Patent Description:
A vehicle glass assembly comprising a glass substrate layer, an electrically conductive layer applied over the window glass, and a harness connected to the conductive layer has been used as a vehicle glass window. Although the harness has been connected to the conductive layer by soldering the conductive layer and an electrical connector of the harness with a lead-containing solder, the End of Life Vehicles Directive <NUM>/<NUM>/EC urges the use of lead-free solders instead.

The use of lead-free solders has led to difficulties in compensating mechanical stresses between the glass substrate layer and the electrical connector, resulting in the occurrence of cracks in the vehicle glass assembly. The mechanical stress may be affected by a junction structure consisting of the solder, the conductive layer and electrical connector. In order to solve the problem, <CIT> and <CIT> disclose glass assemblies having a glass substrate layer and an electrical connection using a connection element made of chromium-containing steel. The connection element has a region which is crimped about a wire cable and connected to the conductive layer, over the glass substrate layer, using lead-free solder.

<CIT> and <CIT> assume that the shape and the material of the connection element are of critical significance with regard to avoiding mechanical stress due to thermal history. According to those prior art documents, the connector made of chromium-containing steel seems to match thermal expansion between the glass substrate layer and the connector better than a copper-based connector, resulting in a reduction of mechanical stress. Although the connector made of chromium-containing steel might bring less mechanical stress than a copper-based connector, the factors to reduce the occurrence of cracks in the window glass are still unclear.

It is an aim herein to provide new and useful methods for producing vehicle glass assemblies comprising an electrically conductive layer over a glass substrate layer, and in which an electrical connector is soldered by lead-free solder onto the conductive layer.

According to one aspect of the present invention, there is provided a method of producing a vehicle glass assembly as defined in claim <NUM>.

We find that when producing vehicle glass assemblies using the above method, mechanical stress between the glass substrate layer and the electrical connector can be relaxed or reduced, and crack occurrence in the glass substrate layer decreased.

In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide an understanding of certain embodiments of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known devices, processes, techniques, and methods are omitted so as not to obscure the description with unnecessary detail. We refer now more particularly to the accompanying drawings, in which like reference numerals indicate like parts/elements throughout the several views.

For better understanding of the present invention, the present invention is described using figures. <FIG> is a schematic view of an embodiment of vehicle glass assembly made by the present invention. <FIG> shows the cross-section of <FIG> at X-Y. In accordance with typical embodiments of the present invention, a vehicle glass assembly <NUM> comprises a glass substrate layer <NUM>, an optional coloured ceramic band <NUM> sintered on a peripheral portion of the glass substrate layer <NUM>, an electrically conductive layer <NUM> which comprises a connecting terminal 3a and an electrically conductive wire pattern 3b sintered on the glass substrate layer <NUM> and/or on the coloured ceramic band <NUM>, a lead-free solder layer <NUM> on the conductive layer <NUM>, and a harness <NUM> which comprises a connector 5a made of a metal plate, metal wire 5b such as copper wire, and an envelope or sheath 5c covering the metal wire. A solder connection is formed between the connector 5a and the electrically conductive layer <NUM> via the lead-free solder layer <NUM>. <FIG> and <FIG> relate to steps (A), (B) and (C), and details are described below.

The vehicle glass assembly <NUM> is produced by a production method comprising:.

If the amount of lead-free solder is smaller than <NUM>, it becomes difficult to achieve enough soldered area at the connecting terminal 3a, resulting in a weaker solder connection. On the other hand, if the amount is larger than <NUM>, the compensation of mechanical stresses between the glass substrate layer <NUM> and the connector 5a may be inadequate, resulting in the occurrence of cracks in the glass substrate layer <NUM>, the conductive layer <NUM>, and/or in the coloured ceramic band <NUM>. In the light of these factors, the amount may typically be between <NUM> and <NUM>, preferably between <NUM> and <NUM>.

