• 专利附录
  • 专利说明
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    • 专利摘要:
    summary lead-free solder alloy and electronic circuit on board the vehicle with increasing density of electronic circuits on board the vehicle, not only appear conventional slits in the connection interfaces, but also between the substrate and the welding fixture or a component and the place where the weld is fixed, but also the occurrence of new problems with cracks in the sn matrix inside the bonded weld. to solve the above problem, a lead-free solder alloy with 1 to 4% by weight of ag, 0.6 to 0.8% by weight of cu, 1 to 5% by weight of sb, 0.01 to 0.2% by mass of ni, the remainder being sn. it is possible to obtain a solder alloy, which can not only withstand the characteristics of rigorous temperature cycles from low temperatures of -40 ° C to high temperatures of 125 ° C, but can also withstand external forces that occur when traveling a stretch in the middle -wire or collision with a vehicle in front of you, for long periods of time, and an electronic circuit device on board the vehicle using said solder alloy.
    公开号:BR112015025125B1
    申请号:R112015025125-0
    申请日:2014-04-03
    公开日:2020-03-24
    发明作者:Shunsaku Yoshikawa；Naoko Hirai；Ken Tachibana；Yoshie TACHIBANA
    申请人:Senju Metal Industry Co., Ltd.；
    IPC主号:
    专利说明:

    WELDING ALLOY, ELECTRONIC CIRCUITS AND ELECTRONIC CIRCUIT UNITS
    TECHNICAL FIELD [001]. The present invention relates to a lead-free solder alloy that has excellent temperature cycle characteristics and is resistant to the impact of a collision or the like, and an electronic circuit unit within a vehicle.
    BACKGROUND OF THE PRESENT INVENTION [002]. Electronic circuits (hereinafter electronic circuits on board vehicles) obtained by soldering electronic parts, such as semiconductors and chip resistor parts for printed circuit boards (hereinafter printed circuit boards) are mounted on a vehicle. This electronic circuit inside a vehicle is used in a unit to electrically control components such as the engine, power steering and brake, and a unit of this type is a part of safety that is very important for the vehicle's journey. In particular, an electronic circuit unit within a vehicle called an ECU (Engine Control Unit) which is provided with an electronic circuit allowing a computer to control the vehicle's path and in particular the operation of the engine, to improve efficiency Fuel consumption must be operable in a steady state without any failure over an extended period of time. In general, the ECU is often placed close to the engine, and in a very strict operating environment. In this specification, the electronic circuit unit within a vehicle is also referred to simply as ECU or Electronic circuit unit ECU.
    [003]. When the engine is put in rotation, its surroundings where this electronic circuit inside a vehicle is positioned, have a high temperature of 125 ° C or more. On the other hand, when the engine speed is stopped, the outdoor air temperature in winter
    Petition 870160078679, of 12/23/2016, p. 9/39
    2/24 reduces to -40 ° C or less in cold regions, such as North America and Siberia. Therefore, the electronic circuit inside a vehicle is exposed to heat cycles in a range ranging from -40 ° C or less to + 125 ° C or more, operating repeatedly and stopping the engine.
    [004]. When the electronic circuit inside a vehicle is exposed for a long period of time to an environment where the temperature varies, thus, the electronic parts and a printed circuit board cause thermal expansion and contraction. However, since there is a big difference between the linear expansion coefficient of electronic parts made mainly of ceramic and this printed circuit board made of an epoxy glass substrate, a certain degree of thermal displacement occurs in each of the portions where the electronic parts are joined to the printed circuit board by welding (hereinafter referred to as solder joint portions) during use, in the mentioned environment and the solder joint portions are pressed repeatedly by these temperature variations. Then, the aforementioned stresses eventually cause the weld joint portions to rupture at their joint interfaces. In the electronic circuit, when a portion of the weld joint is not completely broken, but it is evenly cracked in the proportion of slots of up to 99%, the resistance value of the circuit can increase causing a malfunction, even in the state of electrical conduction. The situation in which a crack occurs in the weld joint portion causes malfunction of the electronic circuit unit inside a vehicle and, in particular, the ECU should be avoided. As described above, the characteristics of the temperature cycle are particularly important for the electronic circuit unit inside a vehicle and, in particular, the ECU, and the solder joint portion, i.e. the solder alloy for use in it as well. it must be usable evenly under the most possible conditions of rigorous temperature.
    Petition 870160078679, of 12/23/2016, p. 10/39
    3/24 [005]. Lead-free solder for vehicles, as defined by patent publication WO 2009 / 011341A comprising: 2.8 to 4% by weight of Ag; 1.5 to 6% by weight of Bi; 0.8 to 1.2% by weight of Cu; at least one selected from the group consisting of Ni, Fe and Co, in a total amount from 0.005 to 0.05% by weight; and a Sn balance is described as a solder for use in an electronic circuit unit within a vehicle and, in particular, an ECU that is under strict conditions of use.
    [006]. A solder material has also been described as defined in patent application JP 2006-524572 A comprising an alloy that is composed, depending on the composition of the simple solder alloy, 10% by weight or less of Ag (silver), 10% by weight or less than Bi (bismuth), 10% by weight or less than Sb (antimony) and 3% by weight or less than Cu (copper), in addition to Sn (tin), as the main constituent, in which the alloy further comprises 1 , 0% by weight or less of Ni (nickel).
    BRIEF DESCRIPTION OF THE DRAWINGS [007]. Figure 1 is a schematic diagram of the periphery of a weld joint portion in a conventional electronic circuit.
    [008]. Figure 2 is a schematic diagram of the periphery of a weld joint portion in an electronic circuit within a vehicle in accordance with the present patent application.
