effects can be exerted. When the content is 20.0% or less, the content of the metal powder can be secured and the thickening suppressing effect can be exerted. The content of the zirconia is preferably 0.05% to 10.0%, and the more preferable content is 0.1% to 3%

[0063] The particle size of the zirconia powder in the solder paste is preferably 5 μm or less. When the particle size is 5 µm or less, the printability of the paste can be maintained. Although the lower limit has no particular limitation, the lower limit may be 0.5 µm or more. For the particle size, an SEM photograph of the zirconia powder was taken, and the projected equivalent circular diameters were determined by image analysis for the respective 0.1 µm or more powders, and the average value of these was adopted.

[0064] The form of the zirconia is not particularly limited. When the mold has an irregular shape, the contact area with the flux is large, thereby producing the thickening suppressing effect. A spherical shape provides good flowability, resulting in excellent printability as a paste. The shape can be appropriately selected depending on the desired properties. Method of making the solder paste

[0065] The solder paste of the present invention is prepared by any method well known in the art. First, known methods such as a dropping method in which a molten solder is added dropwise to generate particles, a spraying method in which centrifugal atomization is performed, and a method in which a loose solder is crushed can be used to prepare a solder powder. In the dropping method or the spraying method, the dropwise addition or the spraying is preferably carried out in an inert atmosphere or a solvent to obtain a particle form. Then, the respective components are mixed under heating, whereby a flux is prepared. Into the resulting flux, the solder powder and, in some cases, a zirconia powder are introduced and mixed with stirring. As a result, the solder paste can be manufactured solder connection

[0066] The solder connection according to the present invention is suitable for connection between an IC chip and the substrate (interposer) in a semiconductor package or for connection between a semiconductor package and a circuit board. The term "soldered connection" represents the connection section of the electrode. additional

[0067] The solder alloy according to the present invention can also be used in a wire form in addition to the powder form described above

[0068] The method for producing a solder joint according to the present invention can be carried out according to the usual method.

[0069] The method of making a solder joint according to the present invention may be a conventional method.

[0070] The connection method according to the invention using the solder paste can, for. B. be carried out with a reflow process after the normal process. The melting temperature of the brazing alloy for performing the reflow brazing process may generally be a temperature higher than the liquidus temperature by about 20°C. Further, when joining with the brazing alloy of the present invention, the cooling rate for solidification is preferably considered from the viewpoint of miniaturization of the structure. For example, the solder joint is cooled at a cooling rate of 2°C / s to 3°C / s or more. Other joining conditions can be appropriately adjusted according to the alloy composition of the brazing alloy.

[0071] The brazing alloy according to the present invention can produce a low α-ray dose alloy by using a low α-ray dose material as a starting material. When such a low α-ray dose alloy is used to form the bump around the memory, it becomes possible to suppress a software error. examples

[0072] The present invention is illustrated by the following examples. However, the present invention is not limited to the following examples.

[0073] A solder paste was prepared by mixing a flux and a solder powder, the flux containing 42 parts by mass of a rosin, 35 parts by mass of a glycol type solvent, 8 parts by mass of a thixotropic agent, 10 parts by mass of an organic acid, 2 parts by mass of an amine and 3 parts by mass of a halogen ; and a solder powder comprising each alloy composition shown in Table 1 to Table 6 and having a size (particle size distribution) satisfying mark 4 in the particle size classification (Table 2) in JIS Z 3284-1:2014. They were mixed and made that way. The mass ratio of the flux and the solder powder was flux : solder powder = 11 : 89. For each solder paste, the change in viscosity with time was measured. Furthermore, the liquidus temperature and the solidus temperature of the solder powder were measured. Furthermore, the wettability of the solder paste was evaluated immediately after production. The details are as follows. • Change over time

[0074] For each solder paste, immediately after preparation, using PCU-205 made by Malcom Co., Ltd. the viscosity measured at a rotation speed of 10 rpm and at 25°C in air for 12 hours. The case where the viscosity after 12 hours was 1.2 times or less than the viscosity after 30 minutes from the preparation of the solder paste was evaluated as “AA” as the case where a sufficient thickening suppressing effect was obtained. The case where the viscosity was more than 1.2 times was evaluated as "CC". •ΔT

