JPWO2015129840A1 - Soldering method and automotive glass - Google Patents

Abstract

Automotive glass and soldering method capable of preventing cracks from occurring over time when soldering one surface of a metal terminal to a silver electrode formed on an automotive glass substrate using a solder alloy and flux I will provide a. The metal terminal is copper or brass, and soldering is performed by setting the ratio of the area of the flux applied on the silver electrode before soldering to the area of one surface of the metal terminal in the range of 3 to 20: 1. .

Description

  The present invention relates to a soldering method for soldering one surface of a metal terminal to a silver electrode formed on an automotive glass substrate using a solder alloy and a flux, and an automotive glass on which the metal terminal is soldered. .

  In recent years, heating wires have been formed on rear glass and the like used in automobiles to prevent fogging, and metal terminals are connected to such heating wires in order to supply current. More specifically, the heating wire is a conductive film containing silver formed on glass, and metal terminals are connected to the conductive film by soldering.

  However, when the metal terminal is soldered to the glass substrate in this way, the glass substrate cracks with time if exposed to a predetermined temperature change due to a difference in thermal expansion coefficient between the solder alloy and the glass. There was a problem.

  On the other hand, Cited Document 1 discloses a solder alloy capable of preventing the glass substrate from cracking and maintaining good bonding strength even when exposed to high or low temperatures.

JP 2012-91216 A

  On the other hand, the inventor has repeated experiments and confirmed that the above-described cracking in the glass substrate can be prevented not only by the composition of the solder alloy but also by the improvement of the soldering method.

  The present invention has been made by the inventor paying attention to the above, and the object of the present invention is to provide a metal terminal on a silver electrode formed on a glass substrate for an automobile using a solder alloy and a flux. In the soldering of one surface, the metal terminal contains copper or brass, and the ratio of the area of the flux applied on the silver electrode before soldering to the area of the one surface of the metal terminal is 3-20. An object of the present invention is to provide an automotive glass and a soldering method capable of preventing the above-described cracking in the glass substrate by performing soldering in a range of: 1.

  The soldering method according to the present invention is a soldering method in which one surface of a metal terminal is soldered to a silver electrode formed on a glass substrate for an automobile using a solder alloy and a flux. Including brass, the ratio of the area of the flux applied on the silver electrode before soldering to the area of one surface of the metal terminal is in the range of 3 to 20: 1.

  In the present invention, the metal terminal contains copper or brass, and the ratio of the area of the flux to the area of the one surface of the metal terminal is 3 to 20: 1 on the glass substrate for an automobile. One surface of the metal terminal is soldered to the formed silver electrode.

  The soldering method according to the present invention is characterized in that the solder alloy is melted using a soldering iron, hot air, infrared rays, resistance, or high frequency.

  In the present invention, one surface of the metal terminal is soldered to the silver electrode formed on the glass substrate for an automobile by melting the solder alloy using a soldering iron, hot air, infrared rays, resistance, or high frequency. Is done.

  The soldering method according to the present invention is characterized in that the metal terminal is plated with tin or a tin alloy, or is not subjected to a surface treatment.

  In the present invention, the metal terminal to be soldered onto the glass substrate for automobiles may have a surface plated with tin or tin alloy, or not subjected to surface treatment. It may be a thing.

  The soldering method according to the present invention is characterized in that the solder alloy contains tin and one or more of silver, zinc, bismuth, and lead.

  In the present invention, the solder alloy used when soldering the metal terminal on the glass substrate for automobile contains tin and one or more of silver, zinc, bismuth, and lead. To do.

  The soldering method according to the present invention is characterized in that the flux applied before soldering is not removed after soldering.

  In the present invention, when the metal terminal is soldered on the glass substrate for automobiles, the flux applied on the glass substrate (silver electrode) is left as it is without being removed after the soldering.

The soldering method according to the present invention is characterized in that a solder alloy amount of 0.18 to 1.43 g / cm ² is used for one surface of the metal terminal.

In this invention, when soldering the said metal terminal on the glass substrate for motor vehicles, the amount of 0.18-1.43g / cm < ² > of solder alloys is used with respect to the one surface of the said metal terminal.