    [009]. Figure 3 is an electron micrograph showing the state of an SnSb intermetallic compound in a solder alloy according to the present invention (Example 5) after 3,000 cycles in the temperature cycle test.
    [0010]. Figure 4 is an electron micrograph showing the state of an SnSb intermetallic compound in a solder alloy according to the comparative example (Comparative Example 4) after 3,000 cycles in the temperature cycle test.
    [0011]. Figure 5 is a schematic diagram showing a
    Petition 870160078679, of 12/23/2016, p. 11/39
    4/24 slit rate calculation method.
    [0012]. Figure 6 is a graph in which the crack occurrence rate and the residual shear force rate in relation to the Sb content (without Bi) are plotted based on Table 2.
    [0013]. Figure 7 is a graph in which the crack occurrence rate is plotted in relation to the Bi content based on Table 2.
    [0014]. Figure 8 is a graph in which the residual shear force rate in relation to the Bi content is plotted based on Table 2.
    Description of the Symbols chip part solder plate Cu (Cu land) burr seam layer intermetallic compound path through which the slit travels SnSb intermetallic compound path through which the cracks are believed to travel
    DETAILED DESCRIPTION OF THE PRESENT INVENTION
    Technical Problems [0015]. As can be seen in the popularization of hybrid vehicles and electric vehicles, there is a transition from mechanical parts to electronic parts in vehicles and electronic circuits for automobiles that had a dimensional space that must also be correspondingly reduced. Therefore, as a matter of course, the electronic circuitry inside a vehicle that has been conventionally welded by melting welding following reflow welding in recent years is welded by two-sided reflow welding, according to which both sides are subject to surface assembly with solder paste. This increased the density of the electronic circuit within a
    Petition 870160078679, of 12/23/2016, p. 12/39
    5/24 vehicle, causing defects in the crack mode that until then had not been detected.
    [0016]. By the way, the present invention in the
    Patent 1 describes a weld alloy with a long service life in a harsh environment. However, a vehicle is used as a means of transport and is therefore less likely to be left at rest in one location and more likely to be used on a road or the like. When the vehicle is thus used on a road, a rough road causes vibrations that are applied to the electronic circuit unit inside a vehicle at all times and the vehicle can be driven on a curb or colliding with a vehicle traveling in the opposite direction. In this way, external forces are often applied to the electronic circuit unit inside a vehicle. In the event of a major accident caused by the vehicle collision, generally, the entire electronic circuit unit inside a vehicle is replaced in simple accidental contact, the vehicle often receives only external replacement. The electronic circuit unit inside a vehicle must withstand not only harsh environments, but also forces applied from the outside.
    [0017]. In particular, newer vehicles are being computerized, along with the popularization of electric vehicles and hybrid vehicles and the electronic circuit units within a vehicle are also made smaller in size and higher in density. Therefore, the solder content in a solder joint portion of an electronic circuit inside a vehicle is also reduced. For example, the solder content in a solder joint portion of a 3216-sized chip piece generally has 1.32 mg on one side, while the solder content for use in an electronic circuit inside of a vehicle is so small that it is below 0.28 mg on one side. Therefore, in a conventional electronic circuit, a portion of the solder fillet sticks out
    Petition 870160078679, of 12/23/2016, p. 13/39
    6/24 on the side of a chip part as in Figure 1, but on a solder joint portion of an electronic circuit inside a vehicle, a solder fillet is hardly formed on the side of a chip part as in Figure 2. Consequently, a new slit mode occurs in which a slit propagates in a substantially straight line, as in Figure 2 in the solder joint portion of the electronic circuit inside a vehicle and can cause a malfunction problem.
    [0018]. The present invention aims to develop a solder alloy that is capable of withstanding for a long period of time not only the rigorous temperature cycle characteristics, including low temperature of -40 ° C and high temperature of 125 ° C, but also an external force caused by driving over a curb or colliding with a vehicle walking in the opposite direction, as well as an electronic circuit unit inside a vehicle using the solder alloy.
    Solution to the Problems [0019]. The inventors of the present invention have found that it is effective to form an alloy of reinforced solid solution by adding an element that can enter the solid solution in the Sn phase. To resist an external force, after a prolonged temperature cycle, Sb is a great element, to form the solid solution and the precipitation of the reinforced alloy, and the addition of Sb in a Sn matrix forms a fine intermetallic compound SnSb and also has the effect of reinforcing precipitation and dispersion. Therefore, the present invention has been completed.
    [0020]. The present invention provides a lead-free solder alloy including:
    1% to 4% by weight of Ag;
    0.6% to 0.8% by weight of Cu;
    1% to 5% by weight of Sb;
    0.01% to 0.2% by weight of Ni; and
    Petition 870160078679, of 12/23/2016, p. 14/39
    7/24 a balance of Sn.
    [0021]. Bi can still be added in an amount of
    1.5% to 5.5% by weight. At least one element selected from Co and Fe can still be added in a total amount of 0.001% to 0.1% by weight.
    [0022]. The alloy according to the present invention has the following characteristics of metallurgical structure: The weld alloy is composed of a structure in which the Sb enters a solid solution in a Sn matrix; the structure is in a state where Sb enters the solid solution in a stable manner at an elevated temperature of, for example, 125 ° C, but Sb gradually enters the solid solution in the Sn matrix in a supersaturated state with decreasing temperature and Sb precipitates as an intermetallic compound SnSb at a low temperature of, for example, -40 ° C.
