WO2017159055A1 - Conductive paste, method for forming conductive pattern, and glass article - Google Patents

Conductive paste, method for forming conductive pattern, and glass article Download PDF

Info

Publication number
WO2017159055A1
WO2017159055A1 PCT/JP2017/002480 JP2017002480W WO2017159055A1 WO 2017159055 A1 WO2017159055 A1 WO 2017159055A1 JP 2017002480 W JP2017002480 W JP 2017002480W WO 2017159055 A1 WO2017159055 A1 WO 2017159055A1
Authority
WO
WIPO (PCT)
Prior art keywords
conductive
glass
conductive paste
resin powder
powder
Prior art date
Application number
PCT/JP2017/002480
Other languages
French (fr)
Japanese (ja)
Inventor
伸一 次本
Original Assignee
株式会社村田製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社村田製作所 filed Critical 株式会社村田製作所
Publication of WO2017159055A1 publication Critical patent/WO2017159055A1/en

Links

Images

Classifications

    • 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
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • 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
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/27—Adaptation for use in or on movable bodies
    • H01Q1/32—Adaptation for use in or on road or rail vehicles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

Definitions

  • the present invention relates to a conductive paste, a method for forming a conductive pattern, and a glass article. More specifically, the present invention relates to a conductive material for forming an antifogging hot wire or antenna pattern attached to a window glass for a vehicle such as an automobile. The present invention relates to a paste, a method for forming a conductive pattern using the conductive paste, and a glass article such as an antifogging glass or a glass with an antenna using the conductive paste.
  • glass articles such as antifogging glass provided with a heat ray for antifogging and glass with an antenna for receiving radio waves from outside the vehicle have been used for the window glass of a vehicle such as an automobile.
  • a conductive paste is usually applied on a glass substrate as a raw material to form a circuit pattern, and current collecting patterns are formed on both ends of the circuit pattern and dried. It is manufactured by performing a baking process later.
  • the conductive film having a predetermined pattern is fixed on the glass substrate, the connection terminals are soldered to the collecting electrodes formed on both ends of the conductive film, and the connection terminals are connected to the power supply terminals via lead wires. ing.
  • Patent Document 1 discloses finely divided particles of a conductive material, silicate compounds such as lead borate, lead silicate, lead borosilicate, metal oxides or oxide precursors, and mixtures thereof.
  • a conductive composition comprising an inorganic binder selected from the group consisting of and a liquid vehicle in which they are dispersed, wherein the total composition comprises 50 to 95 wt% solids, said inorganic binder comprising: Conductive compositions have been proposed that are less than 1.0% of the total solids of the composition.
  • Patent Document 1 includes a solid content of 50 to 95% by mass and reduces the content of the inorganic binder (glass frit) to less than 1.0% of the total solid content, thereby cracking the enamel covering the substrate.
  • the adhesive force can be maintained without causing the occurrence of the phenomenon, and thereby, both the electrical conductivity and the adhesive force are attempted to be achieved.
  • JP 2004-31438 A (Claim 2, paragraph numbers [0009], [0019] to [0021], Table 2, etc.)
  • Patent Document 1 the content of the inorganic binder in the conductive composition is reduced to lower the specific resistance, thereby improving the conductivity.
  • the content of the inorganic binder is as low as less than 1.0%, and thus the adhesion between the conductive film and the glass substrate may be inferior.
  • the present invention has been made in view of such circumstances, and uses a conductive paste that can ensure a good adhesion to a substrate while ensuring a desired low specific resistance, and uses the conductive paste. It is an object of the present invention to provide a method for forming a conductive pattern, and a glass article such as an antifogging glass or a glass with an antenna using the conductive paste.
  • Conductive pastes used to make glass articles such as antifogging glass for vehicles and glass with antennas usually contain conductive powder, glass frit, and an organic vehicle composed of an organic binder and an organic solvent. Yes. Further, in this type of glass article, as described in the section of “Background Art”, the conductive film and the collecting electrode are produced by firing a conductive paste. It is required that the adhesive strength to the is good.
  • the present inventor formed a conductive film on a glass substrate using a conductive paste from such a viewpoint, and conducted earnest research, the decomposition gas of the organic binder generated during firing was confined inside the conductive film, Furthermore, it was found that this decomposition gas gathers at the interface between the conductive film and the glass substrate to form a cavity. As a result of the formation of a large number of cavities filled with the decomposition gas at the interface with the glass substrate, the contact area between the conductive film and the glass substrate is reduced, and thus the adhesion between the glass substrate and the conductive film is reduced. I found out that
  • the present inventor has further conducted intensive research.
  • the conductive paste contains a resin powder that is insoluble in the organic vehicle and burned off by the baking treatment (hereinafter referred to as “insoluble resin powder”).
  • insoluble resin powder a resin powder that is insoluble in the organic vehicle and burned off by the baking treatment
  • the voids formed in the burning trace of the insoluble resin powder function as the above-described cracked gas ventilation holes, thereby suppressing the generation of the cavity filled with the cracked gas.
  • the inventor has obtained knowledge that the adhesion to the substrate can be improved while ensuring a low specific resistance.
  • the conductive paste according to the present invention is a conductive paste containing at least a conductive powder, a glass frit, and an organic vehicle composed of an organic binder and an organic solvent.
  • “having insolubility with respect to the organic vehicle” means that an undissolved solid that does not dissolve in the organic vehicle remains even if the resin powder is added to the organic vehicle and stirred. This includes not only the case where the vehicle does not dissolve in the organic solvent at all, but also the case where it is slightly soluble in the organic solvent but hardly soluble so that an undissolved solid content remains.
  • the temperature at which the insoluble resin powder burns out is preferably 500 to 800 ° C.
  • the insoluble resin powder preferably has an average particle size of 3 to 15 ⁇ m.
  • the average particle diameter means a particle diameter having an integrated cumulative distribution of 50%, that is, a median diameter (hereinafter referred to as “average particle diameter D 50 ”).
  • the content of the insoluble resin powder is more preferably 0.2 to 1 part by weight with respect to 100 parts by weight of the conductive powder.
  • the insoluble resin powder preferably contains at least one selected from the group consisting of polyolefin, polymethacrylic acid ester, and polyacrylic acid ester.
  • Such an insoluble resin powder is insoluble in an organic vehicle and easily burned off by a baking treatment, and therefore can be preferably used for the conductive paste of the present invention.
  • the conductive powder is preferably composed mainly of Ag.
  • the method for forming a conductive pattern according to the present invention includes a conductive powder, a glass frit, an organic vehicle composed of an organic binder and an organic solvent, insoluble in the organic vehicle, and burned off by a baking treatment.
  • a step of applying a conductive paste containing a resin powder on the substrate; and baking the conductive paste applied on the substrate to form a conductive film having a predetermined pattern on the substrate, and at the same time, the resin powder And a step of forming a through-hole penetrating the conductive film in the burnout trace of the resin powder.
  • a through hole for ventilating the decomposition gas of the organic binder is formed in the burned-out trace of the insoluble resin powder, so that the through hole becomes a ventilation hole for the decomposition gas of the organic binder, and the cavity filled with the decomposition gas is the substrate.
  • formation between the conductive film and the conductive film can be suppressed. Therefore, no blister (swelling) is formed between the substrate and the conductive film, and the contact area at the interface increases, so that the adhesion between the substrate and the conductive film can be improved.
  • the specific resistance of the conductive film after firing is 3.4 ⁇ ⁇ cm or less.
  • the glass article according to the present invention is a glass article in which a conductive film is formed on a glass substrate and a connection terminal is bonded to the conductive film. It is characterized by being formed of a paste sintered body.
  • the conductive paste of the present invention is a conductive paste containing at least a conductive powder, glass frit, and an organic vehicle composed of an organic binder and an organic solvent, and is insoluble in the organic vehicle.
  • a void such as a through-hole penetrating the conductive film is formed in the burned-out trace of the insoluble resin powder burned out by the baking.
  • gap functions as a ventilation hole of the decomposition gas produced
  • the formation of the cavity filled with the decomposition gas of the organic binder can be suppressed, so that the contact area with the substrate can be increased, and a desired low specific resistance can be achieved.
  • the through hole for venting the decomposition gas of the organic binder is formed in the burned trace of the insoluble resin powder, the through hole is a ventilation hole for the decomposition gas of the organic binder.
  • the formation of a cavity filled with the decomposition gas between the substrate and the conductive film can be suppressed.
  • the contact area between the substrate and the conductive film increases, and the adhesion between the substrate and the conductive film can be improved.
  • a conductive film is formed on a glass substrate, and a connection terminal is bonded on the conductive film. Because it is formed of a sintered paste of conductive paste, it can improve the adhesion between the glass substrate and the conductive film while ensuring conductivity, and suppresses breakage even when tensile stress is applied to the conductive film Various glass articles such as antifogging glass and glass with an antenna having good mechanical strength can be obtained.
  • FIG. 2 is a cross-sectional view taken along line AA in FIG. 1. It is sectional drawing which shows an example of a dry film
  • FIG. 1 is a front view showing an embodiment of an anti-fogging glass as a glass article manufactured using the conductive paste according to the present invention
  • FIG. 2 is a cross-sectional view taken along the line AA in FIG. It is.
  • the antifogging glass has a plurality of line-shaped conductive films 2 that are thinned and thinned at predetermined intervals on the surface of the glass substrate 1 and are formed in parallel on both ends of the conductive film 2. Electrical electrodes 3a and 3b are formed, and connection terminals (not shown) are soldered and joined to the current collecting electrodes 3a and 3b.
  • a conductive paste is applied on the glass substrate 1 to form a circuit pattern, and current collecting patterns are formed at both ends of the circuit pattern. And current collecting electrodes 3a and 3b are formed.
  • the conductive film 2 and the collecting electrodes 3a and 3b are formed of a sintered body of conductive paste.
  • the conductive film 2 is fixed on the glass substrate 1, and connection terminals (not shown) are soldered to the collecting electrodes 3a and 3b, and are connected to lead wires through the connection terminals.
  • This anti-fog glass is equipped as a windshield or rear glass of a vehicle such as an automobile, for example, and is supplied with power to the conductive film 2 from the power supply terminal via the collector electrodes 3a and 3b. Anti-fogging can be performed.
  • This conductive paste contains conductive powder, glass frit, and an organic vehicle.
  • the organic vehicle is composed of an organic binder and an organic solvent, and an organic binder soluble in the organic solvent is dissolved in the organic solvent.