  The soldering method according to the present invention is characterized in that the soldering temperature is higher by 20 ° C. to 200 ° C. than the liquidus temperature of the solder alloy.

  In the present invention, when the metal terminals are soldered onto the glass substrate for automobiles, the soldering is performed at a soldering temperature 20 ° C. to 200 ° C. higher than the liquidus temperature of the solder alloy.

  An automotive glass according to the present invention is an automotive glass in which one surface of a metal terminal is soldered to a silver electrode formed on one surface using a solder alloy and a flux, and the metal terminal is made of copper or brass. In addition, the ratio of the area of the flux applied onto the silver electrode before soldering and the area of one surface of the metal terminal is in the range of 3 to 20: 1.

  In the present invention, the metal terminal contains copper or brass, and the ratio of the area of the flux on the glass substrate for automobile (silver electrode) and the area of one surface of the metal terminal is 3 to 20: 1. .

  In the automotive glass according to the present invention, the metal terminal is subjected to a plating treatment of tin or a tin alloy, or is not subjected to a surface treatment.

  In the present invention, the metal terminal to be soldered onto the glass substrate for automobiles may have a surface plated with tin or tin alloy, or not subjected to surface treatment. It may be a thing.

  The automotive glass according to the present invention is characterized in that the solder alloy contains tin and one or more of silver, zinc, bismuth, and lead.

  In the present invention, the metal terminal is soldered onto an automotive glass substrate using a solder alloy containing tin and one or more of silver, zinc, bismuth, and lead. ing.

The glass for automobiles according to the present invention is characterized in that a solder alloy amount of 0.18 to 1.43 g / cm ² is used for one surface of the metal terminal.

In this invention, the said metal terminal is soldered on the glass substrate for motor vehicles using the amount of solder alloys of 0.18-1.43g / cm < ² > with respect to the one surface.

  ADVANTAGE OF THE INVENTION According to this invention, when a metal terminal is soldered to the glass substrate for motor vehicles, even if it is a case where it is a case where it is exposed to a predetermined temperature change, it can prevent that a glass plate cracks with time progress.

It is a perspective view which shows the metal terminal used for the soldering method which concerns on this invention. It is a fragmentary sectional view explaining the joining state of the metal terminal joined by the soldering method concerning an embodiment, and a glass substrate. It is explanatory drawing explaining the soldering method which concerns on embodiment.

  In the soldering method according to the present invention, Sn-Zn solder alloy is used to solder metal terminals on a glass substrate for automobiles coated with silver electrodes under certain conditions. Below, the soldering method which concerns on embodiment is explained in full detail based on drawing.

  The composition of the Sn—Zn solder alloy used in the soldering method according to the present invention is 8% by mass of Zn and 0.005% by mass of Mn, with the balance being Sn and inevitable impurities.

  Further, the solder alloy according to the present invention is not limited to the Sn—Zn solder alloy described above. For example, an alloy containing tin and one or more of silver, zinc, bismuth, and lead may be used.

  FIG. 1 is a perspective view showing a metal terminal used in the soldering method according to the present invention. Reference numeral 1 in the figure denotes a metal terminal. The metal terminal 1 is made of, for example, copper or brass.

  The metal terminal 1 is divided into two parts, and a part 11 has an L-shape in vertical section and is in contact with the other part 12. The portion 11 has a plate-like joint portion 111 parallel to a glass substrate (not shown), and a vertical portion 112 extending in a direction perpendicular to the joint portion 111 from the side edge of the other portion 12 of the joint portion 111. Yes. The vertical portion 112 is in contact with the other portion 12 at the surface on the other portion 12 side. The joining part 111 has the joining surface 113 joined to this glass substrate by soldering on the side facing the glass substrate.

  Further, the other portion 12 has a step portion 124 formed with a step of the glass, and the step portion 124 is bonded to the glass substrate by soldering on the side facing the glass substrate. 123. Further, the joining portion 121 has a vertical portion 122 extending from the edge in a direction perpendicular to the joining portion 121 on the other end side, and a strip extending substantially parallel to the joining portion 121 at the end of the vertical portion 122. A flat portion 125 is extended. The vertical portion 122 is in contact with the vertical portion 112 of the portion 11. That is, the vertical part 121 of the part 11 and the vertical part 122 of the other part 12 are in contact with each other.