    [0023]. The present invention further provides an electronic circuit within a vehicle obtained by soldering using the previous solder alloy and an electronic circuit unit within a vehicle provided with the electronic circuit. The term inside a vehicle or for vehicles as used here, means that an electronic circuit, or electronic circuit unit is mounted on a vehicle and more specifically ensures predetermined characteristics and is mountable on a vehicle, even when used, a since it is repeatedly exposed to an environment of rigorous use, that is, an environment where the temperature varies from -40 ° C to 125 ° C. To be more specific, the electronic circuit or electronic circuit unit can withstand a heat cycle test carried out at 3,000 cycles, even under a certain ambient temperature and has a shear test resistance to assess external forces, even under this condition.
    [0024]. The solder alloy of the present invention forms fine Sb, precipitates even after being exposed to a temperature cycle and does not
    Petition 870160078679, of 12/23/2016, p. 15/39
    8/24 causes deterioration of the structure including thickening of a compound due to the following reasons: The solder alloy for vehicles that are to be joined by means of reflow soldering is subjected to a temperature cycle test in a range of -40 ° C up to + 125 ° C, simulating a cold weather region for low temperature and an engine room for high temperature. According to the solder alloy of the present invention, by repeating the process in which the added Sb enters the solid solution again in the Sn matrix in a high temperature state of, for example, 125 ° C and the intermetallic compound SnSb is precipitated in a low temperature state of, for example, -40 ° C, the thickening of the intermetallic compound SnSb is stopped, and the intermetallic compound SnSb once it has been thickened is also dissolved again in the Sn matrix on the high temperature side during the temperature cycle. Consequently, the thin SnSb intermetallic compound is formed to maintain the reinforced solder alloy's precipitation and dispersion.
    [0025]. However, if Sb is added in an amount greater than 5% by weight, for example, 8% by weight, the SnSb compound at the beginning of the temperature test cycle has a large particle size and no fine particles are obtained. In addition, once the liquid state temperature is increased, the Sb added to the solder alloy does not dissolve again, on the high temperature side and is thus maintained in the original form of SnSb crystal grains. Therefore, even if the solder alloy is used repeatedly under the previous temperature cycle, the fine SnSb intermetallic compound is not formed.
    [0026]. In addition, if Sb is added in an amount greater than 5% by weight, the liquid state temperature of the solder alloy is increased. Therefore, it is not possible to carry out welding without increasing the temperature for heating by reflow. Under these high reflow conditions, Cu interconnected to the surface of a
    Petition 870160078679, of 12/23/2016, p. 16/39
    9/24 printed circuit merges with solder, where it is more likely to form a layer of intermetallic compound made of SnCu, such as Cu6Sn5 having a large thickness in portions to weld the printed circuit board, which facilitates the breaking of the board printed circuit board and solder joint portions.
    [0027]. According to the present invention, the Sb added to the solder alloy forms fine precipitates in the form of the SnSb compound in the solder alloy Sn matrix and the state of the precipitates of the thin SnSb intermetallic compound can be maintained in the Sn matrix, even after the temperature cycle ranging from -40 ° C to + 125 ° C to be repeated for approximately 3,000 cycles. SnSb precipitates thus prevent cracks that can easily occur at the interfaces between electronic parts made of ceramics or the like and the weld joint portions.
    [0028]. According to the present invention, even after passing the previous temperature cycle test, the particle size of the intermetallic compound SnSb in the matrix Sn is substantially the same particle size as those of the particles of intermetallic compounds SnSb had before the test, in short, up to 0.6 pm, and indicates that thickening is suppressed. Consequently, even if a crack is formed in the weld, the fine SnSb intermetallic compound prevents the crack from spreading, through which it is possible to suppress the crack's spread.
    Advantageous Effects of the Present Invention [0029]. In the solder alloy according to the present invention, even if a temperature cycle test in the range of -40 ° C to + 125 ° C is repeated for approximately 3,000 cycles, the solder joint portions that have a very large amount small solder, and also have no cracks. Furthermore, even in a case where a crack has occurred, it is prevented from being propagated in the weld, where it is possible
    Petition 870160078679, of 12/23/2016, p. 17/39
    10/24 display excellent temperature cycle characteristics. Even when the solder alloy according to the present invention is used in an environment of use exposed to a temperature cycle ranging from -40 ° C to + 125 ° C, using the solder alloy according to the present invention in a very small amount of weld in a weld of the electronic circuit inside a vehicle with some weld fillets, and including thin weld joint portions prevents cracks in the weld joint portions and suppresses the crack propagation in the weld, even if these occur. Consequently, the electronic circuit within a highly reliable vehicle and the electronic circuit unit within a vehicle can be obtained. In addition, the solder alloy according to the present invention is also prevented from having cracks that can occur at the common interface and have characteristics particularly suitable for welding an ECU unit.
    Preferred Co-configuration of the Present Invention [0030]. When Sb is added to the solder alloy of the present invention in an amount less than 1% by weight, the way that Sb is dispersed in a Sn matrix does not appear, nor does it show the reinforcing effect of the solid solution, since the amount of Sb is very small. In addition, the shear strength of the weld joint portions is also decreased. When Sb is added in an amount greater than 5% by weight, Sb does not reflow at an elevated temperature above 125 ° C, as observed during engine operation under the hot sun due to an increase in liquid state temperature . Consequently, an SnSb intermetallic compound is thickened and crack propagation in the weld cannot be suppressed. In addition, since the peak temperature during assembly increases with increasing liquid state temperature, the Cu interconnected on the surface of a printed circuit board merges with the solder, where a layer of intermetallic compound made
    Petition 870160078679, of 12/23/2016, p. 18/39
    11/24 SnCu, as CuóSnõ and having a great thickness, in the solder portions of the printed circuit board, which facilitates the breaking of the printed circuit board and the solder joint portions. Consequently, the amount of Sb according to the present invention is from 1% to 5% by weight and preferably 3% to 5% by weight. In cases where Bi, which will be described later, must be mixed, the amount of Sb is preferably more than 3%, but up to 5%.