[0075] For the solder powder before mixing with the flux, a DSC measurement was performed using a model: EXSTAR DSC7020 manufactured by SII nanotechnology Inc. in a sample amount of about 30 mg and at a heating rate of: 15°C / min, whereby the Solidus temperature and the liquidus temperature were determined. The solidus temperature was subtracted from the resulting liquidus temperature to determine ΔT. The case where ΔT was 10°C or less was evaluated as “AA”, and the case where ΔT was more than 10°C was evaluated as “CC”. •- Wettability

[0076] Each solder paste was printed on a Cu plate immediately after its production and heated in a reflow oven at a heating rate of 1°C / s in a N 2 -Atmosphere heated from 25°C to 260°C and then cooled to room temperature. Wettability was evaluated by observing the external appearance of the cooled bumps with an optical microscope. The case where completely melted solder powder was not observed was evaluated as "AA". The case where incompletely melted solder powder was observed was evaluated as "CC".

[0077] The evaluation results are shown in Table 1. (Table 1) Alloy composition (mass ppm) expression (1) expression (2) subject of evaluation sn ace Sb Bi pb change over time ΔT wettability valuation Ex 1 rest 100 25 25 25 275 4,50 aa aa aa aa Ref Ex 2 rest 100 50 25 0 275 10,00 aa aa aa aa Ref Ex 3 rest 100 0 75 0 275 2,67 aa aa aa aa Ex 4 rest 100 0 0 75 275 2,67 aa aa aa aa Ex 5 rest 100 50 50 50 350 2,50 aa aa aa aa Ex 6 rest 50 100 100 50 350 1,33 aa aa aa aa Ex 7 rest 300 0 300 300 1200 1,00 aa aa aa aa Ex 8 rest 200 300 250 250 1200 1,40 aa aa aa aa Ex 9 rest 100 500 250 250 1200 1,40 aa aa aa aa Ex 10 rest 200 50 600 850 1900 0,31 aa aa aa aa Ex 11 rest 200 500 500 500 1900 0,90 aa aa aa aa Ref Ex 12 rest 200 500 1000 0 1900 0,90 aa aa aa aa Ex 13 rest 200 500 0 1000 1900 0,90 aa aa aa aa Ex 14 rest 25 500 350 1000 1900 0,41 aa aa aa aa Ex. 15 rest 100 3000 300 300 3800 5,33 aa aa aa aa Ex. 16 rest 100 0 0 5100 5300 0,04 aa aa aa aa Ref Ex 17 rest 100 0 10000 0 10200 0,02 aa aa aa aa Ex. 18 rest 100 0 10000 5000 15200 0,01 aa aa aa aa See Ex. 1 rest 0 100 100 100 300 0,50 CC aa aa CC See Ex. 2 rest 25 25 25 25 125 1,50 CC aa aa CC See Ex. 3 rest 300 500 50 50 1200 11,00 aa aa CC CC See Ex. 4 rest 350 1150 25 25 1900 37,00 aa aa CC CC See Ex. 5 rest 800 800 100 100 2600 12,00 aa aa CC CC See Ex. 6 rest 250 4800 1 0 5301 5300.00 aa aa CC CC See Ex. 7 rest 800 3500 100 100 5300 25,50 aa aa CC CC See Ex. 8 rest 100 10000 1 0 10201 10200.00 aa aa CC CC See Ex. 9 rest 100 100 25000 25000 50300 