  The metal terminal 1 may be plated with tin or tin alloy, or may not be subjected to surface treatment.

Furthermore, the glass substrate is made of SiO _2. Is a commercially available plate glass. As for this glass substrate, the predetermined range of the one surface where the metal terminal 1 is joined is coat | covered with the electrode of silver.

  In the soldering method according to the embodiment, the joining surfaces 113 and 123 of the metal terminal 1 are joined to one surface of the glass substrate by soldering using a Sn—Zn solder alloy.

  In the soldering method according to the embodiment, the solder alloy is melted using a soldering iron. At this time, the temperature of the soldering iron is 20 to 200 ° C. higher than the liquidus temperature of the solder alloy. The present invention is not limited to this. In addition to a soldering iron, soldering may be performed using any one of hot air, infrared rays, resistance, or high frequency.

  That is, when using a soldering iron, the temperature of the soldering iron is heated and soldered with a soldered solder alloy, and when using hot air, infrared rays, resistance, high frequency, etc. The temperature at which the joint is heated and the solder alloy is melted to solder the component or the like is 20 to 200 ° C. higher than the liquidus temperature of the solder alloy.

For example, in this embodiment, the Sn—Zn solder alloy as described above is used as the solder alloy, and the soldering iron temperature is 260 ° C. or 320 ° C. The metal terminal 1 contains copper or brass, and the amount of solder alloy (hereinafter, the amount of alloy per unit area) with respect to the joining surfaces 113 and 123 of the metal terminal 1 is 1.18 g / cm ² .

However, the present invention is not limited to this. The alloy amount per unit area may be a solder alloy amount of 0.18 to 1.43 g / cm ^{2 with} respect to the joint surfaces 113 and 123 of the metal terminal 1.

  FIG. 2 is a partial cross-sectional view for explaining a joined state of the metal terminal 1 and the glass substrate 4 joined by the soldering method according to the embodiment.

  As described above, the film-like silver electrode 3 is formed on one surface of the glass substrate 4, and the flux film 5 is applied on the silver electrode 3. The metal terminal 1 is joined via the silver electrode 3 and the solder alloy 2. More specifically, the silver electrode 3, the flux film 5 and the Sn—Zn solder alloy 2 are interposed in this order between the bonding surfaces 113 and 123 of the glass substrate 4 and the metal terminal 1. However, this embodiment is an example of the present invention. For example, a configuration in which a ceramic layer is present between the glass substrate 4 and the silver electrode 3 may be used.

  As the flux film 5, any one of four types of fluxes, flux A, flux B, flux C, and flux D, is used. Of these four types of fluxes, the flux B is a general-purpose flux, the flux A is specialized for wettability with respect to the silver electrode 3, and the fluxes C and D are further improved from A. The compositions of A to D are shown in Table 1.

Examples of rosins listed in Table 1 include modified rosins, gum rosins, and hydrogenated rosins, and these may be mixed.
The thixotropic agents listed in Table 1 are fatty acid amides or hydrogenated castor oil, halogens are amine chlorides or bromides and fluorine compounds, and organic acids are dicarboxylic acids such as adipic acid or succinic acid, or monocarboxylic acids such as lauric acid. Examples of the acid and the solvent include pentadiol and butyl carbitol.
As other components, cationic or nonionic surfactants or resins such as vinyl acetate copolymers may be blended.

  In the present invention, the flux film 5 occupies a specific area on the silver electrode 3. More specifically, the ratio of the area occupied by the flux film 5 on the silver electrode 3 (hereinafter referred to as the area of the flux) and the area of the bonding surfaces 113 and 123 of the metal terminal 1 is 3 to 20: 1. It is. In the following description, the ratio between the area of the flux and the area of the joint surfaces 113 and 123 of each metal terminal 1 is simply referred to as a flux area ratio.

<Soldering method>
Hereinafter, the soldering method according to the embodiment will be described in detail. FIG. 3 is an explanatory view for explaining a soldering method according to the embodiment of the present invention.