  • the conductive paste contains an insoluble resin powder that is insoluble in the organic vehicle and burns away by the baking treatment, thereby ensuring the desired low specific resistance and the glass substrate 1 and the conductive film. 2 is improved.
  • “having insolubility with respect to the organic vehicle” means that an undissolved solid that does not dissolve in the organic vehicle remains even if the resin powder is added to the organic vehicle and stirred. This includes not only the insoluble case where it does not dissolve at all in the vehicle, but also the case where it is slightly soluble in the organic vehicle but remains insoluble and remains undissolved.
  • a decomposition gas such as CO 2 generated by the thermal decomposition of the organic binder is confined inside the conductive film 2, and this decomposition gas is contained in the glass substrate 1 and the conductive film. Concentrates at the interface with 2 to form a cavity. Therefore, the occupation ratio of the cavity filled with the decomposition gas is increased at the interface, so that the contact area between the glass substrate 1 and the conductive film 2 is decreased, and the adhesion force of the conductive film 2 to the glass substrate 1 may be reduced. There is.
  • the conductive paste contains insoluble resin powder that is insoluble in the organic vehicle and burned off by the baking treatment, thereby burning off the insoluble resin powder during baking and leaving voids in the burned trace.
  • the void By forming the void and functioning as a vent hole for the cracked gas, the cavity filled with the cracked gas is suppressed from remaining at the interface between the glass substrate 1 and the conductive film 2.
  • the conductive paste is a conductive paste containing at least a conductive powder, a glass frit, and an organic vehicle, and is insoluble in the organic vehicle and insoluble resin powder that is burned off by the baking treatment. Therefore, a void such as a through-hole penetrating the conductive film is formed in the firing trace of the insoluble resin powder burnt down by firing. And this space
  • the collector electrodes 3a and 3b to which the lead wires are connected via the connection terminals are preferably subjected to a tensile stress from the outside.
  • Such an insoluble resin powder is not particularly limited as long as it is a resin that is insoluble in an organic vehicle as described above and burns away at a baking treatment, that is, at a baking temperature (eg, 500 to 800 ° C.).
  • a resin powder containing at least one selected from the group consisting of polyolefins such as polypropylene, polymethacrylic acid esters, and polyacrylic acid esters can be preferably used.
  • FIG. 3 is a cross-sectional view schematically showing an example of the state before firing
  • FIG. 4 is a cross-sectional view schematically showing an example of the state after firing.
  • the dry film 4 is formed on the glass substrate 1.
  • the dry film 4 contains conductive powder 5, glass frit 6, insoluble resin powder 7, and organic binder 8.
  • the conductive film 2 is formed and the glass frit 6 is segregated at the interface with the glass substrate 1 as shown in FIG. Further, the insoluble resin powder 7 is thermally decomposed and burned, and voids 9 are formed in the burned trace where the insoluble resin powder 7 was present.
  • voids 9 having various pore sizes are formed according to the size of the particle size of the insoluble resin powder 7, and voids 9 that penetrate the conductive film 2, that is, through-holes 11 can also be formed. These gaps 9 act as ventilation holes.
  • the cracked gas is not filled between the glass substrate 1 and the conductive film 2 and pushes up the conductive film 2, and the formation of blisters (swelling), which will be described later, is suppressed, thereby the glass substrate 1 and the conductive film 2. It is possible to increase the contact area.
  • the insoluble resin powder 7 in the conductive paste, formation of blisters after firing can be suppressed, and as a result, the contact area between the glass substrate 1 and the conductive film 2 can be increased. This makes it possible to effectively improve the fixing force with the glass substrate 1.
  • the average particle diameter D 50 of the insoluble resin powder 7 is preferably a predetermined range.
  • FIG. 5 is a cross-sectional view schematically showing another example of the state before firing
  • FIG. 6 is a cross-sectional view schematically showing another example of the state after firing.
  • diameter D 50 indicates the case where relatively small.
  • the conductive paste is applied and dried on the surface of the glass substrate 1, so that a dry film 4 is formed on the glass substrate 1. Accordingly, the dry film 4 contains the conductive powder 5, the glass frit 6, the insoluble resin powder 7, and the organic binder 8 as in FIG.
  • this dry film 4 is subjected to a baking treatment, as shown in FIG. 6, the conductive film 2 is formed and the glass frit 6 is segregated at the interface with the glass substrate 1.
  • the insoluble resin powder 7 is thermally decomposed and burned out, and voids 9 are formed in the burned-out trace where the insoluble resin powder 7 was present.
  • the gap 9 disappears due to the densification of the conductive film 2, the glass frit 6 penetrates into the gap 9, and the film thickness of the conductive film 2 is smaller. As a result, a very small gap 9 is formed, and the gap 9 may not sufficiently function as a vent hole for cracked gas. As a result, as shown in FIG. 6, the decomposition gas generated inside the conductive film 2 pushes up the conductive film 2 to form a blister 10, thereby reducing the contact area between the glass substrate 1 and the conductive film 2. Invite. Therefore, although the fixing force is improved as compared with the case where the insoluble resin powder 7 is not contained, the improvement effect is reduced.
  • the average particle diameter D 50 of the insoluble resin powder 7 is excessively large, the number of insoluble resin powders 7 in the conductive paste is relatively reduced, and thus the number of voids 9 functioning as ventilation holes is also reduced. As a result, the density of the voids 9 decreases, and in this case, the effect of improving the fixing force may be reduced.
  • the voids 9 can be formed by the baking treatment, and the fixing force can be improved, but the more effective fixing force can be improved.
  • an average particle diameter D 50 of the insoluble resin powder 7 is present is preferably in the range.
  • the average particle diameter D 50 in such a preferable range is 3 to 15 ⁇ m.
  • the average particle diameter D 50 is less than 3 ⁇ m or more than 15 ⁇ m, the fixing effect is improved as compared with the case where the insoluble resin powder 7 is not contained, but the improvement effect is small.
  • the content of the insoluble resin powder is not particularly limited, as long as the insoluble resin powder is contained as described above, since the insoluble resin powder is burnt out by the baking treatment to form voids, From the viewpoint of achieving both the fixing force and the specific resistance, the amount is preferably 0.2 to 1 part by weight with respect to 100 parts by weight of the conductive powder.
  • the content of the insoluble resin powder is less than 0.2 parts by weight with respect to 100 parts by weight of the conductive powder, there is a possibility that a sufficient improvement effect of the fixing force cannot be obtained.
  • the content of the insoluble resin powder exceeds 1 part by weight with respect to 100 parts by weight of the conductive powder, although the fixing force increases, the amount of the insoluble resin powder 7 is relatively increased with respect to the conductive powder 5, There is a possibility that the specific resistance increases and the conductivity decreases.
  • the average particle diameter D 50 of the insoluble resin powder is 3 to 15 ⁇ m, and the content thereof is 0.2 to 100 parts by weight of the conductive powder.
  • the amount is preferably 1 part by weight.
  • the specific resistance suitable for the production of the antifogging glass is 3.4 ⁇ ⁇ cm or less and the fixing strength is 12 N or more.
  • a conductive paste having both conductivity and adhesion can be obtained.
  • the conductive powder is not particularly limited as long as it is a metal powder having good conductivity.
  • a powder containing Ag powder as a main component (for example, 50 wt% or more) is preferably used. be able to.
  • Ag powder may be the main component, and various precious metal powders such as Pd and Pt may be included 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 diameter D 50 of the conductive powder is not particularly limited, but from the viewpoint of ensuring mechanical strength and the like, the average particle diameter D 50 is preferably 0.1 to 5 ⁇ m.
  • the average particle diameter D 50 of the conductive powder is less than 0.1 ⁇ m, the viscosity increases during paste preparation, making it difficult to make a paste.
  • the average particle diameter D 50 of the conductive powder exceeds 5 ⁇ m, The presence of crystal grains with desired grain growth between the conductive powders is insufficient, which may lead to a decrease in mechanical strength.
  • the content of the conductive powder is not particularly limited, but is preferably 50 to 90 wt%.
  • the content of the conductive powder is less than 50 wt%, the content of the glass frit is relatively increased. Therefore, in order to ensure the desired conductivity, the line width is increased or the conductive film is made thicker. There is a risk of increasing costs.
  • the content of the conductive powder exceeds 90 wt%, the conductive powder becomes excessive and it may be difficult to form a paste. Accordingly, the content of the conductive powder is not particularly limited, but is preferably 50 to 90 wt%.
  • the composition of the glass frit is not particularly limited, but from the viewpoint of avoiding a decrease in the sintered density and insufficient sealing at the interface of the conductive film 2, it is necessary to melt and flow at the firing temperature. Since glass articles such as antifogging glass are usually fired at a temperature of about 500 to 800 ° C., it is preferable to use a glass frit whose composition is adjusted to a softening point of about 350 to 600 ° C.
  • glass frit Bi 2 O 3, PbO, SiO 2, B 2 O 3, Al 2 O 3, BaO, CaO, SrO, ZnO, Na 2 O, K It can be selected from various oxides such as 2 O, Li 2 O, Sb 2 O 3 , FeO, and CuO in consideration of the softening point and chemical durability.
  • the average particle diameter D 50 of the glass frit is not particularly limited, but is preferably 0.1 to 5.0 ⁇ m from the viewpoint of the adhesion between the glass substrate 1 and the conductive film 2 and the sinterability of the conductive paste. .
  • the content of the glass frit is not particularly limited, but is preferably 1.5 to 6.0 wt% in consideration of the adhesion between the glass substrate 1 and the conductive film 2 and the solderability with the lead wire.
  • the ratio of the organic binder and the organic solvent constituting the organic vehicle is not particularly limited, and is usually prepared to have a volume ratio of 1 to 3: 7 to 9, for example.
  • an organic binder an ethyl cellulose resin, a nitrocellulose resin, an acrylic resin, an alkyd resin, or these combinations can be used, for example.
  • an organic solvent ⁇ -terpineol, xylene, toluene, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate and the like can be used alone or in combination.
  • a conductive powder such as an Ag powder, a glass frit such as Bi—B—Si, and an insoluble resin powder such as a polypropylene resin that is insoluble in an organic vehicle and burned off by a baking treatment are prepared.
  • an organic vehicle is prepared by blending an organic binder such as ethyl cellulose resin soluble in an organic solvent and an organic solvent such as ⁇ -terpineol in a predetermined ratio.
  • the conductive powder, glass frit, and insoluble resin powder are put into an organic vehicle and dispersed and kneaded using a three-roll mill or the like, thereby producing a conductive paste.
