WO2019073637A1 - Conductive paste, glass article, and method for manufacturing glass article - Google Patents

Conductive paste, glass article, and method for manufacturing glass article Download PDF

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Publication number
WO2019073637A1
WO2019073637A1 PCT/JP2018/023429 JP2018023429W WO2019073637A1 WO 2019073637 A1 WO2019073637 A1 WO 2019073637A1 JP 2018023429 W JP2018023429 W JP 2018023429W WO 2019073637 A1 WO2019073637 A1 WO 2019073637A1
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Prior art keywords
glass
powder
conductive
ceramic
conductor
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PCT/JP2018/023429
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French (fr)
Japanese (ja)
Inventor
松任　隆浩
清水　康介
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株式会社村田製作所
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Publication of WO2019073637A1 publication Critical patent/WO2019073637A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60S—SERVICING, CLEANING, REPAIRING, SUPPORTING, LIFTING, OR MANOEUVRING OF VEHICLES, NOT OTHERWISE PROVIDED FOR
    • B60S1/00—Cleaning of vehicles
    • B60S1/02—Cleaning windscreens, windows or optical devices
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present invention relates to a conductive paste, a glass article, and a method of manufacturing a glass article, more specifically, a conductive paste for forming a heat wire or the like attached to a window glass of a vehicle or the like, and the conductive paste
  • the present invention relates to various glass articles such as wiper-free heat-resistant glass, anti-fog glass, glass antenna and the like, and a method of producing a glass article suitable for producing the glass article.
  • glass articles such as glass articles provided with heat rays for wiper antifreeze and antifogging and glass articles such as a glass antenna receiving radio waves from the outside of a vehicle are used for window glass for vehicles such as automobiles.
  • laminated glass is generally used in consideration of impact resistance.
  • a ceramic layer and a conductor having a predetermined pattern are generally formed on a glass substrate, and the conductor is energized to cause the conductor to generate heat to prevent the wiper from freezing or fogging. Or it receives radio waves from outside the car.
  • a conductor is formed on a surface of a window glass for an automobile, and the conductor is formed on a window glass for a conductor with a conductor in which a shielding layer is formed on the periphery of the surface.
  • a first conductor formed on the shielding layer, and a surface electrically connected to the first conductor and located on the inner side of the shielding layer on the window glass surface A conductive window glass for an automobile is proposed, which is composed of the second conductive material which has a lower resistivity than the first conductive material.
  • a conductive paste is formed by applying a conductive paste (Ag paste) having a glass powder content of 1 to 10 wt% to a black ceramic film having a glass powder content of 20 to 90 wt%, The ceramic film and the conductive film are co-fired to form a conductor (Ag electrode) on the surface of the ceramic layer.
  • a conductive paste Ag paste having a glass powder content of 1 to 10 wt%
  • a black ceramic film having a glass powder content of 20 to 90 wt%
  • Patent Document 1 when the ceramic film and the conductive film are co-fired, the glass component in the conductive film or the ceramic film may be segregated on the surface layer surface of the conductor after firing to form a glass phase.
  • the solder wettability of the conductor is degraded, which may result in a decrease in bonding strength when the conductor and the power supply terminal are connected by soldering.
  • the use of lead-free solder has been required from the viewpoint of reducing environmental load.
  • Such a lead-free solder is inferior in solder wettability to a conventional lead solder and has a narrow temperature range suitable for soldering, and the solder wettability may be further deteriorated to cause a further decrease in bonding strength.
  • the present invention has been made in view of such circumstances, and it is possible to obtain a conductive paste which can obtain a conductor having good solder wettability and good bonding strength with a feeding terminal, and various kinds of conductive pastes using this conductive paste. It is an object of the present invention to provide a glass article and a method of producing a glass article suitable for producing the glass article.
  • Ni powder has the effect of inhibiting the sinterability of the conductive powder. Therefore, when the inventors of the present invention conducted conductive research by using a conductive paste to which Ni powder is added and forming a conductive pattern on a ceramic film containing a glass component, the content of Ni powder is If it is a range of 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder, the conductor after firing even if the conductive paste contains 0.2% by weight or more of glass powder It is possible to suppress the formation of a glass phase on the surface layer surface of the conductor while securing the bonding strength at the interface between the ceramic and the ceramic layer, thereby improving the solder wettability of the conductor surface and the bonding strength of the feeding terminal. We have found that we can
  • the conductive paste according to the present invention is a conductive paste for forming a conductive pattern on a ceramic film containing a glass component, at least the conductive paste.
  • Powder, glass powder, Ni powder, and an organic vehicle, and the content of the glass powder is 0.2 wt% or more, and the content of the Ni powder is 100 parts by weight of the conductive powder
  • it is characterized in that it is 0.125 parts by weight or more and 1.25 parts by weight or less.
  • Ni powder also includes the case where Ni is a main component.
  • the conductive powder preferably contains Ag as a main component.
  • the glass article according to the present invention is a glass article in which a ceramic layer containing a glass component is formed on a glass substrate, and a conductor is formed on the ceramic layer, and the ceramic layer and the conductor
  • the content of the glass powder and the ceramic film containing the glass component is 0.2 wt% or more in the conductive paste, and the content of the Ni powder is 0.125 based on 100 parts by weight of the conductive powder. It is characterized in that it is made of a co-sintered body obtained by co-firing a conductive film of not less than 1 part by weight and not more than 1.25 parts by weight.
  • Ni powder also includes the case where Ni is a main component.
  • the glass component contained in the ceramic film is preferably amorphous.
  • the glass component in the ceramic film is amorphous, it is likely to be fluidized by firing, and the glass component can be effectively permeated into the conductor, and the interfacial bonding force between the ceramic layer and the glass substrate Not only that, the interfacial bonding strength between the conductor and the ceramic layer can be further improved.
  • the conductor preferably has an occupancy of 30% or less in area ratio of the glass component in the surface layer surface.
  • solder wettability of the conductor surface can be secured, and the joint strength of the solder can be improved.
  • the ceramic layer preferably contains an inorganic pigment, and in this case, the inorganic pigment is preferably a black pigment.
  • the periphery of the window glass is restrained by a holding material such as a urethane resin, deterioration of the holding agent due to ultraviolet light is caused by the ceramic layer containing a black inorganic pigment. Therefore, the antiglare function in the car can be secured.
  • the method for producing a glass article according to the present invention further comprises the steps of preparing a ceramic paste containing at least a ceramic powder, a glass component, and an organic vehicle, and at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle.
  • the content of the glass powder is 0.2 wt% or more, and the content of the Ni powder is adjusted to 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder. It is characterized in that it comprises the steps of: preparing a conductive paste; and applying the ceramic paste to a glass substrate to form a ceramic film.
  • the step of applying the ceramic paste to the glass substrate to form a non-fired ceramic film, and applying the conductive paste on the non-fired ceramic film to perform non-baking It is preferable to include the step of forming a conductive film, and the step of co-firing the green ceramic film and the green conductive film.
  • the ceramic powder contains an inorganic pigment.
  • the conductive paste of the present invention is a conductive paste for forming a conductive pattern on a ceramic film containing a glass component, which contains at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle.
  • the content of the glass powder is 0.2 wt% or more
  • the content of the Ni powder is 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder.
  • a ceramic layer containing a glass component is formed on a glass substrate, and a conductor is formed on the ceramic layer, wherein the ceramic layer and the conductor are formed.
  • the content of the glass powder and the ceramic film containing the glass component is 0.2 wt% or more in the conductive paste, and the content of the Ni powder is 0.1 parts by weight to 100 parts by weight of the conductive powder.
  • the conductive film of 125 parts by weight or more and 1.25 parts by weight or less is co-sintered, the glass component in the ceramic film and the glass powder in the conductive paste The interface bonding strength can be secured, and the formation of the glass phase on the surface layer of the conductor can be suppressed, whereby the solder wettability and the bonding strength can be improved.
  • a process of preparing a ceramic paste containing at least a ceramic powder, a glass component, and an organic vehicle, and at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle The content of the glass powder is 0.2 wt% or more, and the content of the Ni powder is 0.125 parts by weight or more and 1.25 parts by weight or less based on 100 parts by weight of the conductive powder. Since the steps of preparing the conductive paste and applying the ceramic paste to a glass substrate to form a ceramic film, various glass articles in which the formation of the glass phase on the surface layer of the conductor is suppressed are facilitated. Can be obtained.
  • FIG. 1 It is a front view which shows one Embodiment (1st Embodiment) of the glass article manufactured using the electrically conductive paste which concerns on this invention. It is AA arrow sectional drawing of FIG. It is principal part sectional drawing which shows typically the 1st modification of the said glass article. It is principal part sectional drawing which shows typically the 2nd modification of the said glass article. It is principal part sectional drawing which shows typically the 3rd modification of the said glass article. It is an important section sectional view showing a 2nd embodiment of a glass article concerning the present invention. It is an imaging figure which shows the test result of the solder wettability test of the sample number 1.
  • FIG. 1st Embodiment It is AA arrow sectional drawing of FIG. It is principal part sectional drawing which shows typically the 1st modification of the said glass article. It is principal part sectional drawing which shows typically the 2nd modification of the said glass article. It is principal part sectional drawing which shows typically the 3rd modification of the said glass article. It is an important section section
  • FIG. 1 It is a plane SEM image of the conductor surface side of sample number 2. It is an imaging figure which shows the test result of the solder wettability test of the sample number 9. It is an imaging figure which shows the test result of the solder wettability test of the sample number 3. FIG. It is an imaging figure which shows the test result of the solder wettability test of the sample number 4. FIG. It is a cross-sectional SEM image of the sample number 1. It is a cross-sectional SEM image of sample number 3.
  • FIG. 1 is a front view showing an embodiment (first embodiment) of a glass article manufactured using the conductive paste according to the present invention, and this embodiment is for wiper antifreeze
  • the figure shows a glass with heat rays (hereinafter referred to as "glass with heat rays").
  • FIG. 2 is a sectional view taken along the line AA of FIG.
  • this heat-ray attached glass is made of laminated glass in which an intermediate film 3 formed of a polyvinyl alcohol resin or the like is interposed between the first glass substrate 1 and the second glass substrate 2, and impact resistance is taken into consideration.
  • the structure is
  • a black ceramic layer 4 is formed along the outer periphery of the first glass substrate 1, and a conductor 5 is formed on the ceramic layer 4 in a predetermined area near the home position of the wiper.
  • the conductor 5 is connected to the feed terminal 7 through the solder 6 and mounted on the front portion of a vehicle such as a car.
  • the conductor 5 In the glass with heat ray, when the conductor 5 is in a low temperature to a low temperature atmosphere, the conductor 5 is energized to generate heat, and the surface temperature of the first glass substrate 1 is raised to cause a malfunction of the wiper due to freezing or the like. Is avoiding. Furthermore, by making the ceramic layer 4 black, it is possible to prevent the holding agent such as urethane resin which restrains the heat-rayed glass from being deteriorated by ultraviolet light.
  • the holding agent such as urethane resin which restrains the heat-rayed glass from being deteriorated by ultraviolet light.
  • the ceramic layer 4 and the conductor 5 have a ceramic film containing a glass component, and the content of the glass powder is 0.2 wt% or more in the conductive paste, and the content of the Ni powder is a conductive powder. Since the conductive film made 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight is made of co-sintered body, the glass component in the ceramic film and the glass powder in the conductive paste Thus, the interfacial bonding strength between the conductor 5 and the ceramic layer 4 can be secured, and the formation of the glass phase on the surface layer of the conductor can be suppressed, whereby the solder wettability and the bonding strength can be improved.
  • the conductive paste for forming the conductor 5 of this type conventionally contains about 0.2 to 10 wt% of glass powder, and thereby it is associated with the glass component penetrating from the ceramic film. The adhesion between the conductor 5 and the ceramic layer 4 is secured.
  • the glass powder contained in the conductive paste and the glass component in the ceramic film flow at the time of firing and segregate to the surface layer surface of the conductor 5 to form a glass phase on the surface layer surface. In this case, the bond strength of the feed terminal 7 may be reduced.
  • Ni powder has the effect of inhibiting the sinterability of the conductive powder. Therefore, by containing a predetermined amount of Ni powder in the conductive paste, even if the conductive paste contains 0.2 wt% or more of glass powder, bonding of the interface between the conductor after firing and the ceramic layer is performed. It is considered possible to suppress the formation of the glass phase on the surface layer of the conductor while securing the force.
  • the said predetermined amount is made into the range of 0.125 weight part or more and 1.25 weight part or less with respect to 100 weight part of electroconductive powder, and Ni powder is contained in the electroconductive paste.
  • the conductive paste contains 0.2 wt% or more of glass powder, it is possible to suppress segregation of the glass component in the ceramic film and the glass powder in the conductive paste to the surface layer of the conductor. To improve solder wettability and bonding strength.
  • the Ni powder has the function of inhibiting the sintering of the conductive powder
  • the conductive powder when the conductive powder contains the Ni powder, the conductive powder has a fine and complicated shape. A large number of voids are created. Therefore, such air gaps become resistance or obstacle and it becomes difficult for the glass component in the ceramic film and the glass powder in the conductive paste to be segregated on the surface layer of the conductor. As a result, the formation of the glass phase on the surface layer of the conductor can be suppressed, and the solder wettability and the joint strength of the solder can be improved.