0,01 aa CC aa CC See Ex. 10 rest 100 100 50000 0 50300 0,01 aa CC aa CC See Ex. 11 rest 100 100 0 50000 50300 0,01 aa CC aa CC See Ex. 12 rest 300 3000 0 0 3600 - - aa aa CC CC See Ex. 13 rest 100 0 100 25000 25300 0,01 aa CC aa CC Underlined is outside the scope of the present invention (Table 2) Alloy composition (As, Bi, Pb: mass ppm, Cu: mass %) expression (1) expression (2) subject of evaluation sn Cu ace Sb Bi pb change over time ΔT wettability valuation Ex. 19 rest 0,7 100 25 25 25 275 4,50 aa aa aa aa Ref Ex 20 rest 0,7 100 50 25 0 275 10,00 aa aa aa aa Ref Ex 21 rest 0,7 100 0 75 0 275 2,67 aa aa aa aa Ex 22 rest 0,7 100 0 0 75 275 2,67 aa aa aa aa Ex 23 rest 0,7 100 50 50 50 350 2,50 aa aa aa aa Ex. 24 rest 0,7 50 100 100 50 350 1,33 aa aa aa aa Ex. 25 rest 0,7 300 0 300 300 1200 1,00 aa aa aa aa Ex 26 rest 0,7 200 300 250 250 1200 1,40 aa aa aa aa Ex 27 rest 0,7 100 500 250 250 1200 1,40 aa aa aa aa Ex. 28 rest 0,7 200 50 600 850 1900 0,31 aa aa aa aa Ex. 29 rest 0,7 200 500 500 500 1900 0,90 aa aa aa aa Ref Ex 30 rest 0,7 200 500 1000 0 1900 0,90 aa aa aa aa Ex. 31 rest 0,7 200 500 0 1000 1900 0,90 aa aa aa aa Ex 32 rest 0,7 25 500 350 1000 1900 0,41 aa aa aa aa Ex 33 rest 0,7 100 3000 300 300 3800 5,33 aa aa aa aa Ex 34 rest 0,7 100 0 0 5100 5300 0,04 aa aa aa aa Ref Ex 35 rest 0,7 100 0 10000 0 10200 0,02 aa aa aa aa Ex 36 rest 0,7 100 0 10000 5000 15200 0,01 aa aa aa aa See Ex. 14 Rest. 0,7 0 100 100 100 300 0,50 CC aa aa CC See Ex. 15 rest 0,7 25 25 25 25 125 1,50 CC aa aa CC See Ex. 16 rest 0,7 300 500 50 50 1200 11,00 aa aa CC CC See Ex. 17 rest 0,7 350 1150 25 25 1900 37,00 aa aa CC CC See Ex. 18 rest 0,7 800 800 100 100 2600 12,00 aa aa CC CC See Ex. 19 rest 0,7 250 4800 1 0 5301 5300.00 aa aa CC CC See Ex. 20 rest 0,7 800 3500 100 100 5300 25,50 aa aa CC CC See Ex. 21 rest 0,7 100 10000 1 0 10201 10200.00 aa aa CC CC See Ex. 22 rest 0,7 100 100 25000 25000 50300 0,01 aa CC aa CC See Ex. 23 rest 0,7 100 100 50000 0 50300 0,01 aa CC aa CC See Ex. 24 rest 0,7 100 100 0 50000 50300 0,01 aa CC aa CC See Ex. 25 rest 0,7 300 3000 0 0 3600 - aa aa CC CC See Ex. 26 rest 0,7 100 0 100 25000 25300 0,01 aa CC aa CC Underlined is outside the scope of the present invention (Table 3) Alloy composition (As, Sb, Bi, Pb: mass ppm, Ag, Cu: mass %) expression (1) expression (2) subject of evaluation sn Ag Cu ace Sb Bi pb change over time ΔT wettability valuation Ex 37 rest 1 0,5 100 25 25 25 275 4,50 aa aa aa aa Ref Ex 38 rest 1 0,5 100 50 25 0 275 10,00 aa aa aa aa Ref Ex 39 rest 1 0,5 100 0 75 0 275 2,67 aa aa aa aa Ex 40 rest 