  • a conductive paste is applied on the glass substrate 1 and dried at a temperature of about 120 to 170 ° C. for a predetermined time (for example, 10 minutes) to obtain a dry film 4.
  • the dried film 4 is subjected to a baking treatment at a baking temperature of about 500 to 800 ° C. for a predetermined time (for example, 5 minutes). Then, the insoluble resin powder is burned out, and voids including through holes are formed in the burned-out trace of the insoluble resin powder, and a conductive film 2 and current collecting electrodes 3a to 3b having a predetermined pattern are formed on the glass substrate 1. Thus, an antifogging glass is produced.
  • the method for forming the conductive pattern includes a conductive powder, a glass frit, an organic vehicle composed of an organic binder and an organic solvent, and an insoluble resin powder that is insoluble in the organic vehicle and burns away in the baking treatment.
  • the method includes a step of forming a void to be ventilated in the burned trace of the insoluble resin powder, the void becomes a ventilation hole for the decomposition gas of the organic binder, Cavity decomposition gas is filled can be prevented from being formed between the substrate and the conductive film. As a result, the contact area between the glass substrate 1 and the conductive film 2 increases, and the adhesion between the substrate and the conductive film can be improved.
  • the anti-fogging since the adhesive force between the glass substrate 1 and the conductive film 2 is improved, the anti-fogging has a good mechanical strength that does not easily break even when a tensile stress is applied to the conductive film 2 and the terminal electrodes 3a and 3b. Glass can be obtained.
  • FIG. 7 is a cross-sectional view of an essential part showing an example of glass with an antenna as a second embodiment of the glass article according to the present invention.
  • the glass with an antenna is a laminated glass in which an intermediate film 14 made of polyvinyl alcohol resin or the like is interposed between a plurality of glass substrates (first and second glass substrates 12 and 13), and has a structure in consideration of impact resistance. It has become.
  • a ceramic layer 15 is formed on the surface of the first glass substrate 12, and further, a receiving unit composed of a single wire or a plurality of wirings having an antenna function is connected to the surface of the ceramic layer 15 and the receiving unit.
  • a conductive film 16 having a rectangular soldering portion is formed.
  • the receiving unit is connected to a connection terminal via a soldering unit, and the connection terminal is connected to a lead wire.
  • this glass with an antenna is equipped as window glass for vehicles, such as a car, for example like anti-fog glass, receives the electric wave from the outside of a car, and is used for a radio and a television.
  • This glass with an antenna is manufactured as follows.
  • a ceramic paste mainly composed of a ceramic material containing glass frit is applied on the first glass substrate 12 and dried.
  • the conductive paste of the present invention is applied on the ceramic paste so as to have a predetermined antenna pattern, dried, and then the ceramic paste and the conductive paste are simultaneously fired to form the conductive film 16.
  • the intermediate film 14 is pasted through an adhesive so that the first glass substrate 12 and the second glass substrate 13 are sandwiched, thereby producing a glass with an antenna.
  • this glass with an antenna by forming the conductive film 16 using the conductive paste of the present invention, as in the first embodiment, the fixing force was improved while ensuring a low specific resistance. An antenna-attached glass having good mechanical strength can be obtained.
  • the present invention is not limited to the above embodiment.
  • the glass substrate 1 is used as a substrate, but it goes without saying that the present invention can also be applied to other substrates such as a ceramic substrate.
  • glass articles such as antifogging glass and glass with an antenna are mounted on the front or rear part of a vehicle or the like, so that the molybdenum silicide that exhibits a design effect by coloring the conductive film forming portion in a dark color. It is also preferable to add a black pigment such as chromium oxide or copper oxide having antiglare action to the conductive paste.
  • the present invention may contain various inorganic components as necessary within a range not affecting the characteristics.
  • Zr, P, V, Ce, Nb, Ta, W, Pd, Ag, Ru, Sn, In, Y, Dy, La, or the like may be contained.
  • the form of inclusion is not particularly limited, and is appropriately selected from oxides, hydroxides, peroxides, halides, carbonates, nitrates, phosphates, sulfates, fluorides, organometallic compounds, and the like. can do.
  • plasticizers such as di-2-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, etc. may be added.
  • Example preparation Ag powder of average particle size D 50 2.0 .mu.m (conductive powder), an average particle diameter D 50 2.0 ⁇ m Bi-B-Si-based glass frit, the average particle size of 1 ⁇ m molybdenum silicide powder, and the average A polypropylene resin powder (insoluble resin powder) having a particle size of 1 to 30 ⁇ m was prepared.
  • the average particle diameter D 50 was measured by a laser diffraction particle size distribution analyzer.
  • an organic vehicle was produced by the following method. That is, the organic cellulose was prepared by mixing the ethyl cellulose resin and ⁇ -terpineol so that the ethyl cellulose resin as the organic binder was 10 wt% and the ⁇ -terpineol as the organic solvent was 90 wt%.
  • Ag powder 80 wt%, glass frit 5 wt%, molybdenum silicide powder: 0.5 wt%, organic vehicle: 14.5 wt%, and further, polypropylene resin powder is added to 100 parts by weight of Ag powder.
  • Polypropylene resin powder was added so as to be 0-2 parts by weight, mixed with a planetary mixer, then dispersed with a three-roll mill and kneaded to prepare conductive pastes of sample numbers 1-9.
  • sample evaluation Prepare slide glass with length: 76 mm, width: 26 mm, thickness: 1.4 mm, use the above conductive paste, screen print so that line total length L: 100 mm, line width W: 0.5 mm, slide A circuit pattern was formed on the glass, and a current collecting pattern of 2 mm in length and 2 mm in width was formed on both ends to obtain a dry film comprising the circuit pattern and the current collecting pattern.
  • this slide glass was dried at a temperature of 150 ° C. for 10 minutes, then baked at a maximum temperature of 600 ° C. for 5 minutes, the dried film was dried, and a sample number in which a conductive film and a collecting electrode were formed on the surface of the slide glass Samples 1 to 9 were prepared.
  • the resistance value of the collecting electrode formed on both ends of the conductive film was measured with a digital resistance meter.
  • a Sn-plated Cu lead wire was soldered and joined to the current collecting electrode, the lead wire was pulled at a constant speed, and the maximum load until peeling was measured to determine the fixing strength of the electrode.
  • Table 1 shows the average particle diameter of polypropylene resin powders used in sample numbers 1 to 9, the content with respect to 100 parts by weight of Ag, and the measurement results (specific resistance, adhesion strength).
  • Sample No. 1 does not contain polypropylene resin powder in the conductive paste, so the specific resistance is as good as 2.6 ⁇ ⁇ cm, but the adhesion strength is as low as 11 N, and it is between the slide glass and the conductive film. It was found that the adhesive strength was inferior.
  • Sample Nos. 2 to 9 have an adhesion strength of 12 N or more, and it was found that the adhesion strength was improved compared to Sample No. 1.
  • Sample No. 2 had an improved fixing strength compared to Sample No. 1, but the fixing strength was 12 N, and the improvement effect was small. This is because the average particle diameter D 50 of the polypropylene resin powder as small as 1 [mu] m, it is impossible to polypropylene resin powder be removed by firing to form a large void that functions as a ventilation hole, decomposition gas conductive film This is probably because the contact area between the conductive film and the slide glass decreased.
  • Sample No. 6 had a fixing strength of 16N and was less than 20N, and the improvement effect was small. This is because the average particle diameter D 50 of the polypropylene resin powder is as large as 30 ⁇ m, so the number of polypropylene resin powders in the conductive paste is small, and even if voids are formed by firing, the density of the voids decreases. This is probably because the contact area between the conductive film and the slide glass decreased.
  • Sample No. 9 had good adhesion strength of 24 N, but the specific resistance increased to 4.3 ⁇ ⁇ cm. This is because the content of the polypropylene resin powder is as large as 2 parts by weight with respect to 100 parts by weight of Ag. Therefore, the content of Ag powder in the conductive paste is relatively decreased, and it is considered that the specific resistance is increased.
  • Sample Nos. 3 to 5, 7, and 8 have an average particle diameter D 50 of polypropylene resin powder of 3 to 15 ⁇ m and a content of 0.2 to 1.0 part by weight with respect to 100 parts by weight of Ag powder. Therefore, the specific resistance was 3.4 ⁇ ⁇ cm or less, the fixing strength was 20 to 25 N, and it was found that a conductive paste with good specific resistance and fixing strength can be obtained.
  • the average particle diameter D 50 of the insoluble resin powder is 3 to 15 ⁇ m, and the content thereof is conductive. It was found that 0.2 to 1.0 parts by weight is effective with respect to 100 parts by weight of the conductive powder.
  • a conductive paste that can be suitably used for glass articles such as an anti-fogging glass for vehicles and a glass with an antenna having good adhesion to the substrate while ensuring a desired specific resistance is realized.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Conductive Materials (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Abstract

This conductive paste contains a conductive powder, a glass frit 6 and an organic vehicle that is composed of an organic binder and an organic solvent, and additionally contains a resin powder that is insoluble in the organic vehicle and is burned down by a firing treatment. A dried film obtained by applying and drying this conductive paste is subjected to a firing treatment, thereby forming a conductive film 2 in a predetermined pattern on a glass substrate 1, while having the resin powder burned down at the same time so that a void 9 is formed in the burned-out space of the resin powder for ventilation of a decomposed gas of the organic binder. A glass article such as antifogging glass and glass with an antenna is obtained using this conductive paste. Consequently, the present invention enables the achievement of: a conducive paste which is capable of ensuring good adhesion to a substrate, while ensuring a desired low resistivity; a method for forming a conductive pattern with use of this conductive paste; and a glass article such as antifogging glass and glass with an antenna, which is obtained using this conductive paste.

Description

導電性ペースト、導電パターンの形成方法、及びガラス物品Conductive paste, method for forming conductive pattern, and glass article
　本発明は、導電性ペースト、導電パターンの形成方法、及びガラス物品に関し、より詳しくは、自動車等の車両用窓ガラスに付設される防曇用の熱線やアンテナパターン等を形成するための導電性ペースト、該導電性ペーストを使用した導電パターンの形成方法、及び該導電性ぺ－ストを使用した防曇ガラスやアンテナ付きガラス等のガラス物品に関する。 The present invention relates to a conductive paste, a method for forming a conductive pattern, and a glass article. More specifically, the present invention relates to a conductive material for forming an antifogging hot wire or antenna pattern attached to a window glass for a vehicle such as an automobile. The present invention relates to a paste, a method for forming a conductive pattern using the conductive paste, and a glass article such as an antifogging glass or a glass with an antenna using the conductive paste.