    [0031]. The solder alloy according to the present invention suppresses the occurrence and propagation of cracks in the weld and also suppresses the occurrence of cracks in the weld joint interface between a ceramic piece and a weld joint portion. For example, welding for a Cu (Cu land) burr seam causes an CuóSm intermetallic compound to form at the joint interface for the Cu (Cu land) burr seam, but the Ni contained in the weld alloy of the the present invention in an amount of 0.01% to 0.2% by weight moves to the portion of the weld interface at the time of welding to form (CuNi) óSn5 instead of CuóSm, thereby increasing the concentration of Ni in the compound layer intermetallic (CuNi) óSn5 at the interface. The intermetallic compound layer thus formed at the welding interface is composed of (CuNi) óSn5 which is finer and uniform in particle size than CuóSn5. The thinner layer of intermetallic compound composed of (CuNi) óSn5 has the effect of suppressing cracks, which can propagate from the interface. In the layer of an intermetallic compound with a large particle size, such as CuóSm, if a crack occurs, it spreads along the large particles and therefore spreads quickly. In contrast, when the particle size is very small, when the tension of a crack occurs, it is dispersed in many directions of particle size and it is therefore possible to decrease the crack propagation.
    Petition 870160078679, of 12/23/2016, p. 19/39
    12/24 [0032]. As described above, in the solder alloy of the present invention, the addition of Ni serves to thin the intermetallic compound of the layer of intermetallic compounds that occur in the vicinity of the welding interface, thus suppressing the occurrence and propagation of cracks if this occurs . Therefore, it is also possible to suppress crack occurrence and propagation from the joint interface. When the Ni content is less than 0.01% by weight, the effect of modifying the interface of a weld joint portion is insufficient due to a small Ni content in the welding interface and therefore there is no effect of crack suppression. When the Ni content is greater than 0.2% by weight, Sb remelting according to the present invention does not occur, due to an increase in the liquid state temperature and the effect of maintaining the particle size of the intermetallic compound SnSb thin is harmed. Accordingly, the Ni content according to the present invention is preferably 0.01% to 0.2% by weight, more preferably 0.02% to 0.1% by weight, and even more preferable if 0, 02% to 0.08%.
    [0033]. The Ag that is added according to the present invention has the effect of improving the weld wettability and the effect of improving the characteristics of the temperature cycle through the formation of a precipitate and the dispersion of the reinforced alloy through the precipitation of a compound of the network type, such as an Ag3Sn intermetallic compound in the weld matrix. When the Ag content is less than 1% by weight, the solder alloy of the present invention does not exhibit the effect of improving wettability or the solder has a firm mesh of intermetallic compound due to a decrease in the amount of Ag3Sn precipitation. When the Ag content is greater than 4% by weight, there is no remelting of Sb added according to the present invention, due to an increase in the liquid state temperature, thus preventing the refining effect of intermetallic compound SnSb. Therefore, Ag is added
    Petition 870160078679, of 12/23/2016, p. 20/39
    13/24 according to the present invention in an amount preferably from 1% to 4% by weight, and more preferable if 3.2% to 3.8% by weight.
    [0034]. The Cu that is added to the solder alloy of the present invention has the effect of preventing Cu contained in the Cu burr seam (Cu land) from dispersion in the solder alloy and the effect of improving the temperature cycle characteristics through precipitation of a thin Cu6Sn5 compound in the weld matrix. When the Cu content in the solder alloy of the present invention is less than 0.6% by weight, the Cu contained in the Cu (Cu land) burr seam is not prevented from dispersing in the solder alloy, whereas when the Cu is added in an amount greater than 0.8% by weight, the Cu6Sn5 intermetallic compound is also precipitated in a large amount at the joint interface. Thus, crack growth is accelerated due to vibrations or another factor.
    [0035]. In the solder alloy of the present invention, the temperature cycle characteristics can be further improved with the addition of Bi. The Sb added in the present invention not only has the effect of forming a precipitation and dispersion of the reinforced alloy through the precipitation of the intermetallic compound SnSb, but also has the effect of distorting an atomic array network and strengthening the Sn matrix by penetrating the array network atomic and being replaced by Sn, thus improving the characteristics of the temperature cycle. If the weld contains Bi, Bi is replaced by Sb in this process and, therefore, the characteristics of the temperature cycle can be further improved, as Bi has a higher atomic weight than Sb and is more effective in distorting the network of the atomic arrangement. In addition, Bi does not prevent the formation of the thin SnSb intermetallic compound to maintain precipitation and dispersion of the reinforced solder alloy. When Bi is added to the solder alloy of the present invention in an amount less than 1.5% by weight, there is no effect of improving the temperature cycle, as Bi is less likely to
    Petition 870160078679, of 12/23/2016, p. 21/39
    14/24 is replaced by Sb to reduce the amount of fine SnSb intermetallic compound. When Bi is added in an amount greater than 5.5% by weight, the ductility of the solder alloy itself is reduced to make the solder alloy harder and more brittle. Thus, crack growth is accelerated due to vibrations or another factor. Bi is added to the solder alloy of the present invention in a preferred amount of 1.5% to 5.5% by weight, more preferable if 3% to 5% by weight, and even more preferable if 3.2% to 5.0% in weight.
    [0036]. In addition, the solder alloy of the present invention can increase the Ni effect according to the present invention by adding Co or Fe or both. In particular, Co exhibits an excellent effect. When Co and Fe are added to the solder alloy of the present invention in a total amount less than 0.001% by weight, the effect of preventing the growth of interfacial cracks through precipitation at the joint interface is not seen, whereas when it is made the addition of an amount greater than 0.1% by weight, the intermetallic compound layer formed by interfacial precipitation has an increased thickness to accelerate crack growth due to vibrations or another factor. Co or Fe, or both, are added according to the present invention in a preferred amount of 0.001% to 0.1% by weight.