  • the content of Ni powder is required to be at least 0.125 parts by weight with respect to 100 parts by weight of the conductive powder.
  • the content of the Ni powder exceeds 1.25 parts by weight with respect to 100 parts by weight of the conductive powder, the Ni powder is easily oxidized during firing to form a Ni oxide, so the conductor surface layer surface Although the formation of the glass phase is suppressed, the solder wettability and the bonding strength may be deteriorated.
  • Ni powder is contained in the conductive paste in the range of 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder. Improve the strength and bonding strength.
  • the conductive powder is not particularly limited as long as it is a metal powder having good conductivity, but in general, Ag powder can be preferably used. In addition, Ag powder may be used as a main component, and various conductive powders such as Pd powder and Pt powder may be contained as subcomponents.
  • the shape of the conductive powder is not particularly limited, and may be, for example, a spherical shape, a flat shape, an irregular shape, or a mixed powder thereof.
  • the average particle size D 50 of the conductive powder is not particularly limited, but it is preferable to use a conductive powder of such a size that clogging does not occur in screen printing, for example, the average particle size D 50
  • a conductive powder having a diameter of 10 ⁇ m or less can be used.
  • the content of the conductive powder in the conductive paste is not particularly limited, but is preferably 50 to 90 wt%.
  • the content of the conductive powder is less than 50 wt%, in order to obtain a standard 3 to 20 ⁇ m thick film conductor 5, it is necessary to use a screen printing plate having a mesh with a large diameter during screen printing. , May cause a reduction in resolution.
  • the content of the conductive powder exceeds 90 wt%, the conductive powder may be excessive to make it difficult to paste. Therefore, the content of the conductive powder is preferably 50 to 90 wt%, although it is not particularly limited.
  • the organic vehicle is prepared such that the binder resin and the organic solvent are, for example, 1 to 3: 7 to 9 in volume ratio.
  • the binder resin is not particularly limited, and, for example, ethyl cellulose resin, nitrocellulose resin, acrylic resin, alkyd resin, or a combination thereof can be used.
  • the organic solvent is not particularly limited, and ⁇ -terpineol, xylene, toluene, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, etc. alone or in combination thereof It can be used.
  • the content of the glass powder is 0.2 wt% or more
  • the content of the Ni powder is 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder. It can be easily produced by dispersing and kneading using a three-roll mill or the like.
  • the present conductive paste contains at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle, and the content of the glass powder is 0.2 wt% or more, and of the Ni powder. Since the content is 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder, there is no excessive formation of Ni oxide and fine particles are obtained between the conductive powders at the time of firing. Since a large number of voids having a complicated shape are formed, it is possible to suppress the formation of a glass phase on the surface layer surface of the conductor after firing, which makes it possible to have good solder wettability and good bonding strength. Sex paste can be obtained.
  • a ceramic paste containing a ceramic powder, a glass component, and an organic vehicle is prepared.
  • the glass component is not particularly limited, and it is necessary to select from among ZnO, Al 2 O 3 , B 2 O 3 , SiO 2 , SiO 2 , TiO 2 , ZrO 2 , alkali metal oxides, alkaline earth metal oxides, etc.
  • the composition can be appropriately selected according to the formula and formulated into a predetermined composition.
  • the ceramic powder preferably those containing black-based inorganic pigments, as a black inorganic pigment may be used Cr 2 O 3, CuO and the like.
  • the glass component is preferably amorphous.
  • Amorphous glass is easily softened at the time of firing and is highly fluid, so it easily penetrates into the conductive film and is fixed in the conductor 5 after firing.
  • organic vehicle one similar to the above-mentioned conductive paste of the present invention can be used.
  • the conductive paste of the present invention is produced by the method described above.
  • a ceramic paste is applied along the outer periphery of the first glass substrate 1 by screen printing and dried to form an unfired ceramic film containing a black inorganic pigment and a glass component.
  • a conductive paste is applied to a lower predetermined area of the ceramic film corresponding to the home position of the wiper, and dried to form a non-fired conductive film.
  • the first glass substrate 1 on which the unfired ceramic film and the unfired conductive film are formed is fired at a temperature of 550 to 650 ° C. for about 5 minutes in a non-reducing atmosphere such as an air atmosphere.
  • the first glass substrate 1 is obtained having the ceramic layer 4 and the conductor 5 in which the ceramic layer 4 and the conductor 5 are co-fired.
  • the glass component penetrates into the inside of the conductor 5, and the bonding strength of the interface between the ceramic layer 4 and the conductor 5 is secured by the combination of the glass powder in the conductive paste and the conductor surface
  • the formation of a glass phase is suppressed. Specifically, the occupancy of the glass phase of the surface layer surface of the conductor 5 is suppressed to 30% or less in area ratio.
  • the intermediate film 3 is attached via an adhesive so that the intermediate film 3 is sandwiched between the first glass substrate 1 and the second glass substrate 2, whereby the above-described glass with heat wire is manufactured.
  • the content of the glass powder is 0.2 wt% or more
  • the content of the Ni powder is 0.125 parts by weight or more and 1.25 parts by weight or less based on 100 parts by weight of the conductive powder.
  • the co-firing process of the unfired ceramic film and the unfired conductive film is exemplified, but a process (post-fire) of forming the unfired conductive film on the fired ceramic film and firing is applied. May be However, the co-firing process is preferable because the bonding strength between the ceramic film and the conductive film can be improved and the process can be simplified.
  • FIG. 3 is a cross-sectional view of main parts schematically showing a first modification of the embodiment.
  • the conductor 5 in contact with the feeding terminal 7 via the solder 6 is made of the conductive paste of the present invention containing Ni, and the conductor 11a of the portion not in contact with the feeding terminal 7 11 b is formed of a sintered body of a conventional conductive paste containing no Ni powder. And thereby, it can suppress that a glass phase is formed in a conductor surface layer surface from the same reason as the above-mentioned, and solder wettability can be obtained and glass with a heat wire with favorable joining strength can be obtained.
  • FIG. 4 is a cross-sectional view of main parts schematically showing a second modified example of the above embodiment.
  • a conductor 12 which is a sintered body of a conventional conductive paste containing no Ni powder is interposed between the conductor 5 and the ceramic layer 4.
  • the conventional conductive paste containing no Ni powder is used as the ceramic film.
  • the conductive paste is applied and dried on the surface to form a conductive film, and the conductive paste is applied and dried only on the portion of the conductive film in contact with the feed terminal 7 to form a conductive film, and a ceramic film and two conductive films Are co-fired to obtain the ceramic layer 4 and the conductors 12 and 5.
  • the glass component in the ceramic film penetrates the conductor 5 made of the conventional conductive paste into the conductor 5, or the glass component in the ceramic film passes through the conductor 12 Since the conductor 5 is formed of the conductive paste of the present invention containing a predetermined amount of Ni powder even if it penetrates into the conductor 5, the Ni oxide is not excessively formed. It is possible to suppress the formation of the glass phase on the surface layer of the conductor, and it is possible to obtain a glass with heat wire having good solder wettability and good bonding strength.
  • FIG. 5 is a cross-sectional view of main parts schematically showing a third modification of the embodiment.
  • a conductor 13 which is a sintered body of a conventional conductive paste containing no Ni powder is formed on the surfaces of the ceramic layer 4 and the conductor 5.
  • the conductive paste is applied and dried on the portion facing the feeding terminal 7.
  • a conventional conductive paste not containing Ni powder is applied on the surface of the conductive film and dried to form a new conductive film, and the ceramic film and the two conductive films are co-formed.
  • the ceramic layer 4 and the conductors 5 and 13 are obtained by firing.
  • the content of the glass component in the ceramic paste is generally known to be large compared to the content of the glass powder in the conductive paste, and hence In order to suppress the formation of the glass phase, it is considered effective to suppress the segregation of the glass component in the ceramic film on the surface layer of the conductor.
  • the conductor 5 made of the conductive paste of the present invention is formed in the portion facing the feeding terminal 7, whereby the glass component in the ceramic film penetrates the conductor 13. Can be suppressed. Therefore, since the formation of the glass phase on the surface layer surface of the conductor 13 is suppressed, it is possible to obtain a glass with heat wire having good solder wettability and good bonding strength.
  • FIG. 6 is a sectional view of an essential part schematically showing a second embodiment of the glass article according to the present invention, and the second embodiment shows a glass antenna.
  • this glass antenna is also made of laminated glass, and an intermediate film 33 is interposed between the first glass substrate 31 and the second glass substrate 32.
  • a ceramic layer 34 is formed on the surface of the first glass substrate 31, and a conductor 35 having a predetermined pattern having an antenna function is formed on the surface of the ceramic layer 34.
  • the conductor 35 is soldered to a feeding terminal (not shown), and is mounted as a window glass for a vehicle such as an automobile as in the first and second embodiments, and receives radio waves from the outside of the vehicle and supplies it to a radio or television. Be done.
  • This glass antenna is produced as follows.
  • a ceramic paste containing a glass component preferably containing a black inorganic pigment
  • the conductive paste of the present invention is applied on the ceramic paste so as to have a predetermined antenna pattern, and dried to form a conductive film.
  • the ceramic film and the conductive film on the first glass substrate 31 are co-fired to produce the ceramic layer 34 and the conductor 35.
  • the interlayer film 33 is pasted with an adhesive so as to be held between the first glass substrate 31 and the second glass substrate 32, thereby producing a glass antenna.
  • the ceramic layer 34 and the conductor 35 have a ceramic film containing a glass component, and the content of the glass powder is 0.2 wt% or more in the conductive paste, and the Ni powder is Since the conductive film having a content of 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder is a co-sintered body, the glass component in the ceramic film and The bonding strength between the conductor 5 and the ceramic layer 4 can be secured by the glass powder in the conductive paste, and the formation of the glass phase on the surface layer of the conductor can be suppressed, whereby the solder wettability and the bonding strength are improved. can do.
  • the present invention is not limited to the above embodiment.
  • a black inorganic pigment is contained in the ceramic layer from the viewpoint of preventing the holding agent such as urethane resin from being deteriorated by ultraviolet light, and the glass antenna is also used in the car.
  • the ceramic layer may not contain the inorganic pigment depending on the application.
  • various inorganic components may be contained in the ceramic layer and the conductor within a range not affecting the characteristics, for example, Zr, P, V, Ce, Nb, Ta, W, Pd, Ag , Ru, Sn, In, Y, Dy, La, etc. may be contained.
  • the content form is also not particularly limited, and oxides, hydroxides, peroxides, halides, carbonates, nitrates, phosphates, sulfates, fluorides, organic metal compounds, etc. are appropriately selected. can do.
  • plasticizers such as di2-ethylhexyl phthalate and dibutyl phthalate
  • a rheology modifier such as a fatty acid amide or a fatty acid, and a thixotropic agent, a thickener, a dispersant or the like may be further added.
  • an organic vehicle was produced by the following method. That is, 10 wt% of ethyl cellulose resin as a binder resin, and 90 wt% of terpineol as an organic solvent were mixed with ethyl cellulose resin and terpineol to prepare an organic vehicle.
  • a slide glass made of soda lime having a length of 76 mm, a width of 26 mm, and a thickness of 1.4 mm, and a black ceramic paste were prepared. Then, the ceramic paste was applied to a slide glass by screen printing so as to form a rectangular shape having a length of 6 mm and a width of 22 mm, and then dried at 150 ° C. for 10 minutes to form a ceramic film on the slide glass. . Then, using screen printing method, apply conductive pastes of sample numbers 1 to 9 on the ceramic film so that regular triangles of 2.0 mm on one side and inverted regular triangles are alternately arranged in a horizontal direction. Then, it was again dried at a temperature of 150 ° C.
  • sample numbers 1 to 9 for solder wettability evaluation The sample of Further, using a plate glass having a thickness of 3 mm, samples of sample numbers 1 to 9 for bonding strength measurement were produced by the same method and procedure as described above.
  • solder wettability was evaluated by setting the solder coverage to be 90% or more in terms of area ratio (A), less than 90% as 70% or more as good (O), and less than 70% as unacceptable (X).
  • Each sample of sample numbers 1 to 9 was placed on a hot plate heated to a temperature of 150 ° C., and a feed terminal was soldered to a conductor.
  • a feed terminal a general commercial product (made by Nishi Nippon Shoko Co., Ltd.) is used, and as in the solderability test, Sn-Pb-Ag based solder is used for the solder, rosin is used for the flux isopropyl alcohol Dissolved in water was used.
  • Table 1 shows the component composition of the conductive paste, the Ni content relative to 100 parts by weight of Ag, and the measurement results.
  • Sample No. 1 has extremely poor solder wettability because the conductive paste does not contain Ni powder, and the bonding strength is as low as 10 N, and the glass phase occupancy of the conductor surface is also 70% in area ratio It got bigger.
  • FIG. 7 shows the test results of the solder wettability test of sample No. 1. As apparent from FIG. 7, it can be seen that the solder is not wet at all on the conductor.
  • Sample No. 2 has a low Ni content of 0.0625 parts by weight with respect to 100 parts by weight of Ag, so the solder wettability is low at 40% in area ratio, inferior in solder wettability, and low in joint strength of 70 N, mechanical It was found that the strength was inferior.
  • FIG. 8 shows a planar SEM photograph of sample No. 2.