　従来より、自動車等の車両の窓ガラスには、防曇用の熱線を配した防曇ガラスや車外からの電波を受信するアンテナ付きガラス等のガラス物品が使用されている。これらのガラス物品、例えば防曇ガラスでは、通常、素材となるガラス基板上に導電性ペーストを塗布して回路パターンを形成すると共に該回路パターンの両端部に集電パターンを形成し、乾燥させた後に焼成処理を行って作製している。これにより所定パターンの導電膜をガラス基板上に固着させると共に、導電膜の両端部に形成した集電電極に接続端子をはんだ付けし、さらにリード線を介して前記接続端子を給電端子に接続している。 Conventionally, glass articles such as antifogging glass provided with a heat ray for antifogging and glass with an antenna for receiving radio waves from outside the vehicle have been used for the window glass of a vehicle such as an automobile. In these glass articles, for example, antifogging glass, a conductive paste is usually applied on a glass substrate as a raw material to form a circuit pattern, and current collecting patterns are formed on both ends of the circuit pattern and dried. It is manufactured by performing a baking process later. As a result, the conductive film having a predetermined pattern is fixed on the glass substrate, the connection terminals are soldered to the collecting electrodes formed on both ends of the conductive film, and the connection terminals are connected to the power supply terminals via lead wires. ing.
　そして、この種の導電ペーストも、従来より、盛んに研究・開発されている。 And this type of conductive paste has been actively researched and developed.
　例えば、特許文献１には、導電性材料の微細に分割された粒子と、ホウ酸鉛、ケイ酸鉛、ホウケイ酸鉛等のケイ酸化合物、金属の酸化物または酸化物前駆体およびそれらの混合物からなる群から選択される無機結合剤と、それらを分散する液体ビヒクルを含む伝導性組成物であって、全組成物は５０～９５質量％の固形分を含み、前記無機結合剤は、該組成物の全固形分の１．０％未満である伝導性組成物が提案されている。 For example, Patent Document 1 discloses finely divided particles of a conductive material, silicate compounds such as lead borate, lead silicate, lead borosilicate, metal oxides or oxide precursors, and mixtures thereof. A conductive composition comprising an inorganic binder selected from the group consisting of and a liquid vehicle in which they are dispersed, wherein the total composition comprises 50 to 95 wt% solids, said inorganic binder comprising: Conductive compositions have been proposed that are less than 1.0% of the total solids of the composition.
　特許文献１は、５０～９５質量％の固形分を含み、かつ無機結合剤（ガラスフリット）の含有量を全固形分の１．０％未満に低減することにより、基板を被覆するエナメルに割れが生じることもなく接着力を維持することができ、これにより導電性と接着力の両立を図ろうとしている。 Patent Document 1 includes a solid content of 50 to 95% by mass and reduces the content of the inorganic binder (glass frit) to less than 1.0% of the total solid content, thereby cracking the enamel covering the substrate. Thus, the adhesive force can be maintained without causing the occurrence of the phenomenon, and thereby, both the electrical conductivity and the adhesive force are attempted to be achieved.
特開２００４－３１１４３８号公報（請求項２、段落番号〔０００９〕、〔００１９〕～〔００２１〕、表２等）JP 2004-31438 A (Claim 2, paragraph numbers [0009], [0019] to [0021], Table 2, etc.)
　特許文献１では、伝導性組成物中の無機結合剤の含有量を低減させて比抵抗を低くし、これにより導電性を向上させている。しかし、無機結合剤の含有量が１．０％未満と少なく、このため導電膜とガラス基板との固着力に劣る場合がある。 In Patent Document 1, the content of the inorganic binder in the conductive composition is reduced to lower the specific resistance, thereby improving the conductivity. However, the content of the inorganic binder is as low as less than 1.0%, and thus the adhesion between the conductive film and the glass substrate may be inferior.
　本発明はこのような事情に鑑みなされたものであって、所望の低比抵抗を確保しつつ基板との間で良好な固着力を確保することができる導電性ペースト、該導電性ペーストを使用した導電パターンの形成方法、及び該導電性ペーストを使用した防曇ガラスやアンテナ付きガラス等のガラス物品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 uses a conductive paste that can ensure a good adhesion to a substrate while ensuring a desired low specific resistance, and uses the conductive paste. It is an object of the present invention to provide a method for forming a conductive pattern, and a glass article such as an antifogging glass or a glass with an antenna using the conductive paste.
　車両用の防曇ガラスやアンテナ付きガラス等のガラス物品の作製に使用される導電性ペーストは、通常、導電性粉末、ガラスフリット、及び有機バインダと有機溶剤で構成される有機ビヒクルを含有している。また、この種のガラス物品では、[背景技術]の項でも述べたように、導電膜や集電電極は導電性ペーストの焼成により作製されるが、斯かる導電性ペーストは、導電性及び基板に対する固着力が良好であることが要請される。 Conductive pastes used to make glass articles such as antifogging glass for vehicles and glass with antennas usually contain conductive powder, glass frit, and an organic vehicle composed of an organic binder and an organic solvent. Yes. Further, in this type of glass article, as described in the section of “Background Art”, the conductive film and the collecting electrode are produced by firing a conductive paste. It is required that the adhesive strength to the is good.
　また、良好な導電性を得るためには導電膜の比抵抗を極力抑制する必要があり、そのためには緻密な導電膜を形成するのが望ましい。 In order to obtain good conductivity, it is necessary to suppress the specific resistance of the conductive film as much as possible. For this purpose, it is desirable to form a dense conductive film.
　本発明者は、斯かる観点から導電性ペーストを使用してガラス基板上に導電膜を形成し、鋭意研究を行ったところ、焼成時に発生する有機バインダの分解ガスが導電膜内部に閉じ込められ、さらにこの分解ガスは導電膜とガラス基板の界面に集まって空洞部を形成することが分かった。そして、分解ガスが充満した空洞部がガラス基板との界面に多数形成される結果、導電膜とガラス基板との接触面積が減少し、このためガラス基板と導電膜との間の固着力が低下することが分かった。 The present inventor formed a conductive film on a glass substrate using a conductive paste from such a viewpoint, and conducted earnest research, the decomposition gas of the organic binder generated during firing was confined inside the conductive film, Furthermore, it was found that this decomposition gas gathers at the interface between the conductive film and the glass substrate to form a cavity. As a result of the formation of a large number of cavities filled with the decomposition gas at the interface with the glass substrate, the contact area between the conductive film and the glass substrate is reduced, and thus the adhesion between the glass substrate and the conductive film is reduced. I found out that
　そこで、本発明者は更に鋭意研究を進めたところ、有機ビヒクルに対して不溶性を有しかつ焼成処理で焼失する樹脂粉末（以下、「不溶性樹脂粉末」という。）を導電性ペースト中に含有させて焼成処理を行うことにより、不溶性樹脂粉末の焼失跡に形成された空隙が上述した分解ガスの換気孔として機能し、これにより分解ガスで充満された空洞部の生成を抑制することができ、低比抵抗を確保しつつ基板との固着力を向上させることができるという知見を得た。 In view of this, the present inventor has further conducted intensive research. As a result, the conductive paste contains a resin powder that is insoluble in the organic vehicle and burned off by the baking treatment (hereinafter referred to as “insoluble resin powder”). By performing the baking treatment, the voids formed in the burning trace of the insoluble resin powder function as the above-described cracked gas ventilation holes, thereby suppressing the generation of the cavity filled with the cracked gas, The inventor has obtained knowledge that the adhesion to the substrate can be improved while ensuring a low specific resistance.
　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、少なくとも導電性粉末と、ガラスフリットと、有機バインダと有機溶剤とからなる有機ビヒクルとを含有した導電性ペーストであって、前記有機ビヒクルに対し不溶性を有しかつ焼成処理で焼失する不溶性樹脂粉末を含んでいることを特徴としている。 The present invention has been made based on such knowledge, and the conductive paste according to the present invention is a conductive paste containing at least a conductive powder, a glass frit, and an organic vehicle composed of an organic binder and an organic solvent. An insoluble resin powder that is insoluble in the organic vehicle and that is burned off by the baking treatment.
　ここで、「有機ビヒクルに対し不溶性を有する」とは、樹脂粉末を有機ビヒクル中に添加して撹拌しても、該有機ビヒクルに溶解しない未溶解の固形物が残留することを意味し、有機ビヒクルの有機溶剤に全く溶解しない場合のみならず、有機溶剤に若干溶解するものの未溶解の固形分が残留する難溶性の場合も含む。 Here, “having insolubility with respect to the organic vehicle” means that an undissolved solid that does not dissolve in the organic vehicle remains even if the resin powder is added to the organic vehicle and stirred. This includes not only the case where the vehicle does not dissolve in the organic solvent at all, but also the case where it is slightly soluble in the organic solvent but hardly soluble so that an undissolved solid content remains.
　また、本発明の導電性ペーストでは、前記不溶性樹脂粉末が焼失する温度は、５００～８００℃が好ましい。 In the conductive paste of the present invention, the temperature at which the insoluble resin powder burns out is preferably 500 to 800 ° C.
　また、本発明の導電性ペーストでは、前記不溶性樹脂粉末は、平均粒径が３～１５μｍであるのが好ましい。 In the conductive paste of the present invention, the insoluble resin powder preferably has an average particle size of 3 to 15 μm.
　この場合は、不溶性樹脂粉末の含有量を調整することにより、比抵抗の上昇を抑制することができ、したがって導電性と基板との固着力とが両立した導電性ペーストを効果的に得ることができる。 In this case, by adjusting the content of the insoluble resin powder, it is possible to suppress an increase in specific resistance, and therefore, it is possible to effectively obtain a conductive paste having both conductivity and adhesion to the substrate. it can.
　尚、本発明では、平均粒径は積算累積分布が５０％の粒径、すなわちメジアン径（以下、「平均粒径Ｄ50」と記す。）をいう。 In the present invention, the average particle diameter means a particle diameter having an integrated cumulative distribution of 50%, that is, a median diameter (hereinafter referred to as “average particle diameter D 50 ”).
　また、本発明の導電性ペーストは、前記不溶性樹脂粉末の含有量が、前記導電性粉末１００重量部に対し０．２～１重量部であるのがより好ましい。 In the conductive paste of the present invention, the content of the insoluble resin powder is more preferably 0.2 to 1 part by weight with respect to 100 parts by weight of the conductive powder.