In the solder connection, if the lead-free solder is spilled out from a space between the flat portions 5d and the connecting terminal 3a, such structure may provide a mechanical stress between the glass substrate layer and the electrical connector. Therefore, not only the block amount but also soldered position on the flat portion 5d at the step A) is important. Thus, at the step (A), the harness <NUM> in which the block 4p is soldered onto the flat portion 5d so as to be away from all edges of the flat portion 5d is used. Through the steps, the vehicle glass assembly <NUM> comes to comprise solder connection in which all lead-free solder is disposed between the flat portions 5d and the connecting terminal 3a. Further, the vehicle glass assembly <NUM> may comprise solder connection in which all lead-free solders recess from all edges of the flat portion 5d, in order that the lead-free solder is certainly not spilled out from the space.

<FIG> is a schematic view showing a harness in the state after step (A). The block 4p made of lead-free solder is soldered onto the flat portion 5d of the connector 5a. The flat portion 5d is made of metal plate; preferably in general the entire connector may be made of a single metal plate. The connector 5a is disposed at the terminal of the metal wire 5b, and the metal wire 5b is connected to at least the flat portion 5d. The metal wire 5b may be crimped with the connector 5a that is preferably a B-crimp. The metal wire 5b - which in practice may be a bundle of plural wires - is typically covered with the envelope or sheath 5c which may be made of e.g. PVC, PE, rubber material, fluororesin or the like. It is generally to be connected to apparatus such as an amplifier, audio equipment, radio equipment, a television, a navigation system, or the like.

The area of the flat portion 5d may typically be between <NUM><NUM> and <NUM><NUM>. If the area is smaller than <NUM><NUM> the solder connection may become weak. On the other hand, the more the area is larger than about <NUM><NUM>, the more mechanical stress tend to be transferred to the glass substrate layer <NUM> (due to brittleness of the lead-free solder and differential thermal expansion coefficients among the glass substrate layer <NUM>, the lead-free solder layer <NUM> and the connector 3a). In the light of these factors, the area may desirably be between <NUM><NUM> and <NUM><NUM>, more preferably between <NUM><NUM> and <NUM><NUM>.

The thickness of the metal plate may also affect the melting process of the block 4p in step (C). The thicker the metal plate, the more heating energy is required when the melting process is carried out and this may lead to more mechanical stress in the solder connection. On the other hand, the less thick the metal plate, the more difficult the connector 3a is for handling and manufacture. In the light of these factors, the thickness of the metal plate may preferably be between <NUM> and <NUM>, more preferably between <NUM> and <NUM>, still more preferably about <NUM>.

The shape of the flat portion 5d may be a rectangle, a square, oval or circle etc. As an example of the material of the metal plate, there can be mentioned Cu or Cu alloy, Fe alloy comprising Ni or Cr such as INVAR <NUM> (FeNi48, consisting of <NUM>% nickel in iron alloy). Among these materials, Fe alloy is preferable, and INVAR <NUM> is the most preferable.

In step (A), the lead-free solder is soldered onto the flat connector portion 5d to form the block 4p. The volume of the block 4p may typically be between <NUM><NUM> and <NUM><NUM>. If the volume is smaller than <NUM><NUM>, the solder connection may sometimes become weak. On the other hand, if the volume is larger than <NUM><NUM>, the compensation of mechanical stresses between the glass substrate layer <NUM> and the connector 5a may sometimes be inadequate, resulting in the occurrence of cracks in the glass substrate layer <NUM>, the conductive layer <NUM>, and/or in the coloured ceramic band <NUM>.

The thickness of the block 4p may also affect the quality of the lead-free solder layer <NUM>. If there is a limited amount of the lead-free solder, an inappropriate thickness of the block 4p may result in an inhomogeneous layer <NUM> with porosity which may cause mechanical stress in the glass substrate layer <NUM>. Considering these factors, the thickness may typically be between <NUM> and <NUM>, preferably between <NUM> and <NUM>.

