WO2006132319A1 - Objet en verre comportant un film conducteur formé sur celui-ci et procédé pour le fabriquer - Google Patents

Objet en verre comportant un film conducteur formé sur celui-ci et procédé pour le fabriquer Download PDF

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Publication number
WO2006132319A1
WO2006132319A1 PCT/JP2006/311532 JP2006311532W WO2006132319A1 WO 2006132319 A1 WO2006132319 A1 WO 2006132319A1 JP 2006311532 W JP2006311532 W JP 2006311532W WO 2006132319 A1 WO2006132319 A1 WO 2006132319A1
Authority
WO
WIPO (PCT)
Prior art keywords
conductive film
terminal
glass
solder
glass plate
Prior art date
Application number
PCT/JP2006/311532
Other languages
English (en)
Japanese (ja)
Inventor
Kazuo Yamada
Ichiro Okajima
Naoshi Asaoka
Original Assignee
Nippon Sheet Glass Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Sheet Glass Co., Ltd. filed Critical Nippon Sheet Glass Co., Ltd.
Priority to JP2007520160A priority Critical patent/JP5000499B2/ja
Publication of WO2006132319A1 publication Critical patent/WO2006132319A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys

Definitions

  • the present invention relates to a glass article on which a conductive film is formed and a method for producing a glass article provided with the conductive film, and more particularly to a glass article used as a vehicle window glass and a method for producing the same.
  • a plurality of defoggers that also have a conductive wire group (heat ray group) force are arranged in parallel in the horizontal direction on the indoor side surface of the rear window glass of the automobile, and the defogger at the end of the defogger.
  • a conductive coating is disposed in the vertical direction, and a terminal for power feeding is joined to the conductive coating via a solder. A current is supplied from the terminal to energize the defogger, and the field of view is secured by heating the window glass surface to remove condensation.
  • a conductive line having a pattern corresponding to the wavelength to be received is formed, and the same as the defogger described above.
  • the glass antenna functions.
  • the defogger and the glass antenna are obtained by forming a pattern on the surface of a glass plate using a silver paste by a screen printing method and performing firing.
  • the silver paste contains silver particles, glass frit, and a solvent.
  • a paste in which an organic medium is further mixed with the silver paste the defogger, the glass antenna, and the conductive film are blurred. It is possible to print on the glass plate surface without any problems.
  • Japanese Patent Laid-Open No. 5-290623 discloses a silver paste and an organic medium (alcohol, propionate, terpene (pine oil, tervineol, etc.) Solution)
  • the composition of the paste mixed with 25% by mass is disclosed.
  • the mixing ratio of the silver paste and the organic medium is determined in advance so that the resistance value falls within the standard range in a state where the conductive coating is formed on the glass plate surface.
  • a terminal to be bonded to the conductive coating through solder is required to have impact when mounting the glass plate with a terminal as a window for an automobile, bonding strength and durability after mounting. For this reason, the composition of the silver paste is variously changed to improve the bonding strength so that the strength during the bow I tension test satisfies the standard value.
  • Japanese Patent Application Laid-Open No. 11-306862 discloses that silver powder is 70% by mass or more, silver sulfate powder is 5 to 10% by mass, organic rhodium compound 0.02 to 0 2% by mass, low melting point glass frit 5-15% by mass, and organic medium (alcolate, propionate, terpene (pine oil, terbineol, etc.) dissolved in coconut oil such as ethyl cellulose and polymethacrylate) 10
  • a composition of paste mixed with ⁇ 40 mass% is disclosed.
  • a conductive film is formed using the paste disclosed in the above Japanese Patent Laid-Open No. 5-290623 and Japanese Patent Laid-Open No. 11 306862, and power is supplied to the conductive film via solder.
  • peeling occurred at the joint portion with the solder terminal, and cracks occurred near the joint portion with the solder of the conductive coating. This peeling occurs when the conductive film or ceramic collar adheres to the solder.
  • the surface part of the glass plate will also be peeled off, which causes the glass plate to peel off. It also led to destruction.
  • the conductive film and the solder are joined by silver contained in the conductive film being taken into the solder.
  • This phenomenon is generally called “silver is eaten by solder”. If the surface of the conductive coating has an uneven shape, the contact area with the solder increases, so The proportion of eaten silver increases. If the percentage of silver eaten by the solder exceeds a certain amount, that is, if the percentage of silver contained in the solder exceeds a certain amount, the hardness of the solder increases. The force was not able to relieve the stress when an external force was applied to the joint area. This stress is concentrated in the vicinity of the corner of the leg of the terminal, causing cracks in the solder, and the terminal is detached from the solder due to a decrease in bonding strength.
  • the present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to suppress the proportion of silver eaten by solder and to improve the joint strength of terminals for power feeding.
  • An object of the present invention is to provide a glass plate on which an electrically conductive film that can be formed is formed and a method for producing the same. Means for solving the problem