　この場合は、不溶性樹脂粉末の平均粒径Ｄ50を調整することにより、固着力の低下を抑制することができ、したがって導電性と基板との固着力とが両立した導電性ペーストを効果的に得ることができる。 In this case, by adjusting the average particle diameter D 50 of the insoluble resin powder, it is possible to suppress a decrease in the adhesive force, thus the conductive paste sticking force and is both conductive and the substrate effectively Obtainable.
　また、本発明の導電性ペーストは、前記不溶性樹脂粉末は、ポリオレフィン、ポリメタクリル酸エステル、及びポリアクリル酸エステルの群から選択された少なくとも１種を含むのが好ましい。 In the conductive paste of the present invention, the insoluble resin powder preferably contains at least one selected from the group consisting of polyolefin, polymethacrylic acid ester, and polyacrylic acid ester.
　斯かる不溶性樹脂粉末は、有機ビヒクルに対し不溶性を有しかつ焼成処理で容易に焼失することから、本発明の導電性ペーストに好んで使用することができる。 Such an insoluble resin powder is insoluble in an organic vehicle and easily burned off by a baking treatment, and therefore can be preferably used for the conductive paste of the present invention.
　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 is preferably composed mainly of Ag.
　また、本発明に係る導電パターンの形成方法は、導電性粉末と、ガラスフリットと、有機バインダと有機溶剤とからなる有機ビヒクルと、該有機ビヒクルに対して不溶性を有しかつ焼成処理で焼失する樹脂粉末とを含む導電性ペーストを基板上に塗布する工程と、前記基板上に塗布された前記導電性ペーストに焼成処理を施し、前記基板上に所定パターンの導電膜を形成すると同時に前記樹脂粉末を焼失させ、前記導電膜を貫通する貫通孔を前記樹脂粉末の焼失跡に形成する工程とを含むことを特徴としている。 In addition, the method for forming a conductive pattern according to the present invention includes a conductive powder, a glass frit, an organic vehicle composed of an organic binder and an organic solvent, insoluble in the organic vehicle, and burned off by a baking treatment. A step of applying a conductive paste containing a resin powder on the substrate; and baking the conductive paste applied on the substrate to form a conductive film having a predetermined pattern on the substrate, and at the same time, the resin powder And a step of forming a through-hole penetrating the conductive film in the burnout trace of the resin powder.
　これにより有機バインダの分解ガスを換気する貫通孔が不溶性樹脂粉末の焼失跡に形成されることから、該貫通孔が有機バインダの分解ガスに対する換気孔となり、前記分解ガスが充満した空洞部が基板と導電膜との間に形成されるのを抑制することができる。したがって、基板と導電膜との間にブリスタ（膨れ）が形成されることもなく、界面の接触面積が増加することから、基板と導電膜との固着力を向上させることができる。 As a result, a through hole for ventilating the decomposition gas of the organic binder is formed in the burned-out trace of the insoluble resin powder, so that the through hole becomes a ventilation hole for the decomposition gas of the organic binder, and the cavity filled with the decomposition gas is the substrate. And formation between the conductive film and the conductive film can be suppressed. Therefore, no blister (swelling) is formed between the substrate and the conductive film, and the contact area at the interface increases, so that the adhesion between the substrate and the conductive film can be improved.
　また、本発明の導電パターンの形成方法は、焼成後の前記導電膜の比抵抗が、３．４μΩ・ｃｍ以下であるのが好ましい。 Moreover, in the method for forming a conductive pattern of the present invention, it is preferable that the specific resistance of the conductive film after firing is 3.4 μΩ · cm or less.
　これにより固着力のみならず低比抵抗で導電性の良好な導電膜を得ることができ、固着力と導電性が両立した所望の導電パターンを得ることができる。 Thereby, it is possible to obtain a conductive film having not only fixing strength but also low specific resistance and good conductivity, and a desired conductive pattern having both fixing strength and conductivity can be obtained.
　また、本発明に係るガラス物品は、ガラス基板上に導電膜が形成され、該導電膜上に接続端子が接合されたガラス物品であって、前記導電膜は、上記いずれかに記載の導電性ペーストの焼結体で形成されてい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 conductive film is formed on a glass substrate and a connection terminal is bonded to the conductive film. It is characterized by being formed of a paste sintered body.
　これにより導電性を確保しつつガラス基板と導電膜との固着力が良好で機械的強度にも優れた防曇ガラスやアンテナ付きガラス等の各種ガラス物品を得ることができる。 This makes it possible to obtain various glass articles such as antifogging glass and glass with an antenna that have good adhesion between the glass substrate and the conductive film and excellent mechanical strength while ensuring conductivity.
　本発明の導電性ペーストによれば、少なくとも導電性粉末と、ガラスフリットと、有機バインダと有機溶剤とからなる有機ビヒクルとを含有した導電性ペーストであって、前記有機ビヒクルに対し不溶性を有しかつ焼成処理で焼失する不溶性樹脂粉末を含んでいるので、焼成により焼失した不溶性樹脂粉末の焼失跡には導電膜を貫通する貫通孔のような空隙が形成される。そして、この空隙が有機バインダの熱分解で発生した分解ガスの換気孔として機能し、これにより分解ガスの発生に起因した界面での空洞部の生成を抑制することが可能となる。 According to the conductive paste of the present invention, it is a conductive paste containing at least a conductive powder, glass frit, and an organic vehicle composed of an organic binder and an organic solvent, and is insoluble in the organic vehicle. In addition, since the insoluble resin powder burned out by the baking treatment is included, a void such as a through-hole penetrating the conductive film is formed in the burned-out trace of the insoluble resin powder burned out by the baking. And this space | gap functions as a ventilation hole of the decomposition gas produced | generated by the thermal decomposition of the organic binder, and it becomes possible to suppress the production | generation of the cavity part in the interface resulting from generation | occurrence | production of decomposition gas by this.
　このように本発明の導電性ペーストを焼成させた場合でも、有機バインダの分解ガスが充満した空洞部の生成を抑制できるので、基板との接触面積が増加させることができ、所望の低比抵抗を確保しつつ基板との固着力が向上したガラス物品の作製に好適な導電性ペーストを得ることが可能となる。 As described above, even when the conductive paste of the present invention is baked, the formation of the cavity filled with the decomposition gas of the organic binder can be suppressed, so that the contact area with the substrate can be increased, and a desired low specific resistance can be achieved. Thus, it is possible to obtain a conductive paste suitable for producing a glass article having improved adhesion to the substrate while securing the above.
　また、本発明の導電パターンの形成方法によれば、有機バインダの分解ガスを換気する貫通孔が不溶性樹脂粉末の焼失跡に形成されることから、該貫通孔が有機バインダの分解ガスに対する換気孔となり、前記分解ガスが充満した空洞部が基板と導電膜との間に形成されるのを抑制することができる。そしてその結果、基板と導電膜との間の接触面積が増加し、基板と導電膜との固着力を向上させることができる。 Further, according to the method for forming a conductive pattern of the present invention, since the through hole for venting the decomposition gas of the organic binder is formed in the burned trace of the insoluble resin powder, the through hole is a ventilation hole for the decomposition gas of the organic binder. Thus, the formation of a cavity filled with the decomposition gas between the substrate and the conductive film can be suppressed. As a result, the contact area between the substrate and the conductive film increases, and the adhesion between the substrate and the conductive film can be improved.
　また、本発明のガラス物品によれば、ガラス基板上に導電膜が形成され、該導電膜上に接続端子が接合されたガラス物品であって、前記導電膜は、上記いずれかに記載の導電性ペーストの焼結体で形成されているので、導電性を確保しつつガラス基板と導電膜との固着力を向上させることができ、導電膜に引張応力が負荷されても破断するのを抑制できる良好な機械的強度を有する防曇ガラスやアンテナ付きガラス等の各種ガラス物品を得ることができる。 In addition, according to the glass article of the present invention, a conductive film is formed on a glass substrate, and a connection terminal is bonded on the conductive film. Because it is formed of a sintered paste of conductive paste, it can improve the adhesion between the glass substrate and the conductive film while ensuring conductivity, and suppresses breakage even when tensile stress is applied to the conductive film Various glass articles such as antifogging glass and glass with an antenna having good mechanical strength can be obtained.
本発明に係る導電性ペーストを使用して作製されたガラス物品としての防曇ガラスの一実施の形態（第１の実施の形態）を示す正面図である。It is a front view which shows one Embodiment (1st Embodiment) of the anti-fog glass as a glass article produced using the electrically conductive paste which concerns on this invention. 図１のＡ－Ａ矢視断面図である。FIG. 2 is a cross-sectional view taken along line AA in FIG. 1. 乾燥膜の一例を模式的に示す断面図である。It is sectional drawing which shows an example of a dry film | membrane typically. 焼結体の一例を模式的に示す断面図である。It is sectional drawing which shows an example of a sintered compact typically. 乾燥膜の他の例を模式的に示す断面図である。It is sectional drawing which shows the other example of a dry film typically. 焼結体の他の例を模式的に示す断面図である。It is sectional drawing which shows the other example of a sintered compact typically. 本発明に係るガラス物品の第２の実施の形態としてのアンテナ付きガラスを模式的に示す断面図である。It is sectional drawing which shows typically the glass with an antenna as 2nd Embodiment of the glass article which concerns on this invention.
　次に、本発明の実施の形態を詳説する。 Next, an 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としての防曇ガラスの一実施の形態を示す正面図であり、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 of an anti-fogging glass as a glass article manufactured using the conductive paste according to the present invention, and FIG. 2 is a cross-sectional view taken along the line AA in FIG. It is.
　この防曇ガラスは、ガラス基板１の表面に所定間隔を有して細線化・薄膜化されたライン状の導電膜２が平行状に複数形成されると共に、導電膜２の両端部には集電電極３ａ、３ｂが形成され、集電電極３ａ、３ｂには不図示の接続端子がはんだ付けされて接合されている。 The antifogging glass has a plurality of line-shaped conductive films 2 that are thinned and thinned at predetermined intervals on the surface of the glass substrate 1 and are formed in parallel on both ends of the conductive film 2. Electrical electrodes 3a and 3b are formed, and connection terminals (not shown) are soldered and joined to the current collecting electrodes 3a and 3b.