    [0037]. As is evident from the description provided above, the solder alloy according to the present invention has excellent thermal cycle characteristics and suppresses the occurrence and propagation of cracks in the weld. Thus, crack growth and propagation are not accelerated, even when the solder alloy is used in an automobile that is used in a state in which it is continuously subject to vibrations, in short, as an alloy within a vehicle. Thus, it appears that the solder alloy according to the present invention, which has especially remarkable characteristics, as described above, is particularly
    Petition 870160078679, of 12/23/2016, p. 22/39
    15/24 suitable for welding an electronic circuit that will be mounted on a car.
    [0038]. The term excellent thermal cycle characteristics as used in the specification refers to a state in which the crack occurrence rate after 3,000 cycles is up to 90%, and the residual shear strength rate after 3,000 cycles, as above, is at minus 30%, even in a thermal cycle test performed at -40 ° C or less and 125 ° C or more.
    [0039]. These characteristics express that the electronic circuit inside a vehicle is not broken, in other words, it is not put into an unusable state or malfunction, even when the solder alloy is used in very strict conditions, as in the previous thermal cycle test. , and the solder alloy is highly reliable as the solder alloy particularly for use in ECU welding. The solder alloy of the present invention also has a high residual shear force rate after the temperature cycle has passed. More specifically, the resistance to external forces, for example, the shear force against external forces that are applied from the outside by a collision, vibrations and the like does not decrease, even after a long period of use. As described above, the solder alloy according to the present invention is a solder alloy that exhibits excellent thermal cycle characteristics, when used more specifically when soldering an electronic circuit inside a vehicle or when soldering an ECU electronic circuit. .
    [0040]. The electronic circuit is a system in which a function is allowed to be fully achieved through an electronic combination of a plurality of electronic parts that have their own functions. Exemplary electronic parts configuring the electronic circuit, as described above, include a chip resistor part, a multiple resistance part, a QFP, a QFN, a
    Petition 870160078679, of 12/23/2016, p. 23/39
    16/24 power, a diode and a capacitor. An electronic circuit is provided incorporating any of these electronic parts on a board for configuring an electronic circuit unit.
    [0041]. According to the present invention, the board configuring the electronic circuit unit, as described above and exemplified by a printed circuit board, is not particularly limited. The plate material is also not particularly limited and an exemplary plate includes a heat resistant plastic plate (for example, FR-4 has a high Tg and a low CTE). The printed circuit board is preferably obtained by treating the Cu (Cu land) burr seam surface with organic substances (OSP materials (Organic Surface Protection)), such as amines and imidazoles.
    [0042]. The lead-free solder according to the present invention is shaped for use in joining the fine solder portions and is generally used in the form of solder paste in reflow soldering, but it can be used as a preform of solder in the shape of a ball, pellet, washer or similar.
    EXAMPLES
    Example 1 [0043]. In Table 1, the liquid state temperature, the SnSb particle size as the initial value and after 1,500 cycles in the temperature cycle test, and the slit rate of the respective solder alloys in Table 1 were measured using the following methods .
    Weld Fusion Test [0044]. Each solder alloy in Table 1 was prepared to measure the solder melting temperature. The solid state temperature was measured by a method according to JIS Z3198-1. The liquid state temperature was not measured by applying JIS Z3198-1, but by the same DSC method (Differential Scanning Calorimetry) as the method of measuring solid state temperature according to JIS
    Petition 870160078679, of 12/23/2016, p. 24/39
    17/24
    Z3198-1. The results are shown in the Liquid state temperature column in Table 1.
    Temperature Cycle Test [0045]. Each solder alloy in Table 1 was atomized to form the solder powder. The solder powder was mixed with the solder by fusion, including pine resin, a solvent, an activator, a thixotropic agent, an organic acid and the like, to prepare the solder paste for each solder alloy. The solder paste was printed on a six-layer printed circuit board (material: FR-4) with a metal mask of 150 pm. Then 3216 chip resistors were assembled by an assembler and subjected to reflow soldering under conditions with a maximum temperature of 235 ° C and a retention time of 40 seconds, thus preparing a test plate. The test plate obtained by welding with each solder alloy was placed in a test apparatus with defined temperature cycles, under conditions of low temperature of -40 ° C, to high temperature + 125 ° C, and a retention time of 30 minutes, removed from the temperature cycle tester after 1,500 cycles following the measurement of the initial value, and observed with an electron microscope with a magnification of 3,500x to measure the average particle size of the SnSb intermetallic compound particles in the Sn matrix of the solder alloy. The results are shown in the Slit Rate and SnSb Particle Size columns in Table 1. In Table 1, * 1 shows that the SnSb intermetallic compound was not observed and the measurement could not be performed, and * 2 indicates that the weld it has a high liquid state temperature and the weld could not be carried out under a reflow condition of 235 ° C.
    Slot Rate [0046]. The occurrence of the crack rate serves to know to what extent the region where cracks occur extends in relation to the assumed crack length. After measuring the size of
    Petition 870160078679, of 12/23/2016, p. 25/39
    18/24 SnSb particle, the crack state was observed using an electron microscope with a magnification of 150x and the total crack length was assumed to measure the crack rate. Slit rate (%) = (total slit length / total slit length assumed) x 100. The total slit length as used here refers to the length of a slit at the time of the complete break. The slit rate is a rate obtained by plunging the total length of a plurality of slits 7 shown in Figure 5 through the length of a path 8 that the slits must follow.