First, an appropriate amount of the solder alloy 2 is placed on the joining surfaces 113 and 123 of the metal terminal 1, and the solder alloy 2 is joined using the flux B with a soldering iron at 250 ° C. As a result, welding is performed so that the solder alloy 2 is deposited on the joint surfaces 113 and 123. At this time, the amount of the solder alloy per unit area is in the range of 0.18 to 1.43 g / cm ² as described above, for example, 1.18 / cm ² or 1.43 g / cm ² . .

  Next, flux A, flux B, flux C, or flux D is applied to a predetermined region on the silver electrode 3 of the glass substrate 4. Such a predetermined region has a flux area ratio in the range of 3 to 20: 1, for example, 4.5, 18, and 20.

  Subsequently, as shown in FIG. 3, the metal terminal 1 is placed on the flux film 5 of the glass substrate 4 so that the solder alloy 2 bonded to the bonding surfaces 113 and 123 faces the glass substrate 4 side. Then, the side surface opposite to the bonding surface 113 in the bonding portion 111 and the side surface opposite to the bonding surface 123 in the stepped portion 124 are heated with the soldering iron 10 or the like to melt the solder alloy 2 and bond to the silver electrode 3. (See FIG. 3). At this time, the heating temperature is, for example, 260 ° C. or 320 ° C.

  Thereafter, a process of removing the remaining flux is generally performed, but in the soldering method according to the present invention, the flux applied on the silver electrode 3 is not removed but is left as it is.

  This is because it was observed that the application area of the flux, that is, the flux area ratio, affects the cracking of the glass substrate, as will be described later. More specifically, the higher the flux area ratio, the less likely the glass substrate will crack. Through the flux, the heat of the soldering iron (or molten solder alloy) is dispersed over a wide area of the glass substrate 4 and the silver electrode 3 and can be prevented from being concentrated locally. This is thought to be because it can be prevented.

  Next, air cooling is performed at room temperature, and the joining by the soldering method according to the embodiment is completed, and the metal terminal 1 is joined to the glass substrate 4 as shown in FIG. Is obtained.

<Evaluation>
A heat cycle test was performed using the sample prepared by the soldering method as described above.

  Such a heat cycle test was carried out by repeating the cycle for each sample, which was held at −30 ° C. for 30 minutes and then held at 80 ° C. for 30 minutes as one cycle. Further, in the process of repeating the cycle, the occurrence of cracks in the glass substrate was observed with the naked eye, and when the occurrence of cracks was observed, the number of cycles repeated until the occurrence of cracks was counted.

  Table 2 shows the results of the heat cycle test for the sample (Example) created by the soldering method according to the present invention and the comparative example. The case where the number of heat cycles was less than 300 and cracks occurred in the glass substrate was “X”, and the case where the number of heat cycles was 300 or more was “◯”.

In the soldering according to the comparative example, the solder alloy is Sn-Zn solder alloy (LF-Z3: Zn-8.0 mass%, Mn-0.005 mass%, Sn-balance), Sn5Sb, or Zn6Al. Yes, the metal terminal contains copper or brass, and the temperature of the soldering iron at the time of soldering is 260 ° C., 310 ° C., 320 ° C. or 450 ° C. The alloy amount per unit area is 0.14 to 1.18 g / cm ² , and the flux area ratio is less than 3 or 18. Further, flux A is used as the flux.

As can be seen from Table 2, in the sample of the comparative example in which the material of the metal terminal is brass, the temperature of the soldering iron is 310 ° C. or 260 ° C., and the flux area ratio is less than 3, the alloy per unit area In the range of 0.14 to 1.18 g / cm ² , all the samples have already been cracked in the heat cycle of less than 300 times.

On the other hand, in the sample of the example in which the material of the metal terminal is brass, the temperature of the soldering iron is 260 ° C. or 320 ° C., and the amount of alloy per unit area is 1.18 g / cm ² , the flux area In any of the ratios 4.5, 18, and 20, the number of heat cycles exceeded 300 times, and it was confirmed that the product had excellent quality. In particular, in the sample of the example where the flux area ratio is 20, the glass substrate does not crack even after the heat cycle of 300 times or more, and has a very excellent quality.