　すなわち、この防曇ガラスは、ガラス基板１上に導電性ペーストが塗布されて回路パターンが形成されると共に回路パターンの両端部には集電パターンが形成され、焼成処理によって所定パターンの導電膜２及び集電電極３ａ、３ｂが形成される。このように導電膜２及び集電電極３ａ、３ｂは、導電性ペーストの焼結体で形成されている。そして、導電膜２がガラス基板１上に固着されると共に、集電電極３ａ、３ｂには接続端子（不図示）がはんだ付けされ、該接続端子を介してリード線と接続されている。 That is, in this anti-fogging glass, a conductive paste is applied on the glass substrate 1 to form a circuit pattern, and current collecting patterns are formed at both ends of the circuit pattern. And current collecting electrodes 3a and 3b are formed. Thus, the conductive film 2 and the collecting electrodes 3a and 3b are formed of a sintered body of conductive paste. The conductive film 2 is fixed on the glass substrate 1, and connection terminals (not shown) are soldered to the collecting electrodes 3a and 3b, and are connected to lead wires through the connection terminals.
　この防曇ガラスは、例えば自動車等の車両のフロントガラスやリアガラスとして装備され、集電電極３ａ、３ｂを介して給電端子から導電膜２に給電され、導電膜２を発熱させることによって窓ガラスの曇り止めを行うことができる。 This anti-fog glass is equipped as a windshield or rear glass of a vehicle such as an automobile, for example, and is supplied with power to the conductive film 2 from the power supply terminal via the collector electrodes 3a and 3b. Anti-fogging can be performed.
　次に、上述した導電膜２及び集電電極３ａ、３ｂを形成するための導電性ペーストについて詳述する。 Next, the conductive paste for forming the conductive film 2 and the collecting electrodes 3a and 3b described above will be described in detail.
　本導電性ペーストは、導電性粉末と、ガラスフリットと、有機ビヒクルとを含有している。また、有機ビヒクルは、有機バインダと有機溶剤とで構成され、有機溶剤に可溶な有機バインダが有機溶剤中に溶解している。 This conductive paste contains conductive powder, glass frit, and an organic vehicle. The organic vehicle is composed of an organic binder and an organic solvent, and an organic binder soluble in the organic solvent is dissolved in the organic solvent.
　さらに、この導電性ペーストには、前記有機ビヒクルに対し不溶性を有しかつ焼成処理で焼失する不溶性樹脂粉末が含有されており、これにより所望の低比抵抗を確保しつつガラス基板１と導電膜２との固着性を向上させている。 Further, the conductive paste contains an insoluble resin powder that is insoluble in the organic vehicle and burns away by the baking treatment, thereby ensuring the desired low specific resistance and the glass substrate 1 and the conductive film. 2 is improved.
　ここで、「有機ビヒクルに対し不溶性を有する」とは、樹脂粉末を有機ビヒクル中に添加して撹拌しても、該有機ビヒクルに溶解しない未溶解の固形物が残留することを意味し、有機ビヒクルに全く溶解しない不溶性の場合のみならず、有機ビヒクルに若干溶解するものの未溶解の固形分が残留する難溶性の場合も含む。 Here, “having insolubility with respect to the organic vehicle” means that an undissolved solid that does not dissolve in the organic vehicle remains even if the resin powder is added to the organic vehicle and stirred. This includes not only the insoluble case where it does not dissolve at all in the vehicle, but also the case where it is slightly soluble in the organic vehicle but remains insoluble and remains undissolved.
　この種の導電性ペーストをガラス基板１上に塗布し乾燥させた後、焼成処理を行うと、有機バインダは熱分解を伴いながら焼失するが、良好な導電性を確保すべく低比抵抗の導電膜２を得るためには、該導電膜２を緻密化する必要がある。 When this kind of conductive paste is applied on the glass substrate 1 and dried, and then subjected to a baking treatment, the organic binder is burned away with thermal decomposition, but a low specific resistance conductive material is required to ensure good conductivity. In order to obtain the film 2, the conductive film 2 needs to be densified.
　しかしながら、緻密な導電膜２を形成しようとすると、有機バインダの熱分解によって生成されたＣＯ２等の分解ガスが導電膜２の内部に閉じ込められ、かつ、この分解ガスはガラス基板１と導電膜２との界面に集中し、空洞部を形成する。したがって、界面では分解ガスが充満した空洞部の占有比率が増加し、このためガラス基板１と導電膜２との接触面積が減少し、ガラス基板１に対する導電膜２の固着力の低下を招くおそれがある。 However, if an attempt is made to form a dense conductive film 2, a decomposition gas such as CO 2 generated by the thermal decomposition of the organic binder is confined inside the conductive film 2, and this decomposition gas is contained in the glass substrate 1 and the conductive film. Concentrates at the interface with 2 to form a cavity. Therefore, the occupation ratio of the cavity filled with the decomposition gas is increased at the interface, so that the contact area between the glass substrate 1 and the conductive film 2 is decreased, and the adhesion force of the conductive film 2 to the glass substrate 1 may be reduced. There is.
　そこで、本実施の形態では、有機ビヒクルに対し不溶性を有しかつ焼成処理で焼失する不溶性樹脂粉末を導電性ペースト中に含有させ、これにより焼成時に不溶性樹脂粉末を焼失させて焼失跡に空隙を形成し、該空隙を分解ガスの換気孔として機能させることにより、分解ガスが充満した空洞部がガラス基板１と導電膜２との界面に残存するのを抑制している。 Therefore, in the present embodiment, the conductive paste contains insoluble resin powder that is insoluble in the organic vehicle and burned off by the baking treatment, thereby burning off the insoluble resin powder during baking and leaving voids in the burned trace. By forming the void and functioning as a vent hole for the cracked gas, the cavity filled with the cracked gas is suppressed from remaining at the interface between the glass substrate 1 and the conductive film 2.
　このように本導電性ペーストは、少なくとも導電性粉末と、ガラスフリットと、有機ビヒクルとを含有した導電性ペーストであって、前記有機ビヒクルに対し不溶性を有しかつ焼成処理で焼失する不溶性樹脂粉末を含んでいるので、焼成により焼失した不溶性樹脂粉末の焼成跡には導電膜を貫通する貫通孔のような空隙が形成される。そして、この空隙が有機バインダの熱分解で発生した分解ガスの換気孔として作用し、分解ガスが充満した界面での空洞部の生成を抑制できる。これにより、ガラス基板１と導電膜２との接触面積が増加し、所望の比抵抗を確保しつつガラス基板１との固着力を向上させることが可能となる。したがって、導電膜２や集電電極３ａ、３ｂに外部からの引張応力が負荷されてもガラス基板から剥離するのを抑制することが可能となる。特に接続端子を介してリード線が接続される集電電極３ａ、３ｂに外部からの引張応力が負荷されやすいため好適である。 As described above, the conductive paste is a conductive paste containing at least a conductive powder, a glass frit, and an organic vehicle, and is insoluble in the organic vehicle and insoluble resin powder that is burned off by the baking treatment. Therefore, a void such as a through-hole penetrating the conductive film is formed in the firing trace of the insoluble resin powder burnt down by firing. And this space | gap acts as a ventilation hole of the cracked gas produced | generated by the thermal decomposition of the organic binder, and can suppress the production | generation of the cavity part in the interface filled with the cracked gas. Thereby, the contact area of the glass substrate 1 and the electrically conductive film 2 increases, and it becomes possible to improve the adhering force with the glass substrate 1 while ensuring a desired specific resistance. Therefore, even if an external tensile stress is applied to the conductive film 2 and the current collecting electrodes 3a and 3b, it is possible to suppress peeling from the glass substrate. In particular, the collector electrodes 3a and 3b to which the lead wires are connected via the connection terminals are preferably subjected to a tensile stress from the outside.
　このような不溶性樹脂粉末としては、上述したように有機ビヒクルに対し不溶性を有しかつ焼成処理、すなわち焼成温度（例えば、５００～８００℃）で焼失する樹脂であれば、特に限定されるものではないが、通常は、ポリプロピレン等のポリオレフィン、ポリメタクリル酸エステル、ポリアクリル酸エステルの群から選択された少なくとも１種を含む樹脂粉末を好んで使用することができる。 Such an insoluble resin powder is not particularly limited as long as it is a resin that is insoluble in an organic vehicle as described above and burns away at a baking treatment, that is, at a baking temperature (eg, 500 to 800 ° C.). In general, however, a resin powder containing at least one selected from the group consisting of polyolefins such as polypropylene, polymethacrylic acid esters, and polyacrylic acid esters can be preferably used.
　次に、本導電性ペーストに不溶性樹脂粉末を含有させた理由を詳述する。 Next, the reason why the conductive paste contains the insoluble resin powder will be described in detail.
　図３は、焼成前の状態の一例を模式的に示す断面図であり、図４は、焼成後の状態の一例を模式的に示す断面図を示している。 FIG. 3 is a cross-sectional view schematically showing an example of the state before firing, and FIG. 4 is a cross-sectional view schematically showing an example of the state after firing.
　すなわち、焼成前は、図３に示すように、ガラス基板１の表面には導電性ペーストが塗布・乾燥されていることから、ガラス基板１上に乾燥膜４が形成されている。この乾燥膜４は、導電性粉末５、ガラスフリット６、不溶性樹脂粉末７、及び有機バインダ８を含有している。 That is, before baking, as shown in FIG. 3, since the conductive paste is applied and dried on the surface of the glass substrate 1, the dry film 4 is formed on the glass substrate 1. The dry film 4 contains conductive powder 5, glass frit 6, insoluble resin powder 7, and organic binder 8.
　次いで、乾燥膜４に焼成処理を施すと、図４に示すように、導電膜２が形成されると共にガラスフリット６はガラス基板１との界面に偏析する。また、不溶性樹脂粉末７は熱分解して焼失し、不溶性樹脂粉末７が存在していた焼失跡には空隙９が形成される。 Next, when the dried film 4 is subjected to a baking treatment, the conductive film 2 is formed and the glass frit 6 is segregated at the interface with the glass substrate 1 as shown in FIG. Further, the insoluble resin powder 7 is thermally decomposed and burned, and voids 9 are formed in the burned trace where the insoluble resin powder 7 was present.
　導電膜２中には不溶性樹脂粉末７の粒径の大きさに応じ様々な孔径の空隙９が形成され、導電膜２を貫通するような空隙９、すなわち貫通孔１１も形成され得る。そしてこれらの空隙９は換気孔として作用する。その結果、分解ガスはガラス基板１と導電膜２との間に充満して導電膜２を押し上げることもなく、後述するブリスタ（膨れ）の形成が抑制され、これによりガラス基板１と導電膜２との接触面積を増加させることが可能となる。 In the conductive film 2, voids 9 having various pore sizes are formed according to the size of the particle size of the insoluble resin powder 7, and voids 9 that penetrate the conductive film 2, that is, through-holes 11 can also be formed. These gaps 9 act as ventilation holes. As a result, the cracked gas is not filled between the glass substrate 1 and the conductive film 2 and pushes up the conductive film 2, and the formation of blisters (swelling), which will be described later, is suppressed, thereby the glass substrate 1 and the conductive film 2. It is possible to increase the contact area.