  • the occupancy of the glass phase in the conductor is about 50%, and the glass component is segregated in large amounts on the surface layer of the conductor.
  • Sample No. 9 has an excess of 2.5 parts by weight of Ni content to 100 parts by weight of Ag, so the glass phase occupancy of the surface layer of the conductor is as low as 10%, but Ni oxide is formed during firing From the results, it was found that the solder wettability amounted to 50% in area ratio and decreased to less than 70%, the solder wettability deteriorated, and the joint strength also decreased to 90 N and the mechanical strength decreased.
  • FIG. 9 shows the test results of the solder wettability test of sample No. 9. As apparent from FIG. 9, it can be seen that the solder is not sufficiently wet and spread on the conductor.
  • sample numbers 3 to 8 have a Ni content in the range of the present invention, so the solder coverage is 70 to 100% in area ratio, the solder wettability is good, and the bonding strength is also 110 to 250 N As a result, it was found that sufficient mechanical strength can be obtained, the glass occupancy rate is also 30% or less, and the solderability is good.
  • the formation of the glass phase on the surface layer of the conductor can be suppressed by containing a predetermined amount of Ni powder, whereby solder wettability and solder can be obtained. It has been found that the bonding strength of can be improved.
  • FIG. 10 shows the test results of the solder wettability test of sample No. 3. As apparent from FIG. 10, it can be seen that the solder is sufficiently wet and spread on the conductor surface.
  • FIG. 11 shows the test results of the solder wettability test of sample No. 4. As apparent from FIG. 11, it can be seen that the solder is wet and spread over the entire surface of the conductor.
  • FIG. 12 is a cross-sectional SEM image of sample No. 1
  • FIG. 13 is a cross-sectional SEM image of sample No. 4.
  • Sample No. 4 contained 0.625 parts by weight of Ni powder with respect to 100 parts by weight of Ag, and thus Ni powder inhibited sintering of the Ag powder, so as shown in FIG. It has been found that a large number of air gaps having a complicated shape are formed, and the air gaps become resistance or obstruction to reduce the occupancy (area ratio) of the glass phase and increase air gaps in the conductor surface layer.
  • the conductive paste contains 0.125 parts by weight or more and 1.25 parts by weight or less of Ni powder based on 100 parts by weight of Ag as the conductive powder, 0.2 wt% or more in the conductive paste Even if the glass powder of the above is contained, it is understood that a glass article having a good solder wettability in which the solder wetness is 70% or more in area ratio, and the mechanical strength of which the bonding strength is 100N or more can be obtained.
  • the window glass for a vehicle is formed of laminated glass in which a conductor is formed on a ceramic layer, formation of a glass phase on the surface layer surface of the conductor can be suppressed, and solder wettability and bonding of solder can be obtained.
  • the strength can be improved, and it is useful for various glass articles such as wiper-free glass for preventing heat rays, anti-fogging glass, and glass antenna.

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Abstract

This conductive paste comprises at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle wherein the content of the glass powder is 0.2 wt% or more and the content of the Ni powder relative to 100 parts by weight of the conductive powder is 0.125 to 1.25 parts by weight. This glass article is composed of a ceramic layer 4 formed on a first glass substrate 1 and a conductor 5 formed on the ceramic layer 4. The ceramic layer 4 contains a glass component. The ceramic layer 4 and the conductor 5 comprise a co-fired body formed by co-firing a ceramic film containing the glass component and a conductive film formed by applying the conductive paste. The above achieves a conductive paste that enables a conductor to be obtained having excellent solder wetting and good bond strength with feed terminals, and various glass articles and a method for manufacturing the same.

Description

導電性ペースト、ガラス物品、及びガラス物品の製造方法Conductive paste, glass article, and method of producing glass article
　本発明は、導電性ペースト、ガラス物品、及びガラス物品の製造方法に関し、より詳しくは、自動車等の車両用窓ガラスに付設される熱線等を形成するための導電性ペースト、及びこの導電性ペーストを使用したワイパー凍結防止用熱線付きガラスや防曇ガラス、ガラスアンテナ等の各種ガラス物品、及びこのガラス物品の製造に適したガラス物品の製造方法に関する。 The present invention relates to a conductive paste, a glass article, and a method of manufacturing a glass article, more specifically, a conductive paste for forming a heat wire or the like attached to a window glass of a vehicle or the like, and the conductive paste The present invention relates to various glass articles such as wiper-free heat-resistant glass, anti-fog glass, glass antenna and the like, and a method of producing a glass article suitable for producing the glass article.
　従来より、自動車等の車両用窓ガラスには、ワイパー凍結防止用や防曇用の熱線を配したガラス物品や車外からの電波を受信するガラスアンテナ等のガラス物品が使用されている。これらのガラス物品では、通常、耐衝撃性を考慮して合わせガラスが広く使用されている。 2. Description of the Related Art Conventionally, glass articles such as glass articles provided with heat rays for wiper antifreeze and antifogging and glass articles such as a glass antenna receiving radio waves from the outside of a vehicle are used for window glass for vehicles such as automobiles. In these glass articles, laminated glass is generally used in consideration of impact resistance.
　この種の合わせガラスは、ガラス基体上にセラミック層及び所定パターンの導体を形成するのが一般的であり、前記導体に通電し、導体を発熱させてワイパーの凍結防止や曇り止めを行ったり、或いは車外からの電波を受信している。 In this type of laminated glass, a ceramic layer and a conductor having a predetermined pattern are generally formed on a glass substrate, and the conductor is energized to cause the conductor to generate heat to prevent the wiper from freezing or fogging. Or it receives radio waves from outside the car.
　例えば、特許文献１には、自動車用窓ガラスの面上に導電体が形成されると共に、該面上の周辺部に遮蔽層が形成された導電体付き自動車用窓ガラスにおいて、前記導電体は、前記遮蔽層に重ねて形成された第１の導電体と、該第１の導電体に電気的に接続されるとともに前記窓ガラス面上の前記遮蔽層の内側に位置する前記面上に形成された第２の導電体とからなり、該第２の導電体は、前記第１の導電体よりも抵抗率を低くした導電体付き自動車用窓ガラスが提案されている。 For example, in Patent Document 1, a conductor is formed on a surface of a window glass for an automobile, and the conductor is formed on a window glass for a conductor with a conductor in which a shielding layer is formed on the periphery of the surface. A first conductor formed on the shielding layer, and a surface electrically connected to the first conductor and located on the inner side of the shielding layer on the window glass surface A conductive window glass for an automobile is proposed, which is composed of the second conductive material which has a lower resistivity than the first conductive material.
　この特許文献１では、ガラス粉末の含有量が１～１０ｗｔ％の導電性ペースト（Ａｇペースト）をガラス粉末の含有量が２０～９０ｗｔ％の黒色状セラミック膜に塗布して導電膜を形成し、セラミック膜と導電膜とを共焼成し、これによりセラミック層の表面に導体（Ａｇ電極）を形成している。 In this patent document 1, a conductive paste is formed by applying a conductive paste (Ag paste) having a glass powder content of 1 to 10 wt% to a black ceramic film having a glass powder content of 20 to 90 wt%, The ceramic film and the conductive film are co-fired to form a conductor (Ag electrode) on the surface of the ceramic layer.
特開２００９－２８６２６０号公報（請求項１、段落番号〔００２８〕、〔００３６〕、図１等）JP, 2009-286260, A (claim 1, paragraph number [0028], [0036], FIG. 1, etc.)
　しかしながら、特許文献１では、セラミック膜と導電膜とを共焼成した場合、導電膜やセラミック膜中のガラス成分が焼成後の導体の表層面に偏析し、ガラス相を形成するおそれがある。そして、このようにガラス相が表層面に形成されると導体のはんだ濡れ性が劣化することから、導体と給電端子とをはんだ接続しようとした場合に接合強度の低下を招くおそれがある。特に、近年では環境負荷の軽減化の観点から無鉛はんだの使用が要請されている。斯かる無鉛はんだは、従来の鉛はんだに比べ、はんだ濡れ性に劣る上にはんだ付けに適した温度範囲も狭く、はんだ濡れ性がより劣化して接合強度の更なる低下を招くおそれがある。 However, in Patent Document 1, when the ceramic film and the conductive film are co-fired, the glass component in the conductive film or the ceramic film may be segregated on the surface layer surface of the conductor after firing to form a glass phase. When the glass phase is formed on the surface as described above, the solder wettability of the conductor is degraded, which may result in a decrease in bonding strength when the conductor and the power supply terminal are connected by soldering. In particular, in recent years, the use of lead-free solder has been required from the viewpoint of reducing environmental load. Such a lead-free solder is inferior in solder wettability to a conventional lead solder and has a narrow temperature range suitable for soldering, and the solder wettability may be further deteriorated to cause a further decrease in bonding strength.
　本発明はこのような事情に鑑みなされたものであって、はんだ濡れ性が良好で給電端子との接合強度が良好な導体を得ることができる導電性ペースト、及びこの導電性ペーストを使用した各種ガラス物品、並びにこのガラス物品の製造に適したガラス物品の製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and it is possible to obtain a conductive paste which can obtain a conductor having good solder wettability and good bonding strength with a feeding terminal, and various kinds of conductive pastes using this conductive paste. It is an object of the present invention to provide a glass article and a method of producing a glass article suitable for producing the glass article.
　Ｎｉ粉末は導電性粉末の焼結性を阻害する作用を有することが知られている。そこで、本発明者らは、Ｎｉ粉末が添加された導電性ペーストを使用し、ガラス成分を含有したセラミック膜上に導電パターンを形成して鋭意研究を行ったところ、Ｎｉ粉末の含有量が、導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下の範囲であれば、導電性ペースト中に０．２ｗｔ％以上のガラス粉末を含有していても、焼成後の導体とセラミック層との界面の接合力を確保しつつ、導体表層面にガラス相が形成されるのを抑制することができ、これにより導体表面のはんだ濡れ性や給電端子の接合強度を向上させることができるという知見を得た。 It is known that Ni powder has the effect of inhibiting the sinterability of the conductive powder. Therefore, when the inventors of the present invention conducted conductive research by using a conductive paste to which Ni powder is added and forming a conductive pattern on a ceramic film containing a glass component, the content of Ni powder is If it is a range of 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder, the conductor after firing even if the conductive paste contains 0.2% by weight or more of glass powder It is possible to suppress the formation of a glass phase on the surface layer surface of the conductor while securing the bonding strength at the interface between the ceramic and the ceramic layer, thereby improving the solder wettability of the conductor surface and the bonding strength of the feeding terminal. We have found that we can
　本発明はこのような知見に基づきなされたものであって、本発明に係る導電性ペーストは、ガラス成分を含有したセラミック膜上に導電パターンを形成するための導電性ペーストであって、少なくとも導電性粉末、ガラス粉末、Ｎｉ粉末、及び有機ビヒクルを含有すると共に、前記ガラス粉末の含有量が、０．２ｗｔ％以上であり、かつ、前記Ｎｉ粉末の含有量が、前記導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下であることを特徴としている。 The present invention has been made based on such findings, and the conductive paste according to the present invention is a conductive paste for forming a conductive pattern on a ceramic film containing a glass component, at least the conductive paste. Powder, glass powder, Ni powder, and an organic vehicle, and the content of the glass powder is 0.2 wt% or more, and the content of the Ni powder is 100 parts by weight of the conductive powder In contrast, it is characterized in that it is 0.125 parts by weight or more and 1.25 parts by weight or less.
　尚、上記「Ｎｉ粉末」にはＮｉを主成分とする場合も含むものとする。 Incidentally, the above "Ni powder" also includes the case where Ni is a main component.
　また、本発明の導電性ペーストは、前記導電性粉末が、Ａｇを主成分としているのが好ましい。 In the conductive paste of the present invention, the conductive powder preferably contains Ag as a main component.
　また、本発明に係るガラス物品は、ガラス成分を含有したセラミック層がガラス基体上に形成されると共に、前記セラミック層上に導体が形成されたガラス物品であって、前記セラミック層と前記導体とは、前記ガラス成分を含有したセラミック膜と、ガラス粉末の含有量が導電性ペースト中で０．２ｗｔ％以上であり、かつＮｉ粉末の含有量が、導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下とされた導電膜とが共焼成された共焼結体からなることを特徴としている。 The glass article according to the present invention is a glass article in which a ceramic layer containing a glass component is formed on a glass substrate, and a conductor is formed on the ceramic layer, and the ceramic layer and the conductor The content of the glass powder and the ceramic film containing the glass component is 0.2 wt% or more in the conductive paste, and the content of the Ni powder is 0.125 based on 100 parts by weight of the conductive powder. It is characterized in that it is made of a co-sintered body obtained by co-firing a conductive film of not less than 1 part by weight and not more than 1.25 parts by weight.
　尚、上記「Ｎｉ粉末」にはＮｉを主成分とする場合も含むものとする。 Incidentally, the above "Ni powder" also includes the case where Ni is a main component.
　また、本発明のガラス物品は、前記セラミック膜に含有される前記ガラス成分が、非晶質であるのが好ましい。 In the glass article of the present invention, the glass component contained in the ceramic film is preferably amorphous.