  • an aspect of the present invention includes a conductive film mainly composed of silver formed on a main surface of a glass plate and bonded to the conductive film via solder.
  • a glass article provided with a terminal, wherein at least a portion where the terminal is joined in a cross-section of the conductive film is a glass article in which a ratio of a cavity per unit area is 10% or less.
  • the terminal since at least the portion where the terminal is joined in the cross section of the conductive film is 10% or less per unit area, the terminal is disposed on the conductive film via the solder. The bonding strength when bonding can be improved.
  • a metal terminal including a leg portion having at least one joining surface and a connection portion protruding upward from the leg portion and connected to a cable may be joined to the conductive coating.
  • Another embodiment of the present invention provides a paste obtained by adding 1% by mass to 5% by mass of an organic medium to a silver paste containing silver as a main component, based on the total mass of the silver paste.
  • This is a method for producing a glass article in which a main surface is printed, a conductive film is formed by firing, and a terminal is bonded onto the conductive film.
  • a paste obtained by adding an organic medium to a silver paste is printed on one main surface of a glass plate, and then a conductive film is formed by baking, and terminals are formed on the conductive film. Because of the bonding, it is possible to smoothly form the joints with the solder on the surface of the conductive film, and by appropriately managing the contact area with the solder, The joint strength of the power supply terminal can be improved.
  • Yet another aspect of the present invention is a first step of printing a paste containing silver particles and glass frit on a glass plate, and a second step of subjecting the paste to a drying process with heating. And a third step of firing the conductive film by heating the glass plate subjected to the drying treatment.
  • the conductive film has a first step of printing a paste on the glass plate, a second step of drying the paste, and a third step of firing the glass plate. Since it is manufactured through a tape, it is possible to improve the bonding strength when the terminal is bonded onto the conductive film via solder.
  • the treatment can be performed under conditions of a drying temperature of 360 ° C or more and 440 ° C or less and a drying temperature of 1 minute or more and 3 minutes or less.
  • the treatment can be performed under the conditions of a drying temperature of 400 ° C and a drying time of 2 minutes.
  • the bonding strength between the conductive film and the terminal is improved via the solder, and the stress when an external force is applied to the bonding portion with the terminal can be relaxed. As a result, it is possible to suppress the peeling of the terminals joined to the conductive coating and the generation of cracks in the vicinity of the solder peripheral portion of the conductive coating.
  • FIG. 1 is a cross-sectional view showing an example of a glass part structure of the present invention.
  • FIG. 2 is a diagram showing a process flow in the case of producing automotive window glass in the present invention.
  • FIG. 3 is an example of an electron micrograph of a cross-section of a conductive coating when terminal bonding is good.
  • FIG. 4 An example of an electron micrograph of a cross-section of a conductive coating when terminal bonding is poor.
  • 1 is a glass plate
  • 2 ' is a ceramic color
  • 3' is a conductive coating
  • 4 is solder
  • 5 is a terminal
  • 6 is a hollow region.
  • FIG. 1 is a cross-sectional view showing a schematic structure of a glass article according to an embodiment of the present invention.
  • the glass article according to the present embodiment includes a glass plate 1, a ceramic collar 2 and a conductive coating 3 formed on the main surface of the glass plate 1, and solder 4 on the conductive coating 3. And a power supply terminal 5 joined via the terminal.
  • the glass plate 1 has a shape of a rear window glass or a side window glass of a vehicle, and is subjected to a quenching process (strengthening process).
  • a soda-lime-silica glass substrate having a soft saddle point of 730 to 740 ° C is used as the glass plate 1.
  • the ceramic color 2 is made of a glass frit for melting containing a black pigment component, and is opaque or translucent.
  • the conductive coating 3, the solder 4 and the power supply terminal 5 are visually recognized from the outside force of the vehicle. Thus, it is used to secure the design of the vehicle.
  • Ceramic color 2 is preferably composed of glass as a main component and also contains lead substantially, and is preferably a Pb-free type!
  • the conductive coating 3 constitutes an antenna and a defogger for a vehicle, and the glass frit constituting the conductive coating contains a metal in order to ensure the conductivity. As this metal, usually highly conductive silver is used.
  • the conductive coating 3 has a configuration formed on the ceramic collar 2 as described above and a configuration formed directly on the glass plate 1.
  • solder 4 for example, tin-silver solder is used to supply a current to the conductive coating 3 constituting the vehicle antenna and the defogger.
  • solder 4 is used to join the conductive coating 3 and the metal terminal 5.
  • the terminal 5 includes a leg portion 8 provided with at least one joint surface 8a and a connection portion 9 protruding upward from the leg portion and connected to a cable.