　このように導電性ペースト中に不溶性樹脂粉末７を含有させることにより、焼成後のブリスタの形成を抑制することができ、その結果、ガラス基板１と導電膜２との接触面積を増加させることが可能となり、これによりガラス基板１との固着力を効果的に向上させることが可能となる。 Thus, by including the insoluble resin powder 7 in the conductive paste, formation of blisters after firing can be suppressed, and as a result, the contact area between the glass substrate 1 and the conductive film 2 can be increased. This makes it possible to effectively improve the fixing force with the glass substrate 1.
　そして、固着力の改善効果を確保するためには、不溶性樹脂粉末７の平均粒径Ｄ50は所定範囲であるのが好ましい。 Then, in order to secure the effect of improving the fixing strength, the average particle diameter D 50 of the insoluble resin powder 7 is preferably a predetermined range.
　図５は、焼成前の状態の他の例を模式的に示す断面図であり、図６は、焼成後の状態の他の例を模式的に示す断面図であり、不溶性樹脂粉末の平均粒径Ｄ50が比較的小さい場合を示している。 FIG. 5 is a cross-sectional view schematically showing another example of the state before firing, and FIG. 6 is a cross-sectional view schematically showing another example of the state after firing. diameter D 50 indicates the case where relatively small.
　焼成前は、図５に示すように、ガラス基板１の表面に導電性ペーストが塗布・乾燥されていることから、ガラス基板１上には乾燥膜４が形成されている。したがって、この乾燥膜４は、図３と同様、導電性粉末５、ガラスフリット６、不溶性樹脂粉末７、及び有機バインダ８を含有している。 Before firing, as shown in FIG. 5, the conductive paste is applied and dried on the surface of the glass substrate 1, so that a dry film 4 is formed on the glass substrate 1. Accordingly, the dry film 4 contains the conductive powder 5, the glass frit 6, the insoluble resin powder 7, and the organic binder 8 as in FIG.
　次いで、この乾燥膜４に焼成処理を施すと、図６に示すように、導電膜２が形成されると共にガラスフリット６はガラス基板１との界面に偏析する。また、図４と同様、不溶性樹脂粉末７は熱分解して焼失し、不溶性樹脂粉末７が存在していた焼失跡には空隙９が形成される。 Next, when this dry film 4 is subjected to a baking treatment, as shown in FIG. 6, the conductive film 2 is formed and the glass frit 6 is segregated at the interface with the glass substrate 1. As in FIG. 4, the insoluble resin powder 7 is thermally decomposed and burned out, and voids 9 are formed in the burned-out trace where the insoluble resin powder 7 was present.
　しかしながら、不溶性樹脂粉末７の平均粒径Ｄ50が小さいと、空隙９が導電膜２の緻密化によって消失したり、空隙９内にガラスフリット６が侵入し、また導電膜２の膜厚に比べて極めて小さい空隙９が形成され、空隙９が分解ガスの換気孔としての機能を十分に発揮しなくなるおそれがある。その結果、この図６に示すように、導電膜２の内部で発生した分解ガスが導電膜２を押し上げてブリスタ１０を形成し、このためガラス基板１と導電膜２との接触面積の減少を招く。したがって、不溶性樹脂粉末７を含有しない場合に比べると固着力は改善されるものの、改善効果は小さくなる。 However, when the average particle diameter D 50 of the insoluble resin powder 7 is small, the gap 9 disappears due to the densification of the conductive film 2, the glass frit 6 penetrates into the gap 9, and the film thickness of the conductive film 2 is smaller. As a result, a very small gap 9 is formed, and the gap 9 may not sufficiently function as a vent hole for cracked gas. As a result, as shown in FIG. 6, the decomposition gas generated inside the conductive film 2 pushes up the conductive film 2 to form a blister 10, thereby reducing the contact area between the glass substrate 1 and the conductive film 2. Invite. Therefore, although the fixing force is improved as compared with the case where the insoluble resin powder 7 is not contained, the improvement effect is reduced.
　一方、不溶性樹脂粉末７の平均粒径Ｄ50が過度に大きくなると、導電性ペースト中の不溶性樹脂粉末７の個数が相対的に減少することから、換気孔として機能する空隙９の個数も減少して該空隙９の存在密度が低下し、この場合も固着力の改善効果は小さくなるおそれがある。 On the other hand, when the average particle diameter D 50 of the insoluble resin powder 7 is excessively large, the number of insoluble resin powders 7 in the conductive paste is relatively reduced, and thus the number of voids 9 functioning as ventilation holes is also reduced. As a result, the density of the voids 9 decreases, and in this case, the effect of improving the fixing force may be reduced.
　すなわち、導電性ペースト中に不溶性樹脂粉末７が含有されていれば、焼成処理により空隙９の形成が可能であり、固着力の改善を図ることはできるが、より効果的な固着力の改善を得るためには、不溶性樹脂粉末７の平均粒径Ｄ50は好ましい範囲が存在する。 That is, if the insoluble resin powder 7 is contained in the conductive paste, the voids 9 can be formed by the baking treatment, and the fixing force can be improved, but the more effective fixing force can be improved. to obtain an average particle diameter D 50 of the insoluble resin powder 7 is present is preferably in the range.
　そして、このような好ましい範囲の平均粒径Ｄ50は、３～１５μｍである。平均粒径Ｄ50が３μｍ未満又は１５μｍを超える場合は、不溶性樹脂粉末７を含有していない場合に比べると固着力は改善されるものの、改善効果は小さい。 The average particle diameter D 50 in such a preferable range is 3 to 15 μm. When the average particle diameter D 50 is less than 3 μm or more than 15 μm, the fixing effect is improved as compared with the case where the insoluble resin powder 7 is not contained, but the improvement effect is small.
　また、不溶性樹脂粉末の含有量についても、上述したように不溶性樹脂粉末が含有されていれば焼成処理により不溶性樹脂粉末は焼失して空隙を形成することから、特に限定されるものではないが、固着力と比抵抗の両立を図る観点からは、好ましくは導電性粉末１００重量部に対し０．２～１重量部である。 Further, the content of the insoluble resin powder is not particularly limited, as long as the insoluble resin powder is contained as described above, since the insoluble resin powder is burnt out by the baking treatment to form voids, From the viewpoint of achieving both the fixing force and the specific resistance, the amount is preferably 0.2 to 1 part by weight with respect to 100 parts by weight of the conductive powder.
　不溶性樹脂粉末の含有量が導電性粉末１００重量部に対し０．２重量部未満になると、固着力の十分な改善効果が得られなくなるおそれがある。一方、不溶性樹脂粉末の含有量が導電性粉末１００重量部に対し１重量部を超えると、固着力は上昇するものの、不溶性樹脂粉末７が導電性粉末５に対し相対的に増量されるため、比抵抗が増加し導電性の低下を招くおそれがある。 When the content of the insoluble resin powder is less than 0.2 parts by weight with respect to 100 parts by weight of the conductive powder, there is a possibility that a sufficient improvement effect of the fixing force cannot be obtained. On the other hand, when the content of the insoluble resin powder exceeds 1 part by weight with respect to 100 parts by weight of the conductive powder, although the fixing force increases, the amount of the insoluble resin powder 7 is relatively increased with respect to the conductive powder 5, There is a possibility that the specific resistance increases and the conductivity decreases.
　したがって、比抵抗及び固着力の双方をより良好なものにするためには、不溶性樹脂粉末の平均粒径Ｄ50を３～１５μｍ、その含有量を導電性粉末１００重量部に対し０．２～１重量部とするのが好ましい。 Therefore, in order to improve both the specific resistance and the fixing force, the average particle diameter D 50 of the insoluble resin powder is 3 to 15 μm, and the content thereof is 0.2 to 100 parts by weight of the conductive powder. The amount is preferably 1 part by weight.
　すなわち、このように不溶性樹脂粉末の平均粒径Ｄ50や含有量を好ましい範囲とすることにより、防曇ガラスの作製に適した、比抵抗が３．４μΩ・ｃｍ以下で固着強度が１２Ｎ以上の導電性と固着力とが両立した導電性ペーストを得ることができる。 That is, by setting the average particle diameter D 50 and the content of the insoluble resin powder in a preferable range as described above, the specific resistance suitable for the production of the antifogging glass is 3.4 μΩ · cm or less and the fixing strength is 12 N or more. A conductive paste having both conductivity and adhesion can be obtained.
　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粉末を主成分（例えば、５０ｗｔ％以上）としたものを好んで使用することができる。例えば、Ａｇ粉末を主成分とし、Ｐｄ、Ｐｔ等の各種貴金属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. Usually, a powder containing Ag powder as a main component (for example, 50 wt% or more) is preferably used. be able to. For example, Ag powder may be the main component, and various precious metal powders such as Pd and Pt may be included as subcomponents.
　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。 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.
　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、機械的強度等を確保する観点からは、平均粒径Ｄ50は、０．１～５μｍが好ましい。導電性粉末の平均粒径Ｄ50が、０．１μｍ未満になるとペースト作製時に粘度が増加してペースト化が困難となり、一方、導電性粉末の平均粒径Ｄ50が５μｍを超えると、焼成時に導電性粉末間での所望の粒成長した結晶粒子の存在が不足し、機械的強度の低下を招くおそれがある。 The average particle diameter D 50 of the conductive powder is not particularly limited, but from the viewpoint of ensuring mechanical strength and the like, the average particle diameter D 50 is preferably 0.1 to 5 μm. When the average particle diameter D 50 of the conductive powder is less than 0.1 μm, the viscosity increases during paste preparation, making it difficult to make a paste. On the other hand, when the average particle diameter D 50 of the conductive powder exceeds 5 μm, The presence of crystal grains with desired grain growth between the conductive powders is insufficient, which may lead to a decrease in mechanical strength.
　また、導電性粉末の含有量も、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、ガラスフリットの含有量が相対的に増加することから、所望の導電性を確保するためには、線幅を広くしたり、導電膜を厚膜化する必要があり、コスト高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。 Further, the content of the conductive powder is not particularly limited, but is preferably 50 to 90 wt%. When the content of the conductive powder is less than 50 wt%, the content of the glass frit is relatively increased. Therefore, in order to ensure the desired conductivity, the line width is increased or the conductive film is made thicker. There is a risk of increasing costs. On the other hand, when the content of the conductive powder exceeds 90 wt%, the conductive powder becomes excessive and it may be difficult to form a paste. Accordingly, the content of the conductive powder is not particularly limited, but is preferably 50 to 90 wt%.