Further, a copper material of the metal terminals are soldered by a soldering iron or hot air 320 ° C., and the alloy weight per unit area is 1.18 g / cm ² or 1.43 g / cm ² Example In this sample, when the flux area ratio was 18, it was confirmed that the glass substrate did not crack even after the heat cycle was repeated 300 times or more and had excellent quality.

  In particular, when the results according to Comparative Examples 10 and 11 are compared with the results according to Example 16, the other sample preparation conditions are the same except for the composition of each sample. Shows different test results. That is, the samples according to Comparative Examples 10 and 11 are Sn5Sb and Zn6Al, respectively, and any of the samples has already cracked in the glass substrate in a heat cycle of less than 300 times. On the other hand, the sample which concerns on Example 16 is Sn3Ag0.5Cu, and has shown the outstanding quality in which the frequency | count of a heat cycle exceeds 300 times.

  The samples according to Comparative Examples 10 and 11 contain tin and zinc, respectively, while the sample according to Example 16 further contains silver in addition to tin. From such test results, it is understood that the effect according to the present invention can be reliably obtained in a solder alloy containing tin as an essential component and further containing one or more of silver, zinc, bismuth, and lead. .

  In Examples 14 and 15, only the soldering method is different, and the other sample preparation conditions are the same. The soldering method of Example 14 is a trowel and the soldering method of Example 15 is hot air, but each sample shows excellent quality in which the number of heat cycles exceeds 300. That is, the effect according to the present invention can be obtained even when soldering is performed using hot air, infrared rays, resistance, high frequency or the like in addition to a soldering iron.

  And in Example 14 and Examples 17-19, only the kind (composition) of the used flux differs, and other sample preparation conditions are the same. In Example 14 and Examples 17 to 19, Flux A, Flux B, Flux C and Flux D are used, respectively, but all samples show excellent quality in which the number of heat cycles exceeds 300 times. . That is, even when any of the above-described fluxes is used, the effect according to the present invention can be obtained.

  As for the flux area ratio, the effect according to the present invention can be obtained even at 20 or more. However, in view of the appearance of automotive glass, the flux area ratio is preferably in the range of 3 to 20: 1.

  As described above, any sample according to the example has good quality regardless of the type of flux used. Furthermore, as can be seen from Table 2, as the flux area ratio increases, the number of heat cycles increases and the cracking of the glass substrate is improved.

DESCRIPTION OF SYMBOLS 1 Metal terminal 3 Silver electrode 4 Glass substrate 10 Soldering iron 113,123 Joining surface (one side)

Claims (11)

  In a soldering method of soldering one surface of a metal terminal to a silver electrode formed on a glass substrate for an automobile using a solder alloy and a flux, the metal terminal includes copper or brass, and before the soldering, the metal terminal A soldering method, wherein the ratio of the area of the flux applied on the silver electrode to the area of one surface of the metal terminal is in the range of 3 to 20: 1.   The soldering method according to claim 1, wherein the solder alloy is melted using a soldering iron, hot air, infrared rays, resistance, or high frequency.   The soldering method according to claim 1, wherein the metal terminal is plated with tin or a tin alloy, or is not subjected to a surface treatment.   4. The soldering method according to claim 1, wherein the solder alloy contains tin and one or more of silver, zinc, bismuth, and lead.   The soldering method according to claim 1, wherein the flux applied before soldering is not removed after soldering. The soldering method according to claim 1, wherein a solder alloy amount of 0.18 to 1.43 g / cm ² is used for one surface of the metal terminal.   The soldering method according to claim 1, wherein the soldering temperature is 20 ° C. to 200 ° C. higher than the liquidus temperature of the solder alloy. In automotive glass, one side of a metal terminal is soldered to a silver electrode formed on one side using a solder alloy and flux.
The metal terminal includes copper or brass, and the ratio of the area of the flux applied on the silver electrode before soldering to the area of one surface of the metal terminal is in the range of 3 to 20: 1. Automotive glass.   The glass for automobile according to claim 8, wherein the metal terminal is plated with tin or tin alloy, or is not subjected to surface treatment.   The automotive glass according to claim 8 or 9, wherein the solder alloy contains tin and one or more of silver, zinc, bismuth, and lead. The automotive glass according to claim 8, wherein an amount of solder alloy of 0.18 to 1.43 g / cm ² is used for one surface of the metal terminal.

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