    [0047]. The results are shown in Table 1.
    Table 1
    Solder composition(% by weight) Liquid state temperature SnSb particle size (pm) Sn Ag Ass Ni Sb Bi Initial 1500 cycles Example 1 Balance 1 0.5 0.01 5 - 227 0.5 0.6 Example 2 Balance 3.4 0.7 0.04 1 - 221 0.4 0.6 Example 3 Balance 3.4 0.7 0.04 5 - 227 0.4 0.6 Example 4 Balance 3.4 0.7 0.04 4 4 221 0.5 0.5 Example 5 Balance 3.4 0.7 0.04 5 4 223 0.4 0.5 Example 6 Balance 3.4 0.7 0.04 2 5 217 0.5 0.6 Example 7 Balance 4 1 0.2 5 - 227 0.4 0.6 ComparativeExample 1 Balance 3.4 0.7 0.04 0.1 - 219 *1 *1 ComparativeExample 2 Balance 3.4 0.7 0.04 8 - 245 *2 *2 ComparativeExample 3 Balance 0.3 0.3 0.4 0.2 1 231 *1 *1 ComparativeExample 4 Balance 3 1 0.04 10 - 257 *2 *2
    [0048]. Table 1 reveals that, even after 1,500 cycles in the temperature cycle test, the SnSb crystal grains do not thicken, but remain unchanged from the initial value.
    [0049]. Figure 3 shows the state of an intermetallic compound
    Petition 870160078679, of 12/23/2016, p. 26/39
    19/24
    SnSb 7 in the solder alloy in Example 5, after 3,000 cycles in the temperature cycle test in which it was performed with an electron microscope with a magnification of 3,500x. The SnSb intermetallic compound in Example 5 is thin and is uniformly dispersed in the weld. Therefore, no matter where the weld alloy has the crack, that crack is prevented from entering the SnSb intermetallic compound.
    [0050]. Figure 4 shows the state of the intermetallic compound
    SnSb 7 in the solder alloy in Comparative Example 4, after 3,000 cycles in the temperature cycle test in which it was performed with an electron microscope with a magnification of 3,500x. The SnSb intermetallic compound, in this comparative example, thickens and it is not possible to prevent cracks in the SnSb intermetallic compound.
    Example 2 [0051]. Then, in Table 2, the crack occurrence rate and the residual shear force rate were measured after 3,000 cycles in the temperature cycle test in the respective weld alloys in Table 2. The method of measuring the occurrence rate of gap was the same as used in Table 1, but the number of cycles was changed to 3,000 cycles. The method of measuring the residual shear force rate is as described below.
    Residual Shear Strength Rate [0052]. The residual shear force ratio serves to know the extent to which the force is maintained after the temperature cycle test in relation to the shear force of the weld joint portion in the initial state. The shear strength test was carried out at room temperature, under conditions of a test rate of 6 mm / min and a test height of 50 pm using a STR-1000 joint strength tester.
    [0053]. The results are compiled in Table 2.
    Petition 870160078679, of 12/23/2016, p. 27/39
    20/24
    Table 2
    Solder composition (% by weight) Average account occurrence rate after 3,000 cycles [%] Residual shear force rate after 3,000 cycles [%] Sn Ag Ass Ni Sb Bi Co Faith Example 1 Balance 1.0 0.5 0.01 5.0 - - - 79.0 25.0 Example 2 Balance 3.4 0.7 0.04 1.0 - - - 87.0 40.0 Example 3 Balance 3.4 0.7 0.04 5.0 - - - 72.0 31.8 Example 5 Balance 3.4 0.7 0.04 5.0 4.0 - - 59.0 54.5 Example 4 Balance 3.4 0.7 0.04 4.0 4.0 - - 63.0 60.0 Example 6 Balance 3.4 0.7 0.04 2.0 5.0 - - 78.0 49.0 Example 7 Balance 4.0 1.0 0.2 5.0 - - - 74.0 31.0 Example 8 Balance 1.0 0.6 0.01 5.0 - - - 85.0 30.0 Example 9 Balance 3.4 0.7 0.04 1.0 1.5 - - 86.0 33.6 Example 10 Balance 3.4 0.7 0.04 1.0 3.0 - - 84.0 41.6 Example 11 Balance 3.4 0.7 0.04 1.0 3.2 - - 84.0 43.6 Example 12 Balance 3.4 0.7 0.04 1.0 3.5 - - 82.0 41.6 Example 13 Balance 3.4 0.7 0.04 1.0 5.0 - - 80.0 39.2 Example 14 Balance 3.4 0.7 0.04 1.0 5.5 - - 82.0 36.6 Example 15 Balance 3.4 0.7 0.04 2.0 - - - 85.0 41.7 Example 16 Balance 3.4 0.7 0.04 2.0 1.5 - - 84.0 48.0 Example 17 Balance 3.4 0.7 0.04 2.0 2.5 - - 82.0 50.0 Example 18 Balance 3.4 0.7 0.04 2.0 3.0 - - 82.0 49.5 Example 19 Balance 3.4 0.7 0.04 2.0 3.2 - - 82.0 49.3 Example 20 Balance 3.4 0.7 0.04 2.0 3.5 - - 80.0 49.1 Example 21 Balance 3.4 0.7 0.04 2.0 5.5 - - 80.0 47.0 Example 22 Balance 3.4 0.7 0.04 3.0 - - - 82.0 38.0 Example 23 Balance 3.4 0.7 0.04 3.0 1.5 - - 78.0 55.0 Example 24 Balance 3.4 0.7 0.04 3.0 3.0 - - 70.0 63.0 Example 25 Balance 3.4 0.7 0.04 3.0 3.2 - - 65.0 65.0 Example 26 Balance 3.4 0.7 0.04 3.0 3.5 - - 68.0 63.0 Example 27 Balance 3.4 0.7 0.04 3.0 5.0 - - 73.0 60.6 Example 28 Balance 3.4 0.7 0.04 3.0 5.5 - - 75.0 58.0