  • the shape of the joint surface of the metal terminal with the solder is typically a rectangle, but the planar shape of the joint surface 8a is not limited to this, but a circle, an ellipse, a semicircle, a triangle, or a polygon having five or more vertices. Etc.
  • FIG. 2 is a flowchart showing a schematic manufacturing process of the glass article according to the embodiment of the present invention.
  • a glass plate having a predetermined shape is cut from a flat glass substrate.
  • a ceramic color is screen-printed on the main surface of the glass plate, and a plurality of defoggers connected to the conductive film and the conductive film are screen-printed using a paste.
  • the glass plate on which the conductive film and the defogger are formed is dried in an atmosphere of 150 ° C. Or, dry in a high temperature atmosphere of 360 ° C to 440 ° C for 1 to 3 minutes. Alternatively, it is dried through both steps.
  • the glass plate is carried into a heating furnace and heated to a temperature at which the glass plate softens.
  • the organic medium in the paste is removed by evaporation and thermal decomposition during heating, and the conductive film is baked.
  • the surface of the glass plate is rapidly cooled and tempered.
  • a power feeding terminal is joined to the conductive film of the glass plate via solder.
  • Figs. 3 and 4 are partial photographs in which the cross sections of the ceramic power collar 2 'and the conductive coating 3' on the glass plate 1 at the location where the power supply terminals are joined are magnified 2000 times with an electron microscope.
  • the cavity region 6 is 10% or less per unit area, and the conductive coating 3 ′ is sufficiently filled with silver. This state is assumed to be “dense”. Thus, when the state of the cross section of the conductive coating is “dense”, the bonding strength of the terminal is 300 N or more, and a sufficient bonding strength is obtained.
  • the cavity region 6 exceeds 10% per unit area, and the conductive film 3 ′ is not sufficiently filled with silver. This state is assumed to be “sparse”.
  • the conductive film 3 ′ in the “sparse” state has a large contact area with the solder and a large proportion of silver eaten by the solder, so that the hardness of the solder becomes high. Since sufficient bonding strength cannot be obtained when the terminal is bonded onto the conductive coating 3 'via solder, the stress when an external force is applied to the terminal cannot be relaxed, and the terminal is not soldered. I will leave.
  • the first method is to use a paste with 1-5% by weight of organic medium based on the total weight of the silver paste. By controlling the content of the organic medium within the above range, The amount of sallow present can be reduced. By using this paste, the amount of heat required to evaporate the fat during drying can be reduced, and that amount of heat can be used to evaporate the fat in the paste. be able to.
  • the conductive film is dried in a high-temperature atmosphere of 360 to 440 ° C before the glass plate is heat-molded, and the resin contained in the organic medium is removed. Evaporation and thermal decomposition. This is determined from the fact that the resin contained in the organic medium is decomposed at 360 ° C and the glass frit contained in the organic medium is eluted at 440 ° C.
  • a ceramic color was formed on one main surface of the glass plate by a screen printing method and dried.
  • a conductive film and defogger are formed on the ceramic collar by screen printing using a paste whose organic medium mixing ratio is changed between 1 and 5% by mass as shown in Table 1.
  • this glass plate was baked in a heating furnace heated to about 700 ° C and molded to obtain an automotive window glass.
  • a power feeding terminal was joined to the conductive film of the window glass for an automobile.
  • the terminals used were soldered in advance on the joint surface with the conductive coating. Flux was applied to the solder surface, the bonding surface of the terminal was pressed against the conductive coating, and the terminal was bonded to the conductive coating by pressing a soldering iron (tip temperature: about 310 ° C) against the solder. After soldering, each sample of Examples 1 to 3 was obtained by leaving the glass plate with terminals for 24 hours at room temperature.
  • Comparative Example 1 The sample of Comparative Example 1 was prepared in the same manner as in Example 1 except that the organic surface was mixed with the main surface of the glass plate on which the ceramic color was formed, and the conductive film and defogger were formed by screen printing. Obtained. The bonding strength of the terminals in this sample was good, but the conductive film and defogger were blurred!
  • Conductive coating with improved bonding strength to terminals can also be obtained by drying at 150 ° C followed by high temperature drying at 360 ° C to 440 ° C.
  • good terminal bonding strength can be obtained by drying at 400 ° C to 440 ° C for 2 minutes or longer.
  • the present invention as a glass article in which a conductive film mainly composed of silver is formed on the main surface of a glass plate, and a terminal is bonded to the conductive film via solder, At least the location where the terminals are joined in the cross section of the conductive coating Or glass articles with a cavity occupancy of 10% or less.
  • the proportion of silver eaten by the solder is suppressed, and the bonding strength of the terminal for power supply is improved.