　このようにセラミック膜中のガラス成分が非晶質の場合は、焼成時により流動化し易く、前記ガラス成分を導体中に効果的に浸透させることができ、セラミック層とガラス基体との界面接合力のみならず、導体とセラミック層との界面接合力をより一層向上させることができる。 As described above, when the glass component in the ceramic film is amorphous, it is likely to be fluidized by firing, and the glass component can be effectively permeated into the conductor, and the interfacial bonding force between the ceramic layer and the glass substrate Not only that, the interfacial bonding strength between the conductor and the ceramic layer can be further improved.
　また、本発明のガラス物品では、前記導体は、表層面における前記ガラス成分の占有率が、面積比率で３０％以下であるのが好ましい。 In the glass article of the present invention, the conductor preferably has an occupancy of 30% or less in area ratio of the glass component in the surface layer surface.
　これにより導体表面のはんだ濡れ性を確保することができ、はんだの接合強度の向上を図ることができる。 Thereby, the solder wettability of the conductor surface can be secured, and the joint strength of the solder can be improved.
　また、本発明のガラス物品は、前記セラミック層が、無機顔料を含有しているのが好ましく、この場合、前記無機顔料は、黒色系顔料であるのが好ましい。 In the glass article of the present invention, the ceramic layer preferably contains an inorganic pigment, and in this case, the inorganic pigment is preferably a black pigment.
　すなわち、車両用窓ガラスでは、窓ガラスの周囲をウレタン系樹脂等の保持材で拘束しているが、セラミック層が黒色系無機顔料を含有することより、紫外光に起因する保持剤の劣化を防止することができ、また車内での防眩作用を確保することが可能となる。 That is, in the window glass for vehicles, although the periphery of the window glass is restrained by a holding material such as a urethane resin, deterioration of the holding agent due to ultraviolet light is caused by the ceramic layer containing a black inorganic pigment. Therefore, the antiglare function in the car can be secured.
　また、本発明に係るガラス物品の製造方法は、少なくともセラミック粉末、ガラス成分、及び有機ビヒクルを含有したセラミックペーストを準備する工程と、少なくとも導電性粉末、ガラス粉末、Ｎｉ粉末、及び有機ビヒクルを含有し、前記ガラス粉末の含有量が０．２ｗｔ％以上であり、かつ前記Ｎｉ粉末の含有量が、前記導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下に調製された導電性ペーストを準備する工程と、前記セラミックペーストをガラス基体に塗布してセラミック膜を形成する工程とを含むことを特徴としている。 The method for producing a glass article according to the present invention further comprises the steps of preparing a ceramic paste containing at least a ceramic powder, a glass component, and an organic vehicle, and at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle. The content of the glass powder is 0.2 wt% or more, and the content of the Ni powder is adjusted to 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder. It is characterized in that it comprises the steps of: preparing a conductive paste; and applying the ceramic paste to a glass substrate to form a ceramic film.
　また、本発明のガラス物品の製造方法は、前記セラミックペーストを前記ガラス基体に塗布して未焼成セラミック膜を形成する工程と、前記未焼成セラミック膜上に前記導電性ペーストを塗布して未焼成導電膜を形成する工程と、前記未焼成セラミック膜と前記未焼成導電膜とを共焼成する工程とを含むのが好ましい。 In the method for producing a glass article of the present invention, the step of applying the ceramic paste to the glass substrate to form a non-fired ceramic film, and applying the conductive paste on the non-fired ceramic film to perform non-baking It is preferable to include the step of forming a conductive film, and the step of co-firing the green ceramic film and the green conductive film.
　また、本発明のガラス物品の製造方法は、前記セラミック粉末が、無機顔料を含むのが好ましい。 In the method of producing a glass article according to the present invention, preferably, the ceramic powder contains an inorganic pigment.
　本発明の導電性ペーストによれば、ガラス成分を含有したセラミック膜上に導電パターンを形成するための導電性ペーストであって、少なくとも導電性粉末、ガラス粉末、Ｎｉ粉末、及び有機ビヒクルを含有すると共に、前記ガラス粉末の含有量が、０．２ｗｔ％以上であり、かつ、前記Ｎｉ粉末の含有量が、前記導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下であるので、Ｎｉ酸化物が形成されることもなく焼成時に導電性粉末間に微細で複雑な形状を有する多数の空隙が形成されることから、焼成後の導体表層面にガラス相が形成されるのを抑制することができ、これによりはんだ濡れ性が良好で接合強度の良好な導電性ペーストを得ることができる。 According to the conductive paste of the present invention, it is a conductive paste for forming a conductive pattern on a ceramic film containing a glass component, which contains at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle. In addition, the content of the glass powder is 0.2 wt% or more, and the content of the Ni powder is 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder. As a result, no Ni oxide is formed and a large number of voids having a fine and complicated shape are formed between conductive powders at the time of firing, so that a glass phase is formed on the conductor surface after firing. As a result, it is possible to obtain a conductive paste having good solder wettability and good bonding strength.
　また、本発明のガラス物品によれば、ガラス成分を含有したセラミック層がガラス基体上に形成されると共に、前記セラミック層上に導体が形成されたガラス物品であって、前記セラミック層と前記導体とは、前記ガラス成分を含有したセラミック膜と、ガラス粉末の含有量が導電性ペースト中で０．２ｗｔ％以上であり、かつＮｉ粉末の含有量が、導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下とされた導電膜とが共焼成された共焼結体からなるので、セラミック膜中のガラス成分及び導電性ペースト中のガラス粉末によって導体とセラミック層との界面接合力を確保できると共に、導体表層面でのガラス相の形成を抑制することができ、これによりはんだ濡れ性や接合強度を改善することができる。 Further, according to the glass article of the present invention, a ceramic layer containing a glass component is formed on a glass substrate, and a conductor is formed on the ceramic layer, wherein the ceramic layer and the conductor are formed. The content of the glass powder and the ceramic film containing the glass component is 0.2 wt% or more in the conductive paste, and the content of the Ni powder is 0.1 parts by weight to 100 parts by weight of the conductive powder. Since the conductive film of 125 parts by weight or more and 1.25 parts by weight or less is co-sintered, the glass component in the ceramic film and the glass powder in the conductive paste The interface bonding strength can be secured, and the formation of the glass phase on the surface layer of the conductor can be suppressed, whereby the solder wettability and the bonding strength can be improved.
　また、本発明のガラス物品の製造方法によれば、少なくともセラミック粉末、ガラス成分、及び有機ビヒクルを含有したセラミックペーストを準備する工程と、少なくとも導電性粉末、ガラス粉末、Ｎｉ粉末、及び有機ビヒクルを含有し、前記ガラス粉末の含有量が０．２ｗｔ％以上であり、かつ前記Ｎｉ粉末の含有量が、前記導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下に調製された導電性ペーストを準備する工程と、前記セラミックペーストをガラス基体に塗布してセラミック膜を形成する工程とを含むので、導体表層面でのガラス相の形成が抑制された各種ガラス物品を容易に得ることができる。 Further, according to the method for producing a glass article of the present invention, a process of preparing a ceramic paste containing at least a ceramic powder, a glass component, and an organic vehicle, and at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle The content of the glass powder is 0.2 wt% or more, and the content of the Ni powder is 0.125 parts by weight or more and 1.25 parts by weight or less based on 100 parts by weight of the conductive powder. Since the steps of preparing the conductive paste and applying the ceramic paste to a glass substrate to form a ceramic film, various glass articles in which the formation of the glass phase on the surface layer of the conductor is suppressed are facilitated. Can be obtained.
本発明に係る導電性ペーストを使用して製造されたガラス物品の一実施の形態（第１の実施の形態）を示す正面図である。BRIEF DESCRIPTION OF THE DRAWINGS It is a front view which shows one Embodiment (1st Embodiment) of the glass article manufactured using the electrically conductive paste which concerns on this invention. 図１のＡ－Ａ矢視断面図である。It is AA arrow sectional drawing of FIG. 上記ガラス物品の第１の変形例を模式的に示す要部断面図である。It is principal part sectional drawing which shows typically the 1st modification of the said glass article. 上記ガラス物品の第２の変形例を模式的に示す要部断面図である。It is principal part sectional drawing which shows typically the 2nd modification of the said glass article. 上記ガラス物品の第３の変形例を模式的に示す要部断面図である。It is principal part sectional drawing which shows typically the 3rd modification of the said glass article. 本発明に係るガラス物品の第２の実施の形態を示す要部断面図である。It is an important section sectional view showing a 2nd embodiment of a glass article concerning the present invention. 試料番号１のはんだ濡れ性試験の試験結果を示す撮像図である。It is an imaging figure which shows the test result of the solder wettability test of the sample number 1. FIG. 試料番号２の導体表層面の平面ＳＥＭ画像である。It is a plane SEM image of the conductor surface side of sample number 2. 試料番号９のはんだ濡れ性試験の試験結果を示す撮像図である。It is an imaging figure which shows the test result of the solder wettability test of the sample number 9. 試料番号３のはんだ濡れ性試験の試験結果を示す撮像図である。It is an imaging figure which shows the test result of the solder wettability test of the sample number 3. FIG. 試料番号４のはんだ濡れ性試験の試験結果を示す撮像図である。It is an imaging figure which shows the test result of the solder wettability test of the sample number 4. FIG. 試料番号１の断面ＳＥＭ画像である。It is a cross-sectional SEM image of the sample number 1. 試料番号３の断面ＳＥＭ画像である。It is a cross-sectional SEM image of sample number 3.
　次に、本発明の実施の形態を詳説する。 Next, the embodiment of the present invention will be described in detail.
　図１は、本発明に係る導電性ペーストを使用して製造されたガラス物品の一実施の形態（第１の実施の形態）を示す正面図であり、本実施の形態は、ワイパー凍結防止用熱線付きガラス（以下、「熱線付きガラス」という。）を示している。図２は図１のＡ－Ａ矢視断面図である。 FIG. 1 is a front view showing an embodiment (first embodiment) of a glass article manufactured using the conductive paste according to the present invention, and this embodiment is for wiper antifreeze The figure shows a glass with heat rays (hereinafter referred to as "glass with heat rays"). FIG. 2 is a sectional view taken along the line AA of FIG.
　すなわち、この熱線付きガラスは、第１のガラス基体１と第２のガラス基体２との間にポリビニルアルコール樹脂等で形成された中間膜３を介在させた合わせガラスからなり、耐衝撃性を考慮した構造とされている。 That is, this heat-ray attached glass is made of laminated glass in which an intermediate film 3 formed of a polyvinyl alcohol resin or the like is interposed between the first glass substrate 1 and the second glass substrate 2, and impact resistance is taken into consideration. The structure is
　この熱線付きガラスは、第１のガラス基体１の外周に沿って黒色系のセラミック層４が形成され、さらにセラミック層４上であって、ワイパーのホームポジション近傍の所定域に導体５が形成されると共に、該導体５ははんだ６を介して給電端子７に接続され、自動車等の車両のフロント部に装備される。 In the heat-rayed glass, a black ceramic layer 4 is formed along the outer periphery of the first glass substrate 1, and a conductor 5 is formed on the ceramic layer 4 in a predetermined area near the home position of the wiper. The conductor 5 is connected to the feed terminal 7 through the solder 6 and mounted on the front portion of a vehicle such as a car.
　本熱線付きガラスは、低温乃至極低温雰囲気にあるときに前記導体５に通電して発熱させ、第１のガラス基体１の表面温度を上昇させることにより、凍結等によりワイパーの動作不良が生じるのを回避している。さらに、セラミック層４を黒色系とすることにより、熱線付きガラスを車体に拘束するウレタン系樹脂等の保持剤が紫外光により劣化するのを防止している。 In the glass with heat ray, when the conductor 5 is in a low temperature to a low temperature atmosphere, the conductor 5 is energized to generate heat, and the surface temperature of the first glass substrate 1 is raised to cause a malfunction of the wiper due to freezing or the like. Is avoiding. Furthermore, by making the ceramic layer 4 black, it is possible to prevent the holding agent such as urethane resin which restrains the heat-rayed glass from being deteriorated by ultraviolet light.
　そして、セラミック層４と導体５とは、ガラス成分を含有したセラミック膜と、ガラス粉末の含有量が導電性ペースト中で０．２ｗｔ％以上であり、かつＮｉ粉末の含有量が、導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下とされた導電膜とが共焼成された共焼結体からなるので、セラミック膜中のガラス成分及び導電性ペースト中のガラス粉末によって導体５とセラミック層４との界面接合力を確保できると共に、導体表層面でのガラス相の形成を抑制することができ、これによりはんだ濡れ性や接合強度を改善することができる。 The ceramic layer 4 and the conductor 5 have a ceramic film containing a glass component, and the content of the glass powder is 0.2 wt% or more in the conductive paste, and the content of the Ni powder is a conductive powder. Since the conductive film made 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight is made of co-sintered body, the glass component in the ceramic film and the glass powder in the conductive paste Thus, the interfacial bonding strength between the conductor 5 and the ceramic layer 4 can be secured, and the formation of the glass phase on the surface layer of the conductor can be suppressed, whereby the solder wettability and the bonding strength can be improved.