    Petition 870160078679, of 12/23/2016, p. 28/39
    21/24
    Solder composition (% by weight) Average account occurrence rate after 3,000 cycles [%] Residual shear force rate after 3,000 cycles [%] Sn Ag Ass Ni Sb Bi Co Faith Example 29 Balance 3.4 0.7 0.04 4.0 - - - 78.0 35.0 Example 30 Balance 3.4 0.7 0.04 4.0 1.5 - - 74.0 45.0 Example 31 Balance 3.4 0.7 0.04 4.0 2.5 - - 73.0 53.0 Example 32 Balance 3.4 0.7 0.04 4.0 3.0 - - 66.0 54.0 Example 33 Balance 3.4 0.7 0.04 4.0 3.2 - - 61.0 55.0 Example 34 Balance 3.4 0.7 0.04 4.0 3.5 - - 64.0 58.0 Example 35 Balance 3.4 0.7 0.04 4.0 5.0 - - 69.0 55.0 Example 36 Balance 3.4 0.7 0.04 4.0 5.5 - - 71.0 48.0 Example 37 Balance 3.4 0.7 0.04 5.0 1.5 - - 65.5 45.0 Example 38 Balance 3.4 0.7 0.04 5.0 2.0 - - 65.0 50.0 Example 39 Balance 3.4 0.7 0.04 5.0 3.0 - - 54.0 51.0 Example 40 Balance 3.4 0.7 0.04 5.0 3.2 - - 49.0 52.0 Example 41 Balance 3.4 0.7 0.04 5.0 3.5 - - 52.0 53.0 Example 42 Balance 3.4 0.7 0.04 5.0 5.0 - - 57.0 57.5 Example 43 Balance 3.4 0.7 0.04 5.0 5.5 - - 59.0 54.9 Example 44 Balance 3.4 0.7 0.04 3.0 3.2 0 - 65.0 65.0 Example 45 Balance 3.4 0.7 0.04 3.0 3.2 0.008 - 58.0 72.0 Example 46 Balance 3.4 0.7 0.04 3.0 3.2 0.05 - 60.0 70.0 Example 47 Balance 3.4 0.7 0.04 3.0 3.2 0.008 0.008 54.0 71.0 ComparativeExample 5 Balance 3.4 0.7 0.04 5.0 7.0 - - 65.0 45.9 ComparativeExample 6 Balance 0.9 0.4 0.009 0.9 - - - 100.0 8.0 ComparativeExample 7 Balance 3.4 0.7 0.04 - - - - 100.0 1.6 ComparativeExample 8 Balance 3.4 0.7 0.04 - 1.5 - - 96.0 13.6 ComparativeExample 9 Balance 3.4 0.7 0.04 - 3.0 94.0 21.6
    Petition 870160078679, of 12/23/2016, p. 29/39
    22/24
    Solder composition (% by weight) Average account occurrence rate after 3,000 cycles [%] Residual shear force rate after 3,000 cycles [%] Sn Ag Ass Ni Sb Bi Co Faith ComparativeExample 10 Balance 3.4 0.7 0.04 - 3.2 - - 94.0 23.6 ComparativeExample 11 Balance 3.4 0.7 0.04 - 3.5 - - 92.0 21.6 ComparativeExample 12 Balance 3.4 0.7 0.04 - 5.0 - - 90.0 19.2 ComparativeExample 13 Balance 3.4 0.7 0.04 - 5.5 - - 92.0 16.6 ComparativeExample 14 Balance 3.4 0.7 0.04 - 7.0 - - 99.0 7.6 ComparativeExample 15 Balance 3.4 0.7 0.04 0.5 - - - 97.0 13.0 ComparativeExample 16 Balance 3.4 0.7 0.04 1.0 7.0 - - 89.0 27.6 ComparativeExample 17 Balance 3.4 0.7 0.04 2.0 7.0 - - 87.0 38.0 ComparativeExample 18 Balance 3.4 0.7 0.04 3.0 7.0 - - 81.0 49.0 ComparativeExample 19 Balance 3.4 0.7 0.04 4.0 7.0 - - 77.0 39.0 ComparativeExample 20 Balance 3.4 0.7 0.04 7.0 - - - 97.0 3.0 ComparativeExample 21 Balance 3.4 0.7 0.04 7.0 1.5 - - 93.0 20.0 ComparativeExample 22 Balance 3.4 0.7 0.04 7.0 3.0 - - 90.0 28.0 ComparativeExample 23 Balance 3.4 0.7 0.04 7.0 3.2 - - 89.0 29.0 ComparativeExample 24 Balance 3.4 0.7 0.04 7.0 3.5 - - 89.0 28.0
    Petition 870160078679, of 12/23/2016, p. 30/39
    23/24
    Solder composition (% by weight) Average account occurrence rate after 3,000 cycles [%] Residual shear force rate after 3,000 cycles [%] Sn Ag Ass Ni Sb Bi Co Faith ComparativeExample 25 Balance 3.4 0.7 0.04 7.0 5.0 - - 90.0 25.6 ComparativeExample 26 Balance 3.4 0.7 0.04 7.0 5.5 - - 90.0 23.0 ComparativeExample 27 Balance 3.4 0.7 0.04 7.0 7.0 - - 96.0 14.0 ComparativeExample 28 Balance 3.4 0.7 0.04 1.0 - 0.15 - 94.0 25.0 ComparativeExample 29 Balance 3.8 0.7 0.2 1.0 2.0 - - 95.0 *2 ComparativeExample 30 Balance 4.1 1.1 0.3 8.0 - - - *2 1.0
    [0054]. Figure 6 shows a graph in which the crack occurrence rate and the residual shear force rate in relation to the Sb content in the weld alloys based on Sn-Ag-Cu-Ni-Sb are plotted in Table 2. When the Sb content is in the range of 1.0% to 5.0% according to the present invention, the crack occurrence rate is up to 90% and the residual shear force rate is 30% or more , and the solder alloy obtained according to the present invention has excellent temperature cycle characteristics and is resistant to the impact of a collision or the like.