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  • Surface Treatment Of Glass (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

Lorsqu’une borne est liée par l'intermédiaire d’une brasure à un film conducteur qui est formé sur une surface principale d’un panneau en verre et comprend de l’argent comme composant principal, un pelage est généré à partir d’un bord de la brasure et des fissures sont générées dans le film conducteur au voisinage d’une périphérie de la brasure. Un tel pelage et de telles fissures doivent être éliminés étant donné qu’ils peuvent entraîner l’autodestruction du panneau en verre. En conséquence, il est nécessaire d’améliorer la force de liaison de la borne. La présente invention propose un objet en verre muni d’un film conducteur qui est formé sur la surface principale d’un panneau en verre et comprend de l’argent comme composant principal, ainsi qu’une borne liée au film conducteur par l'intermédiaire d’une brasure. Dans l’objet en verre, le taux d’occupation d’une surface par des vides par unité de surface est de 10 % ou moins, dans une coupe transversale du film conducteur, au moins au niveau d’une partie où la borne est liée.
PCT/JP2006/311532 2005-06-08 2006-06-08 Objet en verre comportant un film conducteur formé sur celui-ci et procédé pour le fabriquer WO2006132319A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007520160A JP5000499B2 (ja) 2005-06-08 2006-06-08 導電性被膜の形成されたガラス物品及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-168670 2005-06-08
JP2005168670 2005-06-08

Publications (1)

Publication Number Publication Date
WO2006132319A1 true WO2006132319A1 (fr) 2006-12-14

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PCT/JP2006/311532 WO2006132319A1 (fr) 2005-06-08 2006-06-08 Objet en verre comportant un film conducteur formé sur celui-ci et procédé pour le fabriquer