　すなわち、この種の導体５を形成するための導電性ペーストは、従来、０．２～１０ｗｔ％程度のガラス粉末が含有されており、これによりセラミック膜から浸透してくるガラス成分と相俟って導体５とセラミック層４との固着力を確保している。しかしながら、その一方で導電性ペーストに含有されるガラス粉末及びセラミック膜中のガラス成分が焼成時に流動し、導体５の表層面に偏析して該表層面にガラス相を形成し、このためはんだ濡れ性の劣化を招き、給電端子７の接合強度の低下を招くおそれがある。 That is, the conductive paste for forming the conductor 5 of this type conventionally contains about 0.2 to 10 wt% of glass powder, and thereby it is associated with the glass component penetrating from the ceramic film. The adhesion between the conductor 5 and the ceramic layer 4 is secured. However, on the other hand, the glass powder contained in the conductive paste and the glass component in the ceramic film flow at the time of firing and segregate to the surface layer surface of the conductor 5 to form a glass phase on the surface layer surface. In this case, the bond strength of the feed terminal 7 may be reduced.
　ところで、Ｎｉ粉末は導電性粉末の焼結性を阻害する作用を有することが知られている。したがって、所定量のＮｉ粉末を導電性ペースト中に含有させることにより、導電性ペースト中に０．２ｗｔ％以上のガラス粉末を含有していても、焼成後の導体とセラミック層との界面の接合力を確保しつつ、導体表層面にガラス相が形成されるのを抑制することが可能と考えられる。 By the way, it is known that Ni powder has the effect of inhibiting the sinterability of the conductive powder. Therefore, by containing a predetermined amount of Ni powder in the conductive paste, even if the conductive paste contains 0.2 wt% or more of glass powder, bonding of the interface between the conductor after firing and the ceramic layer is performed. It is considered possible to suppress the formation of the glass phase on the surface layer of the conductor while securing the force.
　そこで、本実施の形態では、前記所定量を導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下の範囲とし、Ｎｉ粉末を導電性ペースト中に含有させている。そしてこれにより導電性ペースト中に０．２ｗｔ％以上のガラス粉末を含有していても、セラミック膜中のガラス成分や導電性ペースト中のガラス粉末の導体表層面への偏析を抑制することが可能となり、はんだ濡れ性及び接合強度を改善している。 So, in this Embodiment, the said predetermined amount is made into the range of 0.125 weight part or more and 1.25 weight part or less with respect to 100 weight part of electroconductive powder, and Ni powder is contained in the electroconductive paste. Thus, even if the conductive paste contains 0.2 wt% or more of glass powder, it is possible to suppress segregation of the glass component in the ceramic film and the glass powder in the conductive paste to the surface layer of the conductor. To improve solder wettability and bonding strength.
　すなわち、上述したようにＮｉ粉末は導電性粉末の焼結を阻害する作用を有することから、導電性ペースト中にＮｉ粉末を含有させた場合、導電性粉末間には微細で複雑な形状を有する多数の空隙が生成される。したがって、斯かる空隙が抵抗乃至障害となってセラミック膜中のガラス成分や導電性ペースト中のガラス粉末が導体表層面に偏析し難くなる。その結果導体表層面でのガラス相の形成を抑制することができ、はんだ濡れ性やはんだの接合強度を改善することができる。 That is, as described above, since the Ni powder has the function of inhibiting the sintering of the conductive powder, when the conductive powder contains the Ni powder, the conductive powder has a fine and complicated shape. A large number of voids are created. Therefore, such air gaps become resistance or obstacle and it becomes difficult for the glass component in the ceramic film and the glass powder in the conductive paste to be segregated on the surface layer of the conductor. As a result, the formation of the glass phase on the surface layer of the conductor can be suppressed, and the solder wettability and the joint strength of the solder can be improved.
　そのためにはＮｉ粉末の含有量は、導電性粉末１００重量部に対し少なくとも０．１２５重量部は必要である。一方、Ｎｉ粉末の含有量が、導電性粉末１００重量部に対し１．２５重量部を超えると、Ｎｉ粉末は焼成中に容易に酸化してＮｉ酸化物が生成されることから、導体表層面のガラス相の形成は抑制されるものの、はんだ濡れ性や接合強度の劣化を招くおそれがある。 For this purpose, the content of Ni powder is required to be at least 0.125 parts by weight with respect to 100 parts by weight of the conductive powder. On the other hand, when the content of the Ni powder exceeds 1.25 parts by weight with respect to 100 parts by weight of the conductive powder, the Ni powder is easily oxidized during firing to form a Ni oxide, so the conductor surface layer surface Although the formation of the glass phase is suppressed, the solder wettability and the bonding strength may be deteriorated.
　そこで、本実施の形態では、上述したようにＮｉ粉末を導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下の範囲で導電性ペースト中に含有させ、これによりはんだ濡れ性や接合強度を改善している。 Therefore, in the present embodiment, as described above, Ni powder is contained in the conductive paste in the range of 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder. Improve the strength and bonding strength.
　尚、導電性粉末としては、良好な導電性を有する金属粉であれば特に限定されるものではないが、通常はＡｇ粉末を好んで使用することができる。また、Ａｇ粉末を主成分とし、Ｐｄ粉末、Ｐｔ粉末等の各種導電性粉末を副成分として含有させてもよい。 The conductive powder is not particularly limited as long as it is a metal powder having good conductivity, but in general, Ag powder can be preferably used. In addition, Ag powder may be used as a main component, and various conductive powders such as Pd powder and Pt powder may be contained as subcomponents.
　また、導電性粉末の形状も特に限定されるものではなく、例えば、球形状、扁平状、不定形形状、或いはこれらの混合粉であってもよい。 Further, the shape of the conductive powder is not particularly limited, and may be, for example, a spherical shape, a flat shape, an irregular shape, or a mixed powder thereof.
　さらに、導電性粉末の平均粒径Ｄ50も特に限定されるものではないが、スクリーン印刷で目詰まりが生じない程度の大きさの導電性粉末を使用するのが好ましく、例えば平均粒径Ｄ50が１０μｍ以下の導電性粉末を好んで使用することができる。 Furthermore, the average particle size D 50 of the conductive powder is not particularly limited, but it is preferable to use a conductive powder of such a size that clogging does not occur in screen printing, for example, the average particle size D 50 Preferably, a conductive powder having a diameter of 10 μm or less can be used.
　また、導電性ペースト中の導電性粉末の含有量は、特に限定されるものではないが、５０～９０ｗｔ％が好ましい。導電性粉末の含有量が５０ｗｔ％未満になると、標準的な３～２０μｍの厚膜の導体５を得るためにはスクリーン印刷時に線径の大きなメッシュを有するスクリーン印刷版を使用しなければならず、解像度の低下を招くおそれがある。一方、導電性粉末の含有量が９０ｗｔ％を超えると、導電性粉末が過剰となってペースト化が困難になるおそれがある。したがって、導電性粉末の含有量は、特に限定されないものの、５０～９０ｗｔ％が好ましい。 The content of the conductive powder in the conductive paste is not particularly limited, but is preferably 50 to 90 wt%. When the content of the conductive powder is less than 50 wt%, in order to obtain a standard 3 to 20 μm thick film conductor 5, it is necessary to use a screen printing plate having a mesh with a large diameter during screen printing. , May cause a reduction in resolution. On the other hand, when the content of the conductive powder exceeds 90 wt%, the conductive powder may be excessive to make it difficult to paste. Therefore, the content of the conductive powder is preferably 50 to 90 wt%, although it is not particularly limited.
　また、有機ビヒクルは、バインダ樹脂と有機溶剤とが、例えば体積比率で、１～３：７～９となるように調製されている。尚、バインダ樹脂としては、特に限定されるものではなく、例えば、エチルセルロース樹脂、ニトロセルロース樹脂、アクリル樹脂、アルキド樹脂、又はこれらの組み合わせを使用することができる。また、有機溶剤についても特に限定されるものではなく、α―テルピネオール、キシレン、トルエン、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート等を単独、或いはこれらを組み合わせて使用することができる。 Also, the organic vehicle is prepared such that the binder resin and the organic solvent are, for example, 1 to 3: 7 to 9 in volume ratio. The binder resin is not particularly limited, and, for example, ethyl cellulose resin, nitrocellulose resin, acrylic resin, alkyd resin, or a combination thereof can be used. Also, the organic solvent is not particularly limited, and α-terpineol, xylene, toluene, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, etc. alone or in combination thereof It can be used.
　そして、本導電性ペーストは、ガラス粉末の含有量が０．２ｗｔ％以上、Ｎｉ粉末の含有量が導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下となるように、三本ロールミル等を使用して分散、混錬することにより容易に作製することができる。 And, in the present conductive paste, the content of the glass powder is 0.2 wt% or more, and the content of the Ni powder is 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder. It can be easily produced by dispersing and kneading using a three-roll mill or the like.
　このように本導電性ペーストは、少なくとも導電性粉末、ガラス粉末、Ｎｉ粉末、及び有機ビヒクルを含有すると共に、前記ガラス粉末の含有量が、０．２ｗｔ％以上であり、かつ、前記Ｎｉ粉末の含有量が、前記導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下であるので、Ｎｉ酸化物が過度に形成されることもなく焼成時に導電性粉末間に微細で複雑な形状を有する多数の空隙が形成されることから、焼成後の導体表層面にガラス相が形成されるのを抑制することができ、これによりはんだ濡れ性が良好で接合強度の良好な導電性ペーストを得ることができる。 Thus, the present conductive paste contains at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle, and the content of the glass powder is 0.2 wt% or more, and of the Ni powder. Since the content is 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder, there is no excessive formation of Ni oxide and fine particles are obtained between the conductive powders at the time of firing. Since a large number of voids having a complicated shape are formed, it is possible to suppress the formation of a glass phase on the surface layer surface of the conductor after firing, which makes it possible to have good solder wettability and good bonding strength. Sex paste can be obtained.
　次に、上記熱線付きガラスの製造方法を詳述する。 Next, the method of producing the above-mentioned glass with heat ray will be described in detail.
　まず、セラミック粉末、ガラス成分、及び有機ビヒクルを含有したセラミックペーストを用意する。 First, a ceramic paste containing a ceramic powder, a glass component, and an organic vehicle is prepared.
　ガラス成分としては、特に限定されるものではなく、ＺｎＯ、Ａｌ２Ｏ３、Ｂ２Ｏ３、ＳｉＯ２、ＴｉＯ２、ＺｒＯ２、アルカリ金属酸化物、アルカリ土類金属酸化物等の中から必要に応じて適宜選択し、所定組成に調合して使用することができる。また、セラミック粉末としては黒色系無機顔料を含むものが好ましく、黒色系無機顔料としてはＣｒ２Ｏ３、ＣｕＯ等を使用することができる。 The glass component is not particularly limited, and it is necessary to select from among ZnO, Al 2 O 3 , B 2 O 3 , SiO 2 , SiO 2 , TiO 2 , ZrO 2 , alkali metal oxides, alkaline earth metal oxides, etc. The composition can be appropriately selected according to the formula and formulated into a predetermined composition. As the ceramic powder preferably those containing black-based inorganic pigments, as a black inorganic pigment may be used Cr 2 O 3, CuO and the like.
　さらにガラス成分は、非晶質であるのが好ましい。非晶質ガラスは、焼成時に軟化しやすく、流動性に富むことから、導電膜中に容易に浸透して焼成後の導体５内に固定される。 Furthermore, the glass component is preferably amorphous. Amorphous glass is easily softened at the time of firing and is highly fluid, so it easily penetrates into the conductive film and is fixed in the conductor 5 after firing.
　尚、有機ビヒクルは、上述した本発明の導電性ペーストと同様のものを使用することができる。 As the organic vehicle, one similar to the above-mentioned conductive paste of the present invention can be used.
　次に、本発明の導電性ペーストを、上述した方法で作製する。 Next, the conductive paste of the present invention is produced by the method described above.
　そして、スクリーン印刷法を使用して第１のガラス基体１の外周に沿ってセラミックペーストを塗布して乾燥させ、黒色系の無機顔料及びガラス成分を含有した未焼成のセラミック膜を形成する。 Then, a ceramic paste is applied along the outer periphery of the first glass substrate 1 by screen printing and dried to form an unfired ceramic film containing a black inorganic pigment and a glass component.
　次いで、スクリーン印刷法を使用し、ワイパーのホームポジションに対応するセラミック膜の下部所定領域に導電性ペーストを塗布し、乾燥させて未焼成の導電膜を形成する。 Next, using a screen printing method, a conductive paste is applied to a lower predetermined area of the ceramic film corresponding to the home position of the wiper, and dried to form a non-fired conductive film.
　そして、未焼成のセラミック膜及び未焼成の導電膜が形成された第１のガラス基体１を、大気雰囲気等の非還元性雰囲気中、５５０～６５０℃の温度で５分程度焼成し、これにより、セラミック層４及び導体５が共焼成（co-fire）されたセラミック層４及び導体５を有する第１のガラス基体１を得る。 Then, the first glass substrate 1 on which the unfired ceramic film and the unfired conductive film are formed is fired at a temperature of 550 to 650 ° C. for about 5 minutes in a non-reducing atmosphere such as an air atmosphere. The first glass substrate 1 is obtained having the ceramic layer 4 and the conductor 5 in which the ceramic layer 4 and the conductor 5 are co-fired.