The lead-free solder contains tin as a major component. As examples of lead-free solder, there can be mentioned Sn-Ag based solder, Sn-Ag-Cu based solder and the like. The content of Sn may be e.g. <NUM> mass% to <NUM> mass%, preferably <NUM> mass% to <NUM> mass%. The content of Ag may be e.g. <NUM> mass% to <NUM> mass%, preferably <NUM> mass% to <NUM> mass%. The content of Cu may be e.g. <NUM> mass% to <NUM> mass%, preferably <NUM> mass% to <NUM> mass%.

<FIG> is a cross-sectional view showing the harness and a glass substrate layer before step (C); the cross-sectional view is at X-Y of <FIG>. By means of step (B), the glass substrate layer <NUM> comprising the conductive layer <NUM> is provided. The glass substrate layer optionally comprises the coloured ceramic band <NUM> between the glass substrate layer <NUM> and the conductive layer <NUM>. The glass substrate layer <NUM> preferably has a curved shape, obtainable e.g. by a known process of bending a flat glass sheet. The glass substrate layer <NUM> may be a non-tempered glass, a thermally tempered glass, a chemically tempered glass or a laminated glass. In the laminated glass, the two glasses are preferably non-tempered glasses. This invention can specially be applied to a case in which the glass substrate layer <NUM> is a laminated glass comprising two or more non-tempered glasses (i.e. all glasses are non-tempered glasses) and the conductive layer <NUM> is a hot printed wire. As the material of the glass substrate layer <NUM>, soda-lime silicate glass as defined by ISO16293-<NUM> can be used. The soda-lime silicate glass may comprise a colorant such as iron oxide and cobalt oxide, whereby to present a colour such as pale green, dark green, pale gray, dark gray, pale blue or dark blue.

The coloured ceramic band <NUM> is of a coloured ceramic composition preferably comprising an inorganic heat-resisting pigment and a glass frit that has a lower softening temperature than that of the glass substrate layer <NUM>. Such a peripheral band is well-known, and is sometimes called a frit layer, ceramic band or paint band. The coloured ceramic band <NUM> is used to overlie an adhesion area between the vehicle glass assembly <NUM> and a body flange of a vehicle. It can improve weather resistance of the adhesion area and/or make it invisible by covering it, so that black is preferable as the colour of the coloured ceramic band layer <NUM>. The thickness of the coloured ceramic band may be e.g. <NUM> to <NUM>, preferably <NUM> to <NUM>.

The coloured ceramic band <NUM> can be obtained for example by the following process. That is, a ceramic paste comprising the inorganic heat-resisting pigment, a glass frit and organic solvent is applied on the peripheral portion of the glass substrate layer <NUM> by a screen printing method or the like, and then heated, thereby volatilizing the organic solvent. Subsequently, the composition comprising the inorganic heat-resisting pigment and glass frit is sintered on the glass substrate layer thereby forming the coloured ceramic band <NUM>.

The inorganic heat-resisting pigment is mixed in the colour ceramic to give a desired color. The grain diameter of the inorganic heat-resisting pigment may be e.g. <NUM> to <NUM>, preferably <NUM> to <NUM>, expressed as a D50 value. As the inorganic heat-resisting pigment, known ones can be used. As examples of black pigments, there can be mentioned copper-chromium complex oxide, iron-manganese complex oxide, cobalt-iron-manganese complex oxide, copper-chromium-manganese complex oxide, magnetite and the like.

As examples of blue pigment, there can be mentioned cobalt blue, chromium green, cobalt-zinc-nickel-titanium complex oxide, cobalt-aluminum-chromium complex oxide and the like.

In addition to the above-mentioned, there can be used white pigment (e.g. titanium white, zinc oxide and the like), red pigment (e.g. rouge and the like), yellow pigment (e.g. titanium yellow, titanium-barium-nickel complex oxide, titanium-antimony-nickel complex oxide, titanium-antimony-chromium complex oxide and the like) and other pigments in line with the skilled person's knowledge.