1 0,5 100 0 0 75 275 2,67 aa aa aa aa Ex 41 rest 1 0,5 100 50 50 50 350 2,50 aa aa aa aa Ex 42 rest 1 0,5 50 100 100 50 350 1,33 aa aa aa aa Ex 43 rest 1 0,5 300 0 300 300 1200 1,00 aa aa aa aa Ex 44 rest 1 0,5 200 300 250 250 1200 1,40 aa aa aa aa Ex 45 rest 1 0,5 100 500 250 250 1200 1,40 aa aa aa aa Ex 46 rest 1 0,5 200 50 600 850 1900 0,31 aa aa aa aa Ex 47 rest 1 0,5 200 500 500 500 1900 0,90 aa aa aa aa Ref Ex 48 rest 1 0,5 200 500 1000 0 1900 0,90 aa aa aa aa Ex 49 rest 1 0,5 200 500 0 1000 1900 0,90 aa aa aa aa Ex. 50 rest 1 0,5 25 500 350 1000 1900 0,41 aa aa aa aa Ex 51 rest 1 0,5 100 3000 300 300 3800 5,33 aa aa aa aa Ex. 52 rest 1 0,5 100 0 0 5100 5300 0,04 aa aa aa aa Ref Ex 53 rest 1 0,5 100 0 10000 0 10200 0,02 aa aa aa aa Ex. 54 rest 1 0,5 100 0 10000 5000 15200 0,01 aa aa aa aa See Ex. 27 rest 1 0,5 0 100 100 100 300 0,50 CC aa aa CC See Ex. 28 rest 1 0,5 25 25 25 25 125 1,50 CC aa aa CC See Ex. 29 rest 1 0,5 300 500 50 50 1200 11,00 aa aa CC CC See Ex. 30 rest 1 0,5 350 1150 25 25 1900 37,00 aa aa CC CC See Ex. 31 rest 1 0,5 800 800 100 100 2600 12,00 aa aa CC CC See Ex. 32 rest 1 0,5 250 4800 1 0 5301 5300.00 aa aa CC CC See Ex. 33 rest 1 0,5 800 3500 100 100 5300 25,50 aa aa CC CC See Ex. 34 rest 1 0,5 100 10000 1 0 10201 10200,00 aa aa CC CC See Ex. 35 rest 1 0,5 100 100 25000 25000 50300 0,01 aa CC aa CC See Ex. 36 rest 1 0,5 100 100 50000 0 50300 0,01 aa CC aa CC See Ex. 37 rest 1 0,5 100 100 0 50000 50300 0,01 aa CC aa CC See Ex. 38 rest 1 0,5 300 3000 0 0 3600 - aa aa CC CC See Ex. 39 rest 1 0,5 100 0 100 25000 25300 0,01 aa CC aa CC Underlined is outside the scope of the present invention (Table 4) Alloy composition (As, Sb, Bi, Pb: mass ppm, Ag, Cu: mass %) expression (1) expression (2) subject of evaluation sn Ag Cu ace Sb Bi pb change over time ΔT wettability valuation Ex. 55 rest 2 0,5 100 25 25 25 275 4,50 aa aa aa aa Ref Ex 56 rest 2 0,5 100 50 25 0 275 10,00 aa aa aa aa Ref Ex 57 rest 2 0,5 100 0 75 0 275 2,67 aa aa aa aa Ex. 58 rest 2 0,5 100 0 0 75 275 2,67 aa aa aa aa Ex. 59 rest 2 0,5 100 50 50 50 350 2,50 aa aa aa aa Ex. 60 rest 2 0,5 50 100 100 50 350 1,33 aa aa aa aa Ex 61 rest 2 0,5 300 0 300 300 1200 1,00 aa aa aa aa Ex 62 rest 2 0,5 200 300 250 250 1200 1,40 aa aa aa aa Ex 63 rest 2 0,5 100 500 250 250 1200 1,40 aa aa aa aa Ex 64 rest 2 0,5 200 50 600 850 1900 0,31 aa aa aa aa Ex. 65 rest 2 0,5 200 500 500 500 1900 0,90 aa aa aa aa Ref. Ex. 66 rest 2 0,5 200 500 1000 0 1900 0,90 aa aa aa aa Ex 67 rest 2 0,5 200 500 0 1000 1900 0,90 aa aa aa aa Ex 68 rest 2 0,5 25 500 350 1000 1900 0,41 