　尚、この焼成時にガラス成分は、導体５の内部に浸透し、導電性ペースト中のガラス粉末と相俟ってセラミック層４と導体５との界面の接合力が確保されると共に、導体表層面へのガラス相の形成が抑制される。具体的には導体５の表層面のガラス相の占有率は面積比率で３０％以下に抑制される。 During the firing, the glass component penetrates into the inside of the conductor 5, and the bonding strength of the interface between the ceramic layer 4 and the conductor 5 is secured by the combination of the glass powder in the conductive paste and the conductor surface The formation of a glass phase is suppressed. Specifically, the occupancy of the glass phase of the surface layer surface of the conductor 5 is suppressed to 30% or less in area ratio.
　その後、中間膜３が第１のガラス基体１と第２のガラス基体２とで狭持されるように接着剤を介して貼付し、これにより上述した熱線付きガラスが作製される。 Thereafter, the intermediate film 3 is attached via an adhesive so that the intermediate film 3 is sandwiched between the first glass substrate 1 and the second glass substrate 2, whereby the above-described glass with heat wire is manufactured.
　このように本製造方法によれば、黒色系無機顔料を含むセラミック粉末、ガラス成分、及び有機ビヒクルを含有したセラミックペーストを準備する工程と、少なくとも導電性粉末、ガラス粉末、Ｎｉ粉末、及び有機ビヒクルを含有し、前記ガラス粉末の含有量が０．２ｗｔ％以上であり、かつ前記Ｎｉ粉末の含有量が、前記導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下に調製された導電性ペーストを準備する工程と、前記セラミックペーストをガラス基体に塗布してセラミック膜を形成する工程と、前記セラミック膜上に前記導電性ペーストを塗布して導電膜を形成する工程と、前記導電膜と前記セラミック膜とを共焼成する工程とを含むので、Ｎｉ酸化物が過度に生成されることもなく導体表層面のガラス相の形成が抑制され、はんだ濡れ性が良好で導体５と給電端子７との接合強度が良好な熱線付きガラスを得ることができる。 Thus, according to the present production method, a step of preparing a ceramic paste containing a black-based inorganic pigment, a glass component, and an organic vehicle, and at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle The content of the glass powder is 0.2 wt% or more, and the content of the Ni powder is 0.125 parts by weight or more and 1.25 parts by weight or less based on 100 parts by weight of the conductive powder. Preparing the prepared conductive paste, applying the ceramic paste to a glass substrate to form a ceramic film, applying the conductive paste on the ceramic film to form a conductive film, and Since the step of co-firing the conductive film and the ceramic film is included, there is no excessive formation of Ni oxide, and the glass phase of the surface layer of the conductor Formation is suppressed, can be bonding strength of the solder wettability is a good conductor 5 and the power supply terminal 7 to obtain a good heat ray with glass.
　尚、本製造方法では、未焼成セラミック膜と未焼成導電膜の共焼成プロセスを例示したが、焼成済みのセラミック膜に未焼成導電膜を形成し、焼成するプロセス（post-fire）を適用してもよい。ただし、セラミック膜と導電膜の接合強度の改善やプロセスの簡素化は可能であることから共焼成プロセスの方が好ましい。 In the present manufacturing method, the co-firing process of the unfired ceramic film and the unfired conductive film is exemplified, but a process (post-fire) of forming the unfired conductive film on the fired ceramic film and firing is applied. May be However, the co-firing process is preferable because the bonding strength between the ceramic film and the conductive film can be improved and the process can be simplified.
　図３は上記実施の形態の第１の変形例を模式的に示す要部断面図である。 FIG. 3 is a cross-sectional view of main parts schematically showing a first modification of the embodiment.
　この第１の変形例では、はんだ６を介して給電端子７と接する導体５の部分のみがＮｉを含有した本発明の導電性ペーストで作製され、給電端子７と接していない部分の導体１１ａ、１１ｂはＮｉ粉末を含有していない従来の導電性ペーストの焼結体で形成されている。そしてこれにより、上述と同様の理由から導体表層面にガラス相が形成されるのを抑制することができ、はんだ濡れ性が良好で接合強度の良好な熱線付きガラスを得ることができる。 In the first modification, only the portion of the conductor 5 in contact with the feeding terminal 7 via the solder 6 is made of the conductive paste of the present invention containing Ni, and the conductor 11a of the portion not in contact with the feeding terminal 7 11 b is formed of a sintered body of a conventional conductive paste containing no Ni powder. And thereby, it can suppress that a glass phase is formed in a conductor surface layer surface from the same reason as the above-mentioned, and solder wettability can be obtained and glass with a heat wire with favorable joining strength can be obtained.
　図４は上記実施の形態の第２の変形例を模式的に示す要部断面図である。 FIG. 4 is a cross-sectional view of main parts schematically showing a second modified example of the above embodiment.
　この第２の変形例では、導体５とセラミック層４との間にＮｉ粉末を含有していない従来の導電性ペーストの焼結体である導体１２が介在されている。 In the second modification, a conductor 12 which is a sintered body of a conventional conductive paste containing no Ni powder is interposed between the conductor 5 and the ceramic layer 4.
　すなわち、この第２の変形例では、第１のガラス基体１の表面にセラミックペーストを塗布・乾燥させてセラミック膜を形成した後、Ｎｉ粉末を含有していない従来の導電性ペーストをセラミック膜の表面に塗布・乾燥させて導電膜を形成し、該導電膜上の給電端子７と接する部分にのみ本導電性ペーストを塗布・乾燥させて導電膜を形成し、セラミック膜と２つの導電膜とを共焼成してセラミック層４及び導体１２、５を得ている。 That is, in the second modification, after the ceramic paste is applied and dried on the surface of the first glass substrate 1 to form a ceramic film, the conventional conductive paste containing no Ni powder is used as the ceramic film. The conductive paste is applied and dried on the surface to form a conductive film, and the conductive paste is applied and dried only on the portion of the conductive film in contact with the feed terminal 7 to form a conductive film, and a ceramic film and two conductive films Are co-fired to obtain the ceramic layer 4 and the conductors 12 and 5.
　そして、この第２の変形例では、セラミック膜中のガラス成分が従来の導電性ペーストで作製された導体１２が導体５内に浸透したり、或いはセラミック膜中のガラス成分が導体１２を通過して導体５内に浸透した場合であっても、導体５が、所定量のＮｉ粉末を含有した本発明の導電性ペーストで形成されているので、Ｎｉ酸化物が過度に形成されることもなく導体表層面でのガラス相の形成を抑制することができ、はんだ濡れ性が良好で接合強度の良好な熱線付きガラスを得ることができる。 In the second modification, the glass component in the ceramic film penetrates the conductor 5 made of the conventional conductive paste into the conductor 5, or the glass component in the ceramic film passes through the conductor 12 Since the conductor 5 is formed of the conductive paste of the present invention containing a predetermined amount of Ni powder even if it penetrates into the conductor 5, the Ni oxide is not excessively formed. It is possible to suppress the formation of the glass phase on the surface layer of the conductor, and it is possible to obtain a glass with heat wire having good solder wettability and good bonding strength.
　図５は上記実施の形態の第３の変形例を模式的に示す要部断面図である。 FIG. 5 is a cross-sectional view of main parts schematically showing a third modification of the embodiment.
　この第３の変形例では、セラミック層４及び導体５の表面にＮｉ粉末を含有していない従来の導電性ペーストの焼結体である導体１３が形成されている。 In the third modification, a conductor 13 which is a sintered body of a conventional conductive paste containing no Ni powder is formed on the surfaces of the ceramic layer 4 and the conductor 5.
　すなわち、この第３の変形例では、第１のガラス基体１の表面にセラミックペーストを塗布・乾燥させてセラミック膜を形成した後、給電端子７と対向する部分に本導電性ペーストを塗布・乾燥させて導電膜を形成し、さらにＮｉ粉末を含有していない従来の導電性ペーストを導電膜の表面に塗布・乾燥させて新たな導電膜を形成し、セラミック膜と２つの導電膜とを共焼成してセラミック層４及び導体５、１３を得ている。 That is, in the third modification, after the ceramic paste is applied and dried on the surface of the first glass substrate 1 to form a ceramic film, the conductive paste is applied and dried on the portion facing the feeding terminal 7. And a conventional conductive paste not containing Ni powder is applied on the surface of the conductive film and dried to form a new conductive film, and the ceramic film and the two conductive films are co-formed. The ceramic layer 4 and the conductors 5 and 13 are obtained by firing.
　この種の熱線付きガラスでは、通常、セラミックペースト中のガラス成分の含有量は、導電性ペースト中のガラス粉末の含有量に比べ多量であることが知られており、したがって、導体表層面でのガラス相の形成を抑制するためには、セラミック膜中のガラス成分が導体表層面に偏析するのを抑制するのが効果的と考えられる。 In this type of heat-coated glass, the content of the glass component in the ceramic paste is generally known to be large compared to the content of the glass powder in the conductive paste, and hence In order to suppress the formation of the glass phase, it is considered effective to suppress the segregation of the glass component in the ceramic film on the surface layer of the conductor.
　しかるに、この第３の変形例では、給電端子７と対向する部分に本発明の導電性ペーストで作製された導体５が形成されており、これによりセラミック膜中のガラス成分が導体１３に浸透するのを抑制することができる。したがって、導体１３の表層面でのガラス相の形成が抑制されることから、はんだ濡れ性が良好で接合強度の良好な熱線付きガラスを得ることができる。 However, in the third modification, the conductor 5 made of the conductive paste of the present invention is formed in the portion facing the feeding terminal 7, whereby the glass component in the ceramic film penetrates the conductor 13. Can be suppressed. Therefore, since the formation of the glass phase on the surface layer surface of the conductor 13 is suppressed, it is possible to obtain a glass with heat wire having good solder wettability and good bonding strength.
　図６は、本発明に係るガラス物品の第２の実施の形態を模式的に示す要部断面図であって、本第２の実施の形態はガラスアンテナを示している。 FIG. 6 is a sectional view of an essential part schematically showing a second embodiment of the glass article according to the present invention, and the second embodiment shows a glass antenna.
　このガラスアンテナも、第１の実施の形態と同様、合わせガラスからなり、第１のガラス基体３１と第２のガラス基体３２との間に中間膜３３が介在されている。 As in the first embodiment, this glass antenna is also made of laminated glass, and an intermediate film 33 is interposed between the first glass substrate 31 and the second glass substrate 32.
　そして、第１のガラス基体３１の表面にはセラミック層３４が形成され、該セラミック層３４の表面にはアンテナ機能を有する所定パターンの導体３５が形成されている。導体３５は給電端子（不図示）とはんだ接合され、第１及び第２の実施の形態と同様、自動車等の車両用窓ガラスとして装備され、車外からの電波を受信し、ラジオやテレビに供される。 A ceramic layer 34 is formed on the surface of the first glass substrate 31, and a conductor 35 having a predetermined pattern having an antenna function is formed on the surface of the ceramic layer 34. The conductor 35 is soldered to a feeding terminal (not shown), and is mounted as a window glass for a vehicle such as an automobile as in the first and second embodiments, and receives radio waves from the outside of the vehicle and supplies it to a radio or television. Be done.
　このガラスアンテナは以下のようにして作製される。 This glass antenna is produced as follows.
　すなわち、第１の実施の形態と同様、ガラス成分を含有し、好ましくは黒色系無機顔料を含有したセラミックペーストを第１のガラス基体３１上に塗布し、乾燥させ、セラミック膜を形成する。次いで、このセラミックペースト上に所定のアンテナパターンを有するように本発明の導電性ペーストを塗布し、乾燥させ、導電膜を形成する。そしてその後、第１のガラス基体３１上のセラミック膜及び導電膜を共焼成してセラミック層３４及び導体３５を作製する。その後、中間膜３３が第１のガラス基体３１と第２のガラス基体３２とで狭持されるように接着剤を介して貼付し、これによりガラスアンテナが作製される。 That is, as in the first embodiment, a ceramic paste containing a glass component, preferably containing a black inorganic pigment, is applied onto the first glass substrate 31 and dried to form a ceramic film. Next, the conductive paste of the present invention is applied on the ceramic paste so as to have a predetermined antenna pattern, and dried to form a conductive film. Then, the ceramic film and the conductive film on the first glass substrate 31 are co-fired to produce the ceramic layer 34 and the conductor 35. Thereafter, the interlayer film 33 is pasted with an adhesive so as to be held between the first glass substrate 31 and the second glass substrate 32, thereby producing a glass antenna.
　このように本ガラスアンテナにおいても、セラミック層３４と導体３５とは、ガラス成分を含有したセラミック膜と、ガラス粉末の含有量が導電性ペースト中で０．２ｗｔ％以上であり、かつＮｉ粉末の含有量が、導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下とされた導電膜とが共焼成された共焼結体からなるので、セラミック膜中のガラス成分及び導電性ペースト中のガラス粉末によって導体５とセラミック層４との界面接合力を確保できると共に、導体表層面でのガラス相の形成を抑制することができ、これによりはんだ濡れ性や接合強度を改善することができる。 Thus, also in the present glass antenna, the ceramic layer 34 and the conductor 35 have a ceramic film containing a glass component, and the content of the glass powder is 0.2 wt% or more in the conductive paste, and the Ni powder is Since the conductive film having a content of 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder is a co-sintered body, the glass component in the ceramic film and The bonding strength between the conductor 5 and the ceramic layer 4 can be secured by the glass powder in the conductive paste, and the formation of the glass phase on the surface layer of the conductor can be suppressed, whereby the solder wettability and the bonding strength are improved. can do.