The glass frit is fused through a heating process to form the coloured ceramic band <NUM>. As the glass frit, usual ones can be used. As an example of the glass frit, there can be mentioned borosilicate glass, boron-zinc-silicate glass, bismuth-based glass and the like. A softening temperature of the glass frit may be a lower temperature, for example, <NUM>-<NUM>, preferably <NUM>-<NUM>, than a bending and forming temperature of the glass substrate layer <NUM>. The grain diameter of the glass frit may be <NUM> to <NUM>, preferably <NUM> to <NUM>, further preferably <NUM> to <NUM> (determined as D50). In the coloured ceramic band <NUM>, the content of the glass material made of the glass frit may be <NUM> mass% to <NUM> mass%.

The coloured ceramic band <NUM> can be also obtained through other methods besides the above-mentioned process. As an example of such other processes, there can be mentioned a digital printing process.

The conductive layer <NUM>, preferably sintered on the glass substrate layer <NUM> and/or on the coloured ceramic band <NUM>, comprises the electrically conductive wire pattern 3b and the connecting terminal 3a. The conductive layer <NUM> preferably comprises silver metal (silver or silver alloy) and a glass frit which may be selected from those exemplified above. The thickness of the electrically conductive layer <NUM> may be e.g. <NUM> to <NUM>, preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>.

The conductive layer <NUM> can be obtained through the following process. That is, a silver paste comprising the silver metal, the glass frit and an organic solvent is applied on the glass substrate layer <NUM>, or on coated and dried ceramic colour paste by screen printing method and the like, and then is heated, thereby volatilizing the organic solvent. Subsequently, the composition comprising the silver metal and the glass frit is sintered on the glass substrate layer <NUM> or coloured ceramic band <NUM>, thereby forming the electrically conductive layer <NUM>. As is well-known, the conductive layer <NUM> can be used as a printed hot-wire such as a defogger and defroster, or as an antenna.

The grain diameter of the silver metal may be e.g. <NUM> to <NUM>, preferably <NUM> to <NUM> (determined as D50). In the electrically conductive layer <NUM>, the content of the silver metal may be e.g. <NUM> mass% to <NUM> mass%, preferably <NUM> mass% to <NUM> mass%.

The conductive layer <NUM> can be also obtained by other methods besides the above-mentioned process. As an example of such other processes, there can be mentioned a digital printing process.

By means of step (C), the desired vehicle glass assembly <NUM> is obtained. In step (C), the block 4p is sandwiched between the flat portion 5d and the connecting terminal 3a, and then the block 4p is melted and may be pressed therebetween to form a solder connection between the connector 5a and the connecting terminal 3a, forming the lead-free solder layer <NUM>. Through this process, the lead-free solver layer <NUM> may be thinner than the block 4p in thickness. In the process (reflow process) in which the block 4p is melted, the block 4p may be heated up from a melting temperature of the lead-free solder to <NUM> above the melting temperature. The reflow process may be carried out using a soldering iron or electrical heating of the connector 5a. It is preferable that the reflow process is carried out through the electrical heating of the connector 5a.

The thickness of the lead-free solder layer <NUM> is desirably between <NUM> and <NUM>. If the thickness is more than <NUM>, a difference of thermal expansion behavior between the glass substrate layer <NUM> and the solder layer <NUM> may cause mechanical stress at an interface of the glass substrate layer <NUM> or the electrically conductive layer <NUM> during the melting process, or while using the window glass <NUM> fitted in a vehicle. The mechanical stress may enhance a risk of permanent tensile stress in the glass substrate layer <NUM>, resulting in crack generation in the glass substrate layer <NUM>. On the other hand, if the thickness is less than <NUM> it may enhance a risk of a generation of hot spots at the solder layer during the reflow process. The generation of hot spots may result in a residual stress in the glass substrate layer <NUM>, which then causes cracking in the glass substrate layer <NUM>.