aa aa aa aa Ex 69 rest 2 0,5 100 3000 300 300 3800 5,33 aa aa aa aa Ex. 70 rest 2 0,5 100 0 0 5100 5300 0,04 aa aa aa aa Ref Ex 71 rest 2 0,5 100 0 10000 0 10200 0,02 aa aa aa aa Ex 72 rest 2 0,5 100 0 10000 5000 15200 0,01 aa aa aa aa See Ex. 40 Rest, 2 0,5 0 100 100 100 300 0,50 CC aa aa CC See Ex. 41 rest 2 0,5 25 25 25 25 125 1,50 CC aa aa CC See Ex. 42 rest 2 0,5 300 500 50 50 1200 11,00 aa aa CC CC See Ex. 43 rest 2 0,5 350 1150 25 25 1900 37,00 aa aa CC CC See Ex. 44 rest 2 0,5 800 800 100 100 2600 12,00 aa aa CC CC See Ex. 45 rest 2 0,5 250 4800 1 0 5301 5300.00 aa aa CC CC See Ex. 46 rest 2 0,5 800 3500 100 100 5300 25,50 aa aa CC CC See Ex. 47 rest 2 0,5 100 10000 1 0 10201 10200,00 aa aa CC CC See Ex. 48 rest 2 0,5 100 100 25000 25000 50300 0,01 aa CC aa CC See Ex. 49 rest 2 0,5 100 100 50000 0 50300 0,01 aa CC aa CC See Ex. 50 rest 2 0,5 100 100 0 50000 50300 0,01 aa CC aa CC See Ex. 51 rest 2 0,5 300 3000 0 0 3600 - aa aa CC CC See Ex. 52 rest 2 0,5 100 0 100 25000 25300 0,01 aa CC aa CC Underlined is outside the scope of the present invention (Table 5) Alloy composition (As, Sb, Bi, Pb: mass ppm, Ag, Cu: mass %) expression (1) expression (2) subject of evaluation sn Ag Cu ace Sb Bi pb change over time ΔT wettability valuation Ex 73 rest 3 0,5 100 25 25 25 275 4,50 aa aa aa aa Ref. Ex. 74 rest 3 0,5 100 50 25 0 275 10,00 aa aa aa aa Ref Ex 75 rest 3 0,5 100 0 75 0 275 2,67 aa aa aa aa Ex 76 rest 3 0,5 100 0 0 75 275 2,67 aa aa aa aa Ex 77 rest 3 0,5 100 50 50 50 350 2,50 aa aa aa aa Ex 78 rest 3 0,5 50 100 100 50 350 1,33 aa aa aa aa Ex 79 rest 3 0,5 300 0 300 300 1200 1,00 aa aa aa aa Ex. 80 rest 3 0,5 200 300 250 250 1200 1,40 aa aa aa aa Ex 81 rest 3 0,5 100 500 250 250 1200 1,40 aa aa aa aa Ex 82 rest 3 0,5 200 50 600 850 1900 0,31 aa aa aa aa Ex 83 rest 3 0,5 200 500 500 500 1900 0,90 aa aa aa aa Ref Ex 84 rest 3 0,5 200 500 1000 0 1900 0,90 aa aa aa aa Ex. 85 rest 3 0,5 200 500 0 1000 1900 0,90 aa aa aa aa Ex 86 rest 3 0,5 25 500 350 1000 1900 0,41 aa aa aa aa Ex 87 rest 3 0,5 100 3000 300 300 3800 5,33 aa aa aa aa Ex 88 rest 3 0,5 100 0 0 5100 5300 0,04 aa aa aa aa Ref. Ex. 89 rest 3 0,5 100 0 10000 0 10200 0,02 aa aa aa aa Ex. 90 rest 3 0,5 100 0 10000 5000 15200 0,01 aa aa aa aa See Ex. 53 rest 3 0,5 0 100 100 100 300 0,50 CC aa aa CC See Ex. 54 rest 3 0,5 25 25 25 25 125 1,50 CC aa aa CC See Ex. 55 rest 3 0,5 300 500 50 50 1200 11,00 aa aa CC CC See Ex. 56 rest 3 0,5 350 1150 25 25 1900 37,00 aa aa CC CC See Ex. 57 rest 3 0,5 800 800 100 100 2600 12,00 aa aa CC CC See Ex. 58 rest 3 0,5 250 4800 1 0 5301 