　尚、本発明は上記実施の形態に限定されるものではない。例えば、上述した熱線付きガラスでは、ウレタン系樹脂等の保持剤が紫外光により劣化するのを防止する観点から、黒色系の無機顔料をセラミック層に含有させており、また、ガラスアンテナでも車内での防眩を確保する観点から、黒色系の無機顔料をセラミック層に含有するのが好ましいが、用途によってはセラミック層が無機顔料を含有しないとすることもできる。 The present invention is not limited to the above embodiment. For example, in the glass with heat ray described above, a black inorganic pigment is contained in the ceramic layer from the viewpoint of preventing the holding agent such as urethane resin from being deteriorated by ultraviolet light, and the glass antenna is also used in the car. Although it is preferable to contain a black-based inorganic pigment in the ceramic layer from the viewpoint of securing the anti-glare, the ceramic layer may not contain the inorganic pigment depending on the application.
　また、本発明は、特性に影響を与えない範囲で、セラミック層や導体に各種無機成分を含有していてもよく、例えば、Ｚｒ、Ｐ、Ｖ、Ｃｅ、Ｎｂ、Ｔａ、Ｗ、Ｐｄ、Ａｇ、Ｒｕ、Ｓｎ、Ｉｎ、Ｙ、Ｄｙ、Ｌａ等を含有していてもよい。また、含有形態についても特に限定されるものではなく、酸化物、水酸化物、過酸化物、ハロゲン化物、炭酸塩、硝酸塩、リン酸塩、硫酸塩、フッ化物、有機金属化合物等、適宜選択することができる。 Further, in the present invention, various inorganic components may be contained in the ceramic layer and the conductor within a range not affecting the characteristics, for example, Zr, P, V, Ce, Nb, Ta, W, Pd, Ag , Ru, Sn, In, Y, Dy, La, etc. may be contained. In addition, the content form is also not particularly limited, and oxides, hydroxides, peroxides, halides, carbonates, nitrates, phosphates, sulfates, fluorides, organic metal compounds, etc. are appropriately selected. can do.
　また、本導電性ペーストには、必要に応じて、フタル酸ジ２－エチルヘキシル、フタル酸ジブチル等の可塑剤を１種又はこれらの組み合わせを添加するのも好ましい。また、脂肪酸アマイドや脂肪酸等のレオロジー調整剤を添加するのも好ましく、さらにはチクソトロピック剤、増粘剤、分散剤などを添加してもよい。 In addition, it is also preferable to add one or a combination of plasticizers such as di2-ethylhexyl phthalate and dibutyl phthalate to the conductive paste, as necessary. It is also preferable to add a rheology modifier such as a fatty acid amide or a fatty acid, and a thixotropic agent, a thickener, a dispersant or the like may be further added.
　さらに、上記実施の形態では、ワイパー凍結防止用の熱線付きガラスやガラスアンテナについて説明したが、これ以外の各種ガラス物品、例えば車両のリア部に装備される防曇ガラスにも適用可能なのはいうまでもない。 Furthermore, in the above-described embodiment, although the glass and the glass antenna with a heat ray for preventing the wiper antifreeze are described, various glass articles other than this, for example, antifogging glass installed in the rear part of a vehicle Nor.
　次に、本発明の実施例を具体的に説明する。 Next, an embodiment of the present invention will be specifically described.
〔導電性ペーストの作製〕
　平均粒径Ｄ50が２．０μｍのＡｇ粉末（導電性粉末）、平均粒径Ｄ50が２．０μｍのＢｉ－Ｂ－Ｓｉ－Ｏ系ガラス粉末、及び平均粒径Ｄ50が１．０μｍのＮｉ粉末を用意した。 [Preparation of conductive paste]
Ag powder of average particle size D 50 2.0 .mu.m (conductive powder), an average particle diameter D 50 2.0μm Bi-B-Si-O-based glass powder, and the average particle diameter D 50 1.0μm of Ni powder was prepared.
　次いで、有機ビヒクルを以下の方法で作製した。すなわち、バインダ樹脂としてエチルセルロース樹脂１０ｗｔ％、有機溶剤としてターピネオール９０ｗｔ％となるようにエチルセルロース樹脂とターピネオールとを混合し、有機ビヒクルを作製した。 Then, an organic vehicle was produced by the following method. That is, 10 wt% of ethyl cellulose resin as a binder resin, and 90 wt% of terpineol as an organic solvent were mixed with ethyl cellulose resin and terpineol to prepare an organic vehicle.
　次に、Ａｇ粉末が８０ｗｔ％、ガラス粉末が０．２～５．０ｗｔ％、Ｎｉ含有量が０～２．０ｗｔ％（Ａｇ１００重量部に対して０～２．５重量部）、残部が有機ビヒクルとなるようにこれらＡｇ粉末、ガラス粉末、Ｎｉ粉末及び有機ビヒクルを配合し、プラネタリーミキサで混合した後、三本ロールミルで分散させて混練し、試料番号１～９の導電性ペーストを作製した。 Next, 80 wt% of Ag powder, 0.2 to 5.0 wt% of glass powder, 0 to 2.0 wt% of Ni content (0 to 2.5 parts by weight with respect to 100 parts by weight of Ag), and the balance is organic These Ag powder, glass powder, Ni powder and organic vehicle are blended so as to be a vehicle, mixed by a planetary mixer, dispersed and kneaded by a three-roll mill, and a conductive paste of sample numbers 1 to 9 is prepared did.
［測定試料の作製］
　縦：７６ｍｍ、横：２６ｍｍ、厚み：１．４ｍｍのソーダライムからなるスライドガラス、及び黒色のセラミックペーストを用意した。そして、縦：６ｍｍ、横：２２ｍｍの長方形状となるようにスクリーン印刷して上記セラミックペーストをスライドガラスに塗布した後、１５０℃の温度で１０分間乾燥させ、スライドガラス上にセラミック膜を形成した。次いで、スクリーン印刷法を使用し、一辺が２．０ｍｍの正三角形及び逆正三角形が交互に横方向に列設されるように、試料番号１～９の導電性ペーストをセラミック膜上に塗布し、再び１５０℃の温度で１０分間乾燥させ、セラミック膜上に導電膜を形成した。その後、最高温度６００℃でセラミック膜及び導電膜を５分間共焼成し、セラミック層と導体からなる共焼結体をスライドガラス上に形成し、これによりはんだ濡れ性評価用の試料番号１～９の試料を作製した。また、厚さ３ｍｍの板ガラスを使用し、上述と同様の方法・手順で、接合強度測定用の試料番号１～９の試料を作製した。 [Preparation of measurement sample]
A slide glass made of soda lime having a length of 76 mm, a width of 26 mm, and a thickness of 1.4 mm, and a black ceramic paste were prepared. Then, the ceramic paste was applied to a slide glass by screen printing so as to form a rectangular shape having a length of 6 mm and a width of 22 mm, and then dried at 150 ° C. for 10 minutes to form a ceramic film on the slide glass. . Then, using screen printing method, apply conductive pastes of sample numbers 1 to 9 on the ceramic film so that regular triangles of 2.0 mm on one side and inverted regular triangles are alternately arranged in a horizontal direction. Then, it was again dried at a temperature of 150 ° C. for 10 minutes to form a conductive film on the ceramic film. Thereafter, the ceramic film and the conductive film are co-fired for 5 minutes at a maximum temperature of 600 ° C. to form a co-sintered body composed of the ceramic layer and the conductor on the slide glass, whereby sample numbers 1 to 9 for solder wettability evaluation The sample of Further, using a plate glass having a thickness of 3 mm, samples of sample numbers 1 to 9 for bonding strength measurement were produced by the same method and procedure as described above.
［試料の評価］
（はんだ濡れ性試験）
　試料番号１～９の各試料の導体表面を砂入り消しゴムで研磨し、ロジンをイソプロピルアルコールに溶解させたフラックスを導電体表面に塗布した。次いで、Ｓｎ－Ｐｂ－Ａｇ系はんだが貯留された加熱温度２１０℃のはんだ浴に各試料を５秒間浸漬し、その後引き上げた。そして、各試料のはんだ被覆量を目視で確認し、はんだ濡れ性を評価した。 [Evaluation of sample]
(Solder wettability test)
The conductor surface of each of the sample numbers 1 to 9 was polished with a sand eraser, and a flux in which rosin was dissolved in isopropyl alcohol was applied to the conductor surface. Next, each sample was immersed for 5 seconds in a solder bath at a heating temperature of 210 ° C. where Sn—Pb—Ag based solder was stored, and then pulled up. And the amount of solder coating of each sample was checked visually, and solder wettability was evaluated.
　はんだ濡れ性は、はんだ被覆量が面積比率で９０％以上を優（◎）、９０％未満７０％以上を良（○）、７０％未満を不可（×）とし、評価した。 The solder wettability was evaluated by setting the solder coverage to be 90% or more in terms of area ratio (A), less than 90% as 70% or more as good (O), and less than 70% as unacceptable (X).
（接合強度の測定）
　１５０℃の温度に加熱したホットプレート上に試料番号１～９の各試料を載置し、給電端子を導体にはんだ付けした。ここで、給電端子としては、一般の市販品（西日本商工社製）を使用し、はんだ濡れ性試験と同様、はんだにはＳｎ－Ｐｂ－Ａｇ系はんだを使用し、フラックスにはロジンをイソプロピルアルコールに溶解したものを使用した。 (Measurement of bonding strength)
Each sample of sample numbers 1 to 9 was placed on a hot plate heated to a temperature of 150 ° C., and a feed terminal was soldered to a conductor. Here, as a feeding terminal, a general commercial product (made by Nishi Nippon Shoko Co., Ltd.) is used, and as in the solderability test, Sn-Pb-Ag based solder is used for the solder, rosin is used for the flux isopropyl alcohol Dissolved in water was used.
　次いで、材料試験機(島津製作所社製、オートグラフ)を使用し、該材料試験機に板ガラスを固定して給電端子を引っ張り、該給電端子と板ガラスとが破断するまでの最大荷重を測定し、これを接合強度とした。そして、接合強度が、１００Ｎ以上の試料を良品と判断した。 Then, using a material tester (Autograph, manufactured by Shimadzu Corporation), fix the plate glass to the material tester, pull the feed terminal, and measure the maximum load until the feed terminal and the plate glass break. This was taken as the bonding strength. And, the bonding strength judged that the sample of 100N or more was non-defective.
（ガラス相占有率の測定）
　走査電子顕微鏡（ＳＥＭ）（日本電子社製：ＪＳＭ－ＩＴ３００ＬＶ）及びエネルギー分散型Ｘ線分析装置（ＥＤＸ）（英オックスフォード・インスツルメンツ社製：アズテック・アドバンスＸ－Ｍａｘ２０×２）を使用し、縦５０μｍ、横６４μｍの視野領域で試料を撮像し、画像処理を行って導体表層面のガラス相の占有率を算出し、面積比率を求めた。 (Measurement of glass phase occupancy rate)
Using a scanning electron microscope (SEM) (Nippon Denshi Co., Ltd .: JSM-IT300LV) and an energy dispersive X-ray analyzer (EDX) (British Oxford Instruments Co., Ltd .: Aztec Advance X-Max 20 × 2), 50 μm in length The sample was imaged in a visual field of 64 μm wide, and image processing was performed to calculate the occupancy of the glass phase of the surface layer of the conductor, and the area ratio was determined.
［試料の評価］
　表１は、導電性ペーストの成分組成、Ａｇ１００重量部に対するＮｉ含有量、及び測定結果を示している。 [Evaluation of sample]
Table 1 shows the component composition of the conductive paste, the Ni content relative to 100 parts by weight of Ag, and the measurement results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　試料番号１は、導電性ペースト中にＮｉ粉末が含有されていないため、はんだ濡れ性が極端に劣化し、接合強度も１０Ｎと低く、導体表層面のガラス相占有率も面積比率で７０％と大きくなった。 Sample No. 1 has extremely poor solder wettability because the conductive paste does not contain Ni powder, and the bonding strength is as low as 10 N, and the glass phase occupancy of the conductor surface is also 70% in area ratio It got bigger.
　図７は、試料番号１のはんだ濡れ性試験の試験結果を示している。この図７から明らかなように、導体上にはんだが全く濡れていないのが分かる。 FIG. 7 shows the test results of the solder wettability test of sample No. 1. As apparent from FIG. 7, it can be seen that the solder is not wet at all on the conductor.
　試料番号２は、Ｎｉ含有量がＡｇ１００重量部に対し０．０６２５重量部と少ないため、はんだ濡れ量が面積比率で４０％と低く、はんだ濡れ性に劣り、接合強度も７０Ｎと低く、機械的強度に劣ることが分かった。 Sample No. 2 has a low Ni content of 0.0625 parts by weight with respect to 100 parts by weight of Ag, so the solder wettability is low at 40% in area ratio, inferior in solder wettability, and low in joint strength of 70 N, mechanical It was found that the strength was inferior.
　図８は、試料番号２の平面ＳＥＭ写真を示している。 FIG. 8 shows a planar SEM photograph of sample No. 2.