Considering all these factors, the thickness of the lead-free solder layer <NUM> is preferably between <NUM> and <NUM>.

A base test specimen was provided. The specimen comprises a non-tempered glass substrate layer <NUM> with <NUM> thickness and made of a soda-lime silicate glass defined by ISO16293-<NUM>, and a conductive layer <NUM> comprising an electrically conductive wire pattern 3b and a connecting terminal 3a as shown in <FIG>, <FIG> and <FIG>. The shape and area of the connecting terminal 3a was, respectively, a rectangle and <NUM><NUM>. This corresponds to step (B) of the method.

A harness <NUM> comprising a connector 5a, metal (copper) wire 5b and a PVC sheath 5c covering the wire 5b was provided as shown in <FIG>. The connector 5a was made of Invar <NUM> (FeNi48 alloy) metal plate with <NUM> thickness, and was a B-crimp clamping the metal wire 5b. The connector 5a had a flat portion 5d of rectangular shape and <NUM><NUM> area. A lead-free solder made of Sn (<NUM> mass%)-Ag (<NUM> mass%)-Cu (<NUM> mass%) was soldered onto the flat portion 5d to form block 4p. The 4p on the flat portion 5d was away from all edges of the flat portions 5d. In this example, the soldered amount was <NUM>, and the volume and thickness of the block 4p were respectively <NUM><NUM> and <NUM>. This corresponds to step (A) of the method.

The block 4p was placed on the connecting terminal 3a so as to be sandwiched between the flat portion 5d and the connecting terminal 3a. The connecting terminal 3a was electrically heated so that block 4p is melted to form a solder connection between the connector and the connecting terminal. This corresponds to step (C) of the method. Through the step (C), the lead-free solder did not spill out a space between the flat portions 5d and the connecting terminal 3a. In this experiment, the soldered specimen was taken to be the vehicle glass assembly <NUM>.

The following heat cycle tests were conducted for <NUM> samples made in accordance with Example <NUM>.

No cracks were observed in the glass substrate layer <NUM> for any of the <NUM> samples in the heat cycle tests.

The procedure of Example <NUM> was repeated with the exception that the amount of lead-free solder was <NUM>, and the volume and thickness of the block 4p were respectively <NUM><NUM> and <NUM>. No cracks were observed in the glass substrate layer <NUM> for any of the samples in the heat cycle tests.

The procedure of Example <NUM> was repeated with the exception that the amount of lead-free solder was <NUM>, and the volume and thickness of the block 4p were respectively <NUM><NUM> and <NUM>. In the heat cycle tests cracking was observed for <NUM> out of <NUM> samples in this comparative example.

Claim 1:
A method of producing a vehicle glass assembly, comprising:
(A) providing a harness (<NUM>) comprising
a metal wire (5b),
a connector (5a) at a terminal of the metal wire (5b), comprising a flat portion (5d) made of a metal plate, and
a block (4p) of lead-free solder, containing tin as a major component, soldered on the flat portion (5d) of the connector (5a);
(B) providing a glass substrate layer (<NUM>) over which a conductive layer (<NUM>), comprising an electrically conductive wire pattern (3b) and a connecting terminal (3a), is formed;
(C) sandwiching the block (4p) between the flat portion (5d) of the connector and the connecting terminal (3a) of the conductive layer (<NUM>), and then melting the block to form a lead-free solder layer (<NUM>) as a solder connection between the connector (5a) and the connecting terminal (3a);
wherein
the amount of the lead-free solder is between <NUM> and <NUM>,
the solder block (4p) on the flat portion (5d) is away from all the edges of the flat portion (5d), and
in the solder connection, all the lead-free solder of the solder layer (<NUM>) is disposed between the flat portion (5d) and the connecting terminal (3a).