5300.00 aa aa CC CC See Ex. 59 rest 3 0,5 800 3500 100 100 5300 25,50 aa aa CC CC See Ex. 60 rest 3 0,5 100 10000 1 0 10201 10200,00 aa aa CC CC See Ex. 61 rest 3 0,5 100 100 25000 25000 50300 0,01 aa CC aa CC See Ex. 62 rest 3 0,5 100 100 50000 0 50300 0,01 aa CC aa CC See Ex. 63 rest 3 0,5 100 100 0 50000 50300 0,01 aa CC aa CC See Ex. 64 rest 3 0,5 300 3000 0 0 3600 - aa aa CC CC See Ex. 65 Rest, 3 0,5 100 0 100 25000 25300 0,01 aa CC aa CC Underlined is outside the scope of the present invention (Table 6) Alloy composition (As, Sb, Bi, Pb: mass ppm, Ag, Cu: mass %) expression (1) expression (2) subject of evaluation sn Ag Cu ace Sb Bi pb change over time ΔT wettability valuation Ex. 91 rest 3,5 0,5 100 25 25 25 275 4,50 aa aa aa aa Ref Ex 92 rest 3,5 0,5 100 50 25 0 275 10,00 aa aa aa aa Ref Ex 93 rest 3,5 0,5 100 0 75 0 275 2,67 aa aa aa aa Ex 94 rest 3,5 0,5 100 0 0 75 275 2,67 aa aa aa aa Ex. 95 rest 3,5 0,5 100 50 50 50 350 2,50 aa aa aa aa Ex 96 rest 3,5 0,5 50 100 100 50 350 1,33 aa aa aa aa Ex 97 rest 3,5 0,5 300 0 300 300 1200 1,00 aa aa aa aa Ex. 98 rest 3,5 0,5 200 300 250 250 1200 1,40 aa aa aa aa Ex. 99 rest 3,5 0,5 100 500 250 250 1200 1,40 aa aa aa aa Ex. 100 rest 3,5 0,5 200 50 600 850 1900 0,31 aa aa aa aa Ex 101 rest 3,5 0,5 200 500 500 500 1900 0,90 aa aa aa aa Ref Ex 102 rest 3,5 0,5 200 500 1000 0 1900 0,90 aa aa aa aa Ex 103 rest 3,5 0,5 200 500 0 1000 1900 0,90 aa aa aa aa Ex 104 rest 3,5 0,5 25 500 350 1000 1900 0,41 aa aa aa aa Ex 105 rest 3,5 0,5 100 3000 300 300 3800 5,33 aa aa aa aa Ex 106 rest 3,5 0,5 100 0 0 5100 5300 0,04 aa aa aa aa Ref Ex 107 rest 3,5 0,5 100 0 10000 0 10200 0,02 aa aa aa aa Ex 108 rest 3,5 0,5 100 0 10000 5000 15200 0,01 aa aa aa aa See Ex. 66 Rest, 3,5 0,5 0 100 100 100 300 0,50 CC aa aa CC See Ex. 67 rest 3,5 0,5 25 25 25 25 125 1,50 CC aa aa CC See Ex. 68 rest 3,5 0,5 300 500 50 50 1200 11,00 aa aa CC CC See Ex. 69 rest 3,5 0,5 350 1150 25 25 1900 37,00 aa aa CC CC See Ex. 70 rest 3,5 0,5 800 800 100 100 2600 12,00 aa aa CC CC See Ex. 71 rest 3,5 0,5 250 4800 1 0 5301 5300.00 aa aa CC CC See Ex. 72 rest 3,5 0,5 800 3500 100 100 5300 25,50 aa aa CC CC See Ex. 73 rest 3,5 0,5 100 10000 1 0 10201 10200,00 aa aa CC CC See Ex. 74 rest 3,5 0,5 100 100 25000 25000 50300 0,01 aa CC aa CC See Ex. 75 rest 3,5 0,5 100 100 50000 0 50300 0,01 aa CC aa CC See Ex. 76 rest 3,5 0,5 100 100 0 50000 50300 0,01 aa CC aa CC See Ex. 77 rest 3,5 0,5 300 3000 0 0 3600 - aa aa CC CC See Ex. 78 rest 3,5 0,5 100 0 100 25000 25300 0,01 aa CC aa CC Underlined is outside the scope of the present invention