　この図８に示すように、導体中のガラス相の占有率が５０％程度であり、ガラス成分が導体表層面に大量に偏析していることが分かる。 As shown in FIG. 8, it can be seen that the occupancy of the glass phase in the conductor is about 50%, and the glass component is segregated in large amounts on the surface layer of the conductor.
　一方、試料番号９は、Ｎｉ含有量がＡｇ１００重量部に対し２．５重量部と過剰であるため、導体表層面のガラス相占有率は１０％と低いものの、焼成中にＮｉ酸化物が生成されることから、はんだ濡れ量が面積比率で５０％となって７０％未満に低下し、はんだ濡れ性が劣化し、接合強度も９０Ｎとなって機械的強度も低下することが分かった。 On the other hand, Sample No. 9 has an excess of 2.5 parts by weight of Ni content to 100 parts by weight of Ag, so the glass phase occupancy of the surface layer of the conductor is as low as 10%, but Ni oxide is formed during firing From the results, it was found that the solder wettability amounted to 50% in area ratio and decreased to less than 70%, the solder wettability deteriorated, and the joint strength also decreased to 90 N and the mechanical strength decreased.
　図９は、試料番号９のはんだ濡れ性試験の試験結果を示している。この図９から明らかなように、導体上にはんだが十分に濡れ拡がっていないのが分かる。 FIG. 9 shows the test results of the solder wettability test of sample No. 9. As apparent from FIG. 9, it can be seen that the solder is not sufficiently wet and spread on the conductor.
　これに対し試料番号３～８は、Ｎｉ含有量が本発明範囲内であるので、はんだ被覆量が面積比率で７０～１００％であり、はんだ濡れ性が良好であり、接合強度も１１０～２５０Ｎとなって十分な機械的強度を得ることができ、ガラス占有率も３０％以下であり、はんだ付け性が良好であることが分かった。 On the other hand, sample numbers 3 to 8 have a Ni content in the range of the present invention, so the solder coverage is 70 to 100% in area ratio, the solder wettability is good, and the bonding strength is also 110 to 250 N As a result, it was found that sufficient mechanical strength can be obtained, the glass occupancy rate is also 30% or less, and the solderability is good.
　また、ガラス粉末の含有量が０．２ｗｔ％以上であっても、Ｎｉ粉末を所定量含有させることにより、導体表層面のガラス相の形成を抑制することができ、これによりはんだ濡れ性及びはんだの接合強度が改善できることが分かった。 In addition, even if the content of the glass powder is 0.2 wt% or more, the formation of the glass phase on the surface layer of the conductor can be suppressed by containing a predetermined amount of Ni powder, whereby solder wettability and solder can be obtained. It has been found that the bonding strength of can be improved.
　図１０は、試料番号３のはんだ濡れ性試験の試験結果を示している。この図１０から明らかなように、導体表面にははんだが十分に濡れ拡がっているのが分かる。 FIG. 10 shows the test results of the solder wettability test of sample No. 3. As apparent from FIG. 10, it can be seen that the solder is sufficiently wet and spread on the conductor surface.
　図１１は、試料番号４のはんだ濡れ性試験の試験結果を示している。この図１１から明らかなように、導体表面の全域にはんだが濡れ拡がっているのが分かる。 FIG. 11 shows the test results of the solder wettability test of sample No. 4. As apparent from FIG. 11, it can be seen that the solder is wet and spread over the entire surface of the conductor.
　図１２は、試料番号１の断面ＳＥＭ画像であり、図１３は、試料番号４の断面ＳＥＭ画像である。 FIG. 12 is a cross-sectional SEM image of sample No. 1, and FIG. 13 is a cross-sectional SEM image of sample No. 4.
　試料番号１は、導電性ペースト中にＮｉ粉末が含有されていないため、図１２に示すように、導体表層面でのガラス相の占有率（面積比率）が大きいことが分かった。 In Sample No. 1, since the conductive paste did not contain Ni powder, it was found that the occupancy (area ratio) of the glass phase on the surface layer surface of the conductor was large, as shown in FIG.
　これに対し試料番号４は、Ａｇ１００重量部に対し０．６２５重量部のＮｉ粉末が含有されているので、Ｎｉ粉末がＡｇ粉末の焼結を阻害することから、図１３に示すように、微細で複雑な形状を有する多数の空隙が形成され、斯かる空隙が抵抗乃至障害となってガラス相の占有率（面積比率）は小さくなり、導体表面層に空隙が増えることが分かった。 On the other hand, Sample No. 4 contained 0.625 parts by weight of Ni powder with respect to 100 parts by weight of Ag, and thus Ni powder inhibited sintering of the Ag powder, so as shown in FIG. It has been found that a large number of air gaps having a complicated shape are formed, and the air gaps become resistance or obstruction to reduce the occupancy (area ratio) of the glass phase and increase air gaps in the conductor surface layer.
　以上より、導電性粉末としてのＡｇ１００重量部に対し０．１２５重量部以上１．２５重量部以下のＮｉ粉末が導電性ペースト中に含有されていれば、導電性ペースト中に０．２ｗｔ％以上のガラス粉末が含有されていても、はんだ濡れ量が面積比率で７０％以上の良好なはんだ濡れ性を有し、接合強度が１００Ｎ以上の機械的強度が良好なガラス物品が得られることが分かった。 From the above, if the conductive paste contains 0.125 parts by weight or more and 1.25 parts by weight or less of Ni powder based on 100 parts by weight of Ag as the conductive powder, 0.2 wt% or more in the conductive paste Even if the glass powder of the above is contained, it is understood that a glass article having a good solder wettability in which the solder wetness is 70% or more in area ratio, and the mechanical strength of which the bonding strength is 100N or more can be obtained The
　セラミック層上に導体を形成した合わせガラスで車両用の窓ガラスを形成した場合であっても、導体表層面にガラス相が形成されるのを抑制することができ、はんだ濡れ性やはんだの接合強度を向上させることができ、ワイパー凍結防止用熱線付きガラスや防曇ガラス、ガラスアンテナ等の各種ガラス物品に有用である。 Even when the window glass for a vehicle is formed of laminated glass in which a conductor is formed on a ceramic layer, formation of a glass phase on the surface layer surface of the conductor can be suppressed, and solder wettability and bonding of solder can be obtained. The strength can be improved, and it is useful for various glass articles such as wiper-free glass for preventing heat rays, anti-fogging glass, and glass antenna.
１、３１　第１のガラス基体（ガラス基体）
４、３４　セラミック層
５、３５　導体 1, 31 1st glass substrate (glass substrate)
4, 34 ceramic layers 5, 35 conductors

Claims (10)

  1. 　ガラス成分を含有したセラミック膜上に導電パターンを形成するための導電性ペーストであって、
    　少なくとも導電性粉末、ガラス粉末、Ｎｉ粉末、及び有機ビヒクルを含有すると共に、
    　前記ガラス粉末の含有量が、０．２ｗｔ％以上であり、
    　かつ、前記Ｎｉ粉末の含有量が、前記導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下であることを特徴とする導電性ペースト。     A conductive paste for forming a conductive pattern on a ceramic film containing a glass component, comprising:
    And at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle
    The content of the glass powder is 0.2 wt% or more,
    And, the content of the Ni powder is 0.125 parts by weight or more and 1.25 parts by weight or less with respect to 100 parts by weight of the conductive powder.
  2. 　前記導電性粉末は、Ａｇを主成分としていることを特徴とする請求項１記載の導電性ペースト。 The said electrically conductive powder has Ag as a main component, The electrically conductive paste of Claim 1 characterized by the above-mentioned.
  3. 　ガラス成分を含有したセラミック層がガラス基体上に形成されると共に、前記セラミック層上に導体が形成されたガラス物品であって、
    　前記セラミック層と前記導体とは、前記ガラス成分を含有したセラミック膜と、ガラス粉末の含有量が導電性ペースト中で０．２ｗｔ％以上であり、かつＮｉ粉末の含有量が、導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下とされた導電膜とが共焼成された共焼結体からなることを特徴とするガラス物品。     A glass article, wherein a ceramic layer containing a glass component is formed on a glass substrate, and a conductor is formed on the ceramic layer,
    In the conductive paste, the ceramic layer and the conductor each have a content of 0.2 wt% or more of a ceramic film containing the glass component and a glass powder, and a content of Ni powder is 100 wt% of the conductive powder. A glass article comprising a co-sintered body obtained by co-firing a conductive film of 0.125 parts by weight or more and 1.25 parts by weight or less with respect to parts by weight.
  4. 　前記セラミック膜に含有される前記ガラス成分は、非晶質であることを特徴とする請求項３記載のガラス物品。 The glass article according to claim 3, wherein the glass component contained in the ceramic film is amorphous.
  5. 　前記導体は、表層面における前記ガラス相の占有率が、面積比率で３０％以下であることを特徴とする請求項３又は請求項４記載のガラス物品。 The glass article according to claim 3 or 4, wherein an occupancy ratio of the glass phase in a surface layer surface of the conductor is 30% or less in area ratio.
  6. 　前記セラミック層は、無機顔料を含有していることを特徴とする請求項３乃至請求項５のいずれかに記載のガラス物品。 The glass article according to any one of claims 3 to 5, wherein the ceramic layer contains an inorganic pigment.
  7. 　前記無機顔料は、黒色系顔料であることを特徴とする請求項６記載のガラス物品。 The glass article according to claim 6, wherein the inorganic pigment is a black pigment.
  8. 　少なくともセラミック粉末、ガラス成分、及び有機ビヒクルを含有したセラミックペーストを準備する工程と、
    　少なくとも導電性粉末、ガラス粉末、Ｎｉ粉末、及び有機ビヒクルを含有し、前記ガラス粉末の含有量が０．２ｗｔ％以上であり、かつ前記Ｎｉ粉末の含有量が、前記導電性粉末１００重量部に対し０．１２５重量部以上１．２５重量部以下に調製された導電性ペーストを準備する工程と、
    　前記セラミックペーストをガラス基体に塗布してセラミック膜を形成する工程と、
    　を含むことを特徴とするガラス物品の製造方法。     Providing a ceramic paste containing at least a ceramic powder, a glass component, and an organic vehicle;
    Containing at least a conductive powder, a glass powder, a Ni powder, and an organic vehicle, the content of the glass powder is 0.2 wt% or more, and the content of the Ni powder is 100 parts by weight of the conductive powder Preparing a conductive paste prepared to at least 0.125 parts by weight and at most 1.25 parts by weight;
    Applying the ceramic paste to a glass substrate to form a ceramic film;
    A method of producing a glass article comprising:
  9. 　前記セラミックペーストを前記ガラス基体に塗布して未焼成セラミック膜を形成する工程と、
    　前記未焼成セラミック膜上に前記導電性ペーストを塗布して未焼成導電膜を形成する工程と、
    　前記未焼成セラミック膜と前記未焼成導電膜とを共焼成する工程とを含む請求項８記載のガラス物品の製造方法。     Applying the ceramic paste to the glass substrate to form an unfired ceramic film;
    Applying the conductive paste onto the unfired ceramic film to form an unfired conductive film;
    The method for producing a glass article according to claim 8, comprising the step of co-firing the unfired ceramic film and the unfired conductive film.
  10. 　前記セラミック粉末は、無機顔料を含むことを特徴とする請求項８又は請求項９記載のガラス物品の製造方法。 The method according to claim 8 or 9, wherein the ceramic powder contains an inorganic pigment.
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* Cited by examiner, † Cited by third party
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WO2023145710A1 (en) * 2022-01-28 2023-08-03 Ａｇｃ株式会社 Windshield for vehicle and manufacturing method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51106635A (en) * 1975-03-17 1976-09-21 Fujitsu Ltd METARAIZUYOPEESUTOSOSEIBUTSU
JPH09180541A (en) * 1995-12-27 1997-07-11 Murata Mfg Co Ltd Conductive paste, conductive body using it, and ceramic substrate
JPH11232927A (en) * 1998-02-13 1999-08-27 Murata Mfg Co Ltd Conductive paste
JP2003246644A (en) * 2001-12-21 2003-09-02 Shoei Chem Ind Co Glass and conductor paste obtained by using the same
JP2009286260A (en) * 2008-05-29 2009-12-10 Asahi Glass Co Ltd Window glass for automobile with electric conductor and its manufacturing method
JP2012022841A (en) * 2010-07-13 2012-02-02 Shoei Chem Ind Co Conductive paste

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51106635A (en) * 1975-03-17 1976-09-21 Fujitsu Ltd METARAIZUYOPEESUTOSOSEIBUTSU
JPH09180541A (en) * 1995-12-27 1997-07-11 Murata Mfg Co Ltd Conductive paste, conductive body using it, and ceramic substrate
JPH11232927A (en) * 1998-02-13 1999-08-27 Murata Mfg Co Ltd Conductive paste
JP2003246644A (en) * 2001-12-21 2003-09-02 Shoei Chem Ind Co Glass and conductor paste obtained by using the same
JP2009286260A (en) * 2008-05-29 2009-12-10 Asahi Glass Co Ltd Window glass for automobile with electric conductor and its manufacturing method
JP2012022841A (en) * 2010-07-13 2012-02-02 Shoei Chem Ind Co Conductive paste

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023145710A1 (en) * 2022-01-28 2023-08-03 Ａｇｃ株式会社 Windshield for vehicle and manufacturing method thereof

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