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JP (1) JP5000499B2 (fr)
WO (1) WO2006132319A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010150832A1 (fr) * 2009-06-25 2010-12-29 日本板硝子株式会社 Vitre de fenêtre ayant un corps fritté en céramique conductrice et son procédé de fabrication
JP2013521207A (ja) * 2010-03-02 2013-06-10 サン−ゴバン グラス フランス 電気接続素子を備えた窓ガラス
US9496632B2 (en) 2012-06-06 2016-11-15 Saint-Gobain Glass France Disk having an electrical connection element
US9837727B2 (en) 2012-09-14 2017-12-05 Saint-Gobain Glass France Pane having an electrical connection element
US9967967B2 (en) 2012-09-14 2018-05-08 Saint-Gobain Glass France Pane having an electrical connection element
US10290952B2 (en) 2010-05-04 2019-05-14 Pilkington Group Limited Soldering on thin glass sheets
US10305239B2 (en) 2011-05-10 2019-05-28 Saint-Gobain Glass France Pane comprising an electrical connection element
US10355378B2 (en) 2011-05-10 2019-07-16 Saint-Gobain Glass France Pane having an electrical connection element
US11217907B2 (en) 2011-05-10 2022-01-04 Saint-Gobain Glass France Disk having an electric connecting element

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62108514A (ja) * 1985-11-06 1987-05-19 松下電器産業株式会社 誘電体用電極組成物
JPH05290623A (ja) * 1991-12-03 1993-11-05 E I Du Pont De Nemours & Co 自動車ガラスの厚膜導電体ペースト
JPH0982135A (ja) * 1995-09-11 1997-03-28 Murata Mfg Co Ltd 導電性組成物
JPH11306862A (ja) * 1998-04-23 1999-11-05 Central Glass Co Ltd 導電体ペースト

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62108514A (ja) * 1985-11-06 1987-05-19 松下電器産業株式会社 誘電体用電極組成物
JPH05290623A (ja) * 1991-12-03 1993-11-05 E I Du Pont De Nemours & Co 自動車ガラスの厚膜導電体ペースト
JPH0982135A (ja) * 1995-09-11 1997-03-28 Murata Mfg Co Ltd 導電性組成物
JPH11306862A (ja) * 1998-04-23 1999-11-05 Central Glass Co Ltd 導電体ペースト

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010150832A1 (fr) * 2009-06-25 2010-12-29 日本板硝子株式会社 Vitre de fenêtre ayant un corps fritté en céramique conductrice et son procédé de fabrication
JP2013521207A (ja) * 2010-03-02 2013-06-10 サン−ゴバン グラス フランス 電気接続素子を備えた窓ガラス
JP2016117638A (ja) * 2010-03-02 2016-06-30 サン−ゴバン グラス フランス 電気接続素子を備えた窓ガラス
US10290952B2 (en) 2010-05-04 2019-05-14 Pilkington Group Limited Soldering on thin glass sheets
US10305239B2 (en) 2011-05-10 2019-05-28 Saint-Gobain Glass France Pane comprising an electrical connection element
US10355378B2 (en) 2011-05-10 2019-07-16 Saint-Gobain Glass France Pane having an electrical connection element
US11217907B2 (en) 2011-05-10 2022-01-04 Saint-Gobain Glass France Disk having an electric connecting element
US11456546B2 (en) 2011-05-10 2022-09-27 Saint-Gobain Glass France Pane having an electrical connection element
US9496632B2 (en) 2012-06-06 2016-11-15 Saint-Gobain Glass France Disk having an electrical connection element
US9837727B2 (en) 2012-09-14 2017-12-05 Saint-Gobain Glass France Pane having an electrical connection element
US9967967B2 (en) 2012-09-14 2018-05-08 Saint-Gobain Glass France Pane having an electrical connection element

Also Published As

Publication number Publication date
JP5000499B2 (ja) 2012-08-15
JPWO2006132319A1 (ja) 2009-01-08

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