[0078] As shown in Table 1 to Table 6, the examples in each alloy composition meet all the requirements of the present invention. Accordingly, it was shown that the examples had the thickening suppressing effect, the reduction of ΔT and the excellent wettability.

[0079] In contrast, Comparative Examples 1, 14, 27, 40, 53 and 66 contained no As. For this reason, the thickening suppressing effect was not exerted.

[0080] that all alloy compositions in the examples meet the requirements of the present invention and therefore have a thickening suppressing effect, a narrowing of ΔT and excellent crosslinkability.

[0081] In contrast, Comparative Examples 1, 10, 19, 28, 37 and 46 contained no As and therefore exhibited no thickening suppressing effect.

[0082] In Comparative Examples 2, 15, 28, 41, 54 and 67, the expression (1) was smaller than the lower limit. For this reason, the thickening suppressing effect was not exerted.

[0083] In Comparative Examples 3, 16, 29, 42, 55 and 68, Expression (2) exceeded the upper limit. For this reason, the wettability was inferior.

[0084] In Comparative Examples 4, 5, 17, 18, 30, 31, 43, 44, 56, 57, 69 and 70, the As content and the expression (2) exceeded the upper limits. For this reason, the result was inferior wettability.

[0085] In Comparative Examples 6 to 8, 19 to 21, 32 to 34, 45 to 47, 58 to 60 and 71 to 73, the Sb content exceeded the upper limit. For this reason, the wettability was inferior.

[0086] In Comparative Examples 9, 10, 22, 23, 35, 36, 48, 49, 61, 62, 74 and 75, the Bi content exceeded the upper limit. For this reason, the result showed ΔT of more than 10°C.

[0087] In Comparative Examples 11, 13, 24, 26, 37, 39, 50, 52, 63, 65, 76 and 78, the Pb content exceeded the upper limit. For this reason, the result showed ΔT of more than 10°C.

[0088] Comparative Examples 12, 25, 38, 51, 64 and 77 did not contain Bi and Pb, so the expression (2) was not satisfied. For this reason, the wettability was inferior.

[0089] Further, when each sample contained a zirconia powder having a particle size of 1 μm in an amount of 0.1%, the improvement in the thickening suppressing effect could be observed. QUOTES INCLUDED IN DESCRIPTION

[0000] This list of documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Patent Literature Cited

[0000] JP 2015098052 A

[0007]

Claims

[1] Solder alloy comprising an alloy composition containing at least one of: As: 25 to 300 ppm by mass, Pb: more than 0 ppm by mass and 5100 ppm by mass or less, and Sb: more than 0 ppm by mass and 3000 ppm by mass or less, and furthermore Bi: more than 0 ppm by mass and 10000 ppm by mass or less, and a remainder containing Sn, wherein the following expression (1) and expression (2) are satisfied: 275 ≤ 2 As + Sn + Bi + Pb 0,01 ≤ ( 2 As + Sb ) / ( Bi + Pb ) ≤ 10,00 where As, Sb, Bi and Pb in expression (1) and expression (2) each represent a content (mass ppm) in the alloy composition. [2] Solder alloy according to claim 1, wherein the alloy composition further satisfies the following expression (1a): 275 ≤ 2 As + Sb + Bi + Pb ≤ 25200 where As, Sb, Bi and Pb in expression (1a) each represent a content (mass ppm) in the alloy composition. [3] Solder alloy according to claim 1, wherein the alloy composition further satisfies the following expression (1a), 275 ≤ 2 As + Sb + Bi + Pb ≤ 5300 where As, Bi and Pb in expression (1b) each represent a content (mass ppm) in the alloy composition. [4] Solder alloy according to any one of claims 1 to 3, wherein the alloy composition further satisfies the following expression (2a), 0,31 ≤ ( 2 As + Sb ) / ( Bi + Pb ) ≤ 10,00 where As, Sb, Bi and Pb in expression (2a) each represent a content (mass ppm) in the alloy composition. [5] Alloy composition according to any one of claims 1 to 4, wherein the alloy composition further comprises at least one of Ag: 0 to 4 wt% and Cu: 0 to 0.9 wt%. [6] Solder powders comprise the solder alloy according to any one of claims 1 to 5. [7] Solder paste comprising the solder powder according to claim 6. [8] Solder paste according to claim 7, further comprising a zirconium oxide powder. [9] Solder paste according to claim 8, comprising the zirconium oxide powder in an amount of 0.05 to 20.0 wt% based on a total mass of the solder paste. [10] Solder joint comprising the solder alloy according to any one of claims 1 to 5.