    [0055]. Figure 7 shows a graph in which the crack occurrence rate is plotted on the basis of Sb content in relation to the Bi content in the weld alloys based on Sn-Ag-Cu-Ni-Sb-Bi in Table 2. When the Bi content is in the range of 1.5% to 5.5% according to the present invention, and the Sb content is 1% to 5%, the rate of crack occurrence is up to 90%, and the temperature cycle characteristics are excellent and the
    Petition 870160078679, of 12/23/2016, p. 31/39
    24/24 occurrence of cracks can be suppressed.
    [0056]. Figure 8 shows a graph in which the residual shear force rate is plotted on the basis of Sb content in relation to the Bi content in the weld alloys based on Sn-Ag-Cu-Ni-Sb-Bi in Table 2 When the Bi content is in the range of 1.5% to 5.5% according to the present invention, and the Sb content is 1% to 5%, the residual shear force rate is 30% or more. The weld alloys are resistant to the impact of a collision or the like and the occurrence of cracks can be suppressed.
    [0057]. Consequently, in the solder alloy according to the present invention, the SnSb crystal grains do not thicken, but remain unchanged from the initial value, even under strict temperature conditions ranging from -40 ° C to + 125 ° C, which they are necessary for the substrate of the automobile ECU, and as a result, the occurrence of cracks which can occur from inside the weld, in comparison with other weld alloys, can also be reduced.
    Industrial Applicability [0058]. The lead-free solder alloy according to the present invention can be a weld that has a shape not only for melt welding, but also for melt welding, such as an ingot shape, a bar shape or a linear shape, or a rosin core weld having a manual weld shape.
    权利要求:
    Claims (11)
    [1]
    1. Lead-free solder alloy characterized by the fact that it comprises:
    1% to 4% by weight of Ag;
    0.6% to 0.8% by weight of Cu;
    3% to 5% by weight of Sb;
    0.01% to 0.2% by weight of Ni;
    5% to 5.5% by weight of Bi;
    optionally 0.001 to 0.1% despite Co; and a balance of Sn.
    [2]
    2. WELDING ALLOY according to claim 1, characterized by the fact that it comprises Co in a total amount of 0.001% to 0.1% by weight.
    [3]
    3. WELDING ALLOY according to claim 1 or 2, characterized by the fact that it comprises Ag in a total amount of 3.2% to 3.8% by weight.
    [4]
    4. WELDING ALLOY according to either of claims 1 or 3, characterized by the fact that a residual shear force rate after 3,000 cycles of a temperature cycle test in relation to an initial value is 30% or more.
    [5]
    5. WELDING ALLOY according to any one of claims 1 to 4, characterized by the fact that the solder alloy is joined to a plate that has been subjected to a Cu-OSP process.
    [6]
    6. ELECTRONIC CIRCUIT IN A VEHICLE characterized by the fact that it comprises a portion of the solder joint, composed of the solder alloy as defined by one of claims 1 to 5.
    [7]
    7. ELECTRONIC CIRCUIT ECU characterized by the fact that it comprises a portion of solder joint, composed of the lead-free solder alloy as defined by one of claims 1 to 5.
    [8]
    8. ELECTRONIC CIRCUIT UNIT IN A VEHICLE
    Petition 870190126388, of 12/02/2019, p. 15/33
    2/2 characterized by the fact that it comprises the electronic circuit as defined by claim 6.
    [9]
    9. ECU ELECTRONIC CIRCUIT UNIT characterized by the fact that it comprises an electronic ECU circuit as defined by claim 7.
    [10]
    10. USE OF WELDING ALLOY as defined by claims 1 to 5, characterized by the fact that it is for a solder joint portion of an electronic circuit in a vehicle.
    [11]
    11. USE according to claim 10, characterized by the fact that the 5, characterized by the fact that the lead-free solder alloy is used for reflow soldering, especially for two-sided reflow soldering.
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    同族专利:
    公开号 | 公开日
    JP5811304B2|2015-11-11|
    KR102038189B1|2019-10-29|
    EP2982469B1|2019-01-09|
    KR20160148036A|2016-12-23|
    EP2982469A1|2016-02-10|
    PT2982469T|2019-04-23|
    EP2982469A4|2016-06-29|
    BR112015025125A2|2017-07-18|
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    US20160056570A1|2016-02-25|
    HUE042401T2|2019-06-28|
    PH12015502283A1|2016-02-01|
    KR20150126385A|2015-11-11|
    JP2015077601A|2015-04-23|
    MY158373A|2016-09-26|
    ES2718523T3|2019-07-02|
    MX2015013942A|2017-07-28|
    JPWO2014163167A1|2017-02-16|
    CN105142856A|2015-12-09|
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    法律状态:
    2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-03| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-02-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-03-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/04/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2013-077289|2013-04-02|
    JP2013077289A|JP2015077601A|2013-04-02|2013-04-02|Lead-free solder alloy|
    PCT/JP2014/059902|WO2014163167A1|2013-04-02|2014-04-03|Lead-free solder alloy and in-vehicle electronic circuit|
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