　また、ガラスフリットの組成は、特に限定されないが、焼結密度の低下や導電膜２の界面での封止不足を回避する観点からは、焼成温度で溶融し流動させる必要がある。そして、防曇ガラス等のガラス物品では、通常、５００～８００℃程度の温度で焼成されることから、軟化点が３５０～６００℃程度に組成調整されたガラスフリットを使用するのが好ましい。 Further, the composition of the glass frit is not particularly limited, but from the viewpoint of avoiding a decrease in the sintered density and insufficient sealing at the interface of the conductive film 2, it is necessary to melt and flow at the firing temperature. Since glass articles such as antifogging glass are usually fired at a temperature of about 500 to 800 ° C., it is preferable to use a glass frit whose composition is adjusted to a softening point of about 350 to 600 ° C.
　尚、ガラスフリットの構成成分については特に限定されるものではなく、Ｂｉ２Ｏ３、ＰｂＯ、ＳｉＯ２、Ｂ２Ｏ３、Ａｌ２Ｏ３、ＢａＯ、ＣａＯ、ＳｒＯ、ＺｎＯ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏ、Ｓｂ２Ｏ３、ＦｅＯ、ＣｕＯなどの各種酸化物から、軟化点や化学的耐久性を考慮して選定することができる。 Incidentally, there is no particular limitation on the components of glass frit, Bi 2 O 3, PbO, SiO 2, B 2 O 3, Al 2 O 3, BaO, CaO, SrO, ZnO, Na 2 O, K It can be selected from various oxides such as 2 O, Li 2 O, Sb 2 O 3 , FeO, and CuO in consideration of the softening point and chemical durability.
　また、ガラスフリットの平均粒径Ｄ50も、特に限定されないが、ガラス基板１と導電膜２との固着性や導電性ペーストの焼結性の観点からは、０．１～５．０μｍが好ましい。 Further, the average particle diameter D 50 of the glass frit is not particularly limited, but is preferably 0.1 to 5.0 μm from the viewpoint of the adhesion between the glass substrate 1 and the conductive film 2 and the sinterability of the conductive paste. .
　また、ガラスフリットの含有量も、特に限定されないが、ガラス基板１と導電膜２との固着性やリード線とのはんだ付け性を考慮すると、１．５～６．０ｗｔ％が好ましい。 Further, the content of the glass frit is not particularly limited, but is preferably 1.5 to 6.0 wt% in consideration of the adhesion between the glass substrate 1 and the conductive film 2 and the solderability with the lead wire.
　有機ビヒクルを構成する有機バインダと有機溶剤との比率も特に限定されるものではなく、通常は、例えば体積比率で、１～３：７～９となるように調製される。また、有機バインダとしては、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、有機溶剤としては、α―ターピネオール、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。 The ratio of the organic binder and the organic solvent constituting the organic vehicle is not particularly limited, and is usually prepared to have a volume ratio of 1 to 3: 7 to 9, for example. Moreover, as an organic binder, an ethyl cellulose resin, a nitrocellulose resin, an acrylic resin, an alkyd resin, or these combinations can be used, for example. As the organic solvent, α-terpineol, xylene, toluene, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate and the like can be used alone or in combination.
　次に、本発明の導電パターンの形成方法を含む上記防曇ガラスの製造方法を説明する。 Next, a method for producing the above antifogging glass including the method for forming a conductive pattern of the present invention will be described.
　まず、Ａｇ粉末等の導電性粉末、Ｂｉ－Ｂ－Ｓｉ系等のガラスフリット、有機ビヒクルに対し不溶性を有しかつ焼成処理で焼失するポリプロピレン樹脂等の不溶性樹脂粉末を用意する。 First, a conductive powder such as an Ag powder, a glass frit such as Bi—B—Si, and an insoluble resin powder such as a polypropylene resin that is insoluble in an organic vehicle and burned off by a baking treatment are prepared.
　また、有機溶剤に可溶なエチルセルロース樹脂等の有機バインダとα－ターピネオール等の有機溶剤とを所定比率に配合して有機ビヒクルを作製する。 Further, an organic vehicle is prepared by blending an organic binder such as ethyl cellulose resin soluble in an organic solvent and an organic solvent such as α-terpineol in a predetermined ratio.
　次いで、導電性粉末、ガラスフリット、及び不溶性樹脂粉末を有機ビヒクル中に投入し、三本ロールミル等で使用して分散・混練し、これにより導電性ペーストを作製する。 Next, the conductive powder, glass frit, and insoluble resin powder are put into an organic vehicle and dispersed and kneaded using a three-roll mill or the like, thereby producing a conductive paste.
　次いで、スクリーン印刷等の印刷法を使用し、ガラス基板１上に導電性ペーストを塗布し、１２０～１７０℃程度の温度で所定時間（例えば、１０分）乾燥し、乾燥膜４を得る。 Next, using a printing method such as screen printing, a conductive paste is applied on the glass substrate 1 and dried at a temperature of about 120 to 170 ° C. for a predetermined time (for example, 10 minutes) to obtain a dry film 4.
　次に、この乾燥膜４に５００～８００℃程度の焼成温度で所定時間（例えば、５分）焼成処理を施す。すると不溶性樹脂粉末が焼失し、該不溶性樹脂粉末の焼失跡には貫通孔を含む空隙が形成されると共に、ガラス基板１上には所定パターンの導電膜２及び集電電極３ａ～３ｂが形成され、これにより防曇ガラスが作製される。 Next, the dried film 4 is subjected to a baking treatment at a baking temperature of about 500 to 800 ° C. for a predetermined time (for example, 5 minutes). Then, the insoluble resin powder is burned out, and voids including through holes are formed in the burned-out trace of the insoluble resin powder, and a conductive film 2 and current collecting electrodes 3a to 3b having a predetermined pattern are formed on the glass substrate 1. Thus, an antifogging glass is produced.
　このように本導電パターンの形成方法は、導電性粉末と、ガラスフリットと、有機バインダと有機溶剤とからなる有機ビヒクルと、該有機ビヒクルに対し不溶性を有しかつ焼成処理で焼失する不溶性樹脂粉末とを用意する工程と、前記導電性粉末、前記ガラスフリット及び前記不溶性樹脂粉末を前記有機ビヒクル中で混練してペースト化し、導電性ペーストを作製する工程と、前記導電性ペーストを基板上に塗布して乾燥し、乾燥膜を作製する工程と、前記乾燥膜に焼成処理を施し、前記基板上に所定パターンの導電膜を形成すると同時に前記不溶性樹脂粉末を焼失させ、前記有機バインダの分解ガスを換気する空隙を前記不溶性樹脂粉末の焼失跡に形成する工程を含むので、前記空隙が有機バインダの分解ガスに対する換気孔となり、前記分解ガスが充満した空洞部が基板と導電膜との間に形成されるのを抑制することができる。そしてその結果、ガラス基板１と導電膜２との間の接触面積が増加し、基板と導電膜との固着力を向上させることができる。 As described above, the method for forming the conductive pattern includes a conductive powder, a glass frit, an organic vehicle composed of an organic binder and an organic solvent, and an insoluble resin powder that is insoluble in the organic vehicle and burns away in the baking treatment. Preparing the conductive powder, the glass frit and the insoluble resin powder in the organic vehicle to form a paste, and applying the conductive paste on the substrate. And drying to produce a dry film, and subjecting the dry film to a baking treatment to form a conductive film having a predetermined pattern on the substrate, and simultaneously burning off the insoluble resin powder, and decomposing the organic binder decomposition gas. Since the method includes a step of forming a void to be ventilated in the burned trace of the insoluble resin powder, the void becomes a ventilation hole for the decomposition gas of the organic binder, Cavity decomposition gas is filled can be prevented from being formed between the substrate and the conductive film. As a result, the contact area between the glass substrate 1 and the conductive film 2 increases, and the adhesion between the substrate and the conductive film can be improved.
　このようにガラス基板１と導電膜２との固着力が向上することから、導電膜２や端子電極３ａ、３ｂに引張応力が負荷されても容易には破断しない機械的強度の良好な防曇ガラスを得ることができる。 Thus, since the adhesive force between the glass substrate 1 and the conductive film 2 is improved, the anti-fogging has a good mechanical strength that does not easily break even when a tensile stress is applied to the conductive film 2 and the terminal electrodes 3a and 3b. Glass can be obtained.
　図７は、本発明に係るガラス物品の第２の実施の形態としてのアンテナ付きガラスの一例を示す要部断面図である。 FIG. 7 is a cross-sectional view of an essential part showing an example of glass with an antenna as a second embodiment of the glass article according to the present invention.
　このアンテナ付きガラスは、複数のガラス基板（第１及び第２のガラス基板１２、１３）の間にポリビニルアルコール樹脂等からなる中間膜１４が介在した合わせガラスとされ、耐衝撃性を考慮した構造となっている。 The glass with an antenna is a laminated glass in which an intermediate film 14 made of polyvinyl alcohol resin or the like is interposed between a plurality of glass substrates (first and second glass substrates 12 and 13), and has a structure in consideration of impact resistance. It has become.
　そして、第１のガラス基板１２の表面にはセラミック層１５が形成され、さらに該セラミック層１５の表面にはアンテナ機能を有する単線又は複数の配線からなる受信部と、該受信部に接続された矩形形状のはんだ付け部とを備えた導電膜１６が形成されている。また、受信部ははんだ付け部を介して接続端子に接続され、かつ該接続端子はリード線に接続されている。そして、このアンテナ付きガラスは、防曇ガラスと同様、例えば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。 Then, a ceramic layer 15 is formed on the surface of the first glass substrate 12, and further, a receiving unit composed of a single wire or a plurality of wirings having an antenna function is connected to the surface of the ceramic layer 15 and the receiving unit. A conductive film 16 having a rectangular soldering portion is formed. The receiving unit is connected to a connection terminal via a soldering unit, and the connection terminal is connected to a lead wire. And this glass with an antenna is equipped as window glass for vehicles, such as a car, for example like anti-fog glass, receives the electric wave from the outside of a car, and is used for a radio and a television.
　このアンテナ付きガラスは以下のようにして作製される。 This glass with an antenna is manufactured as follows.
　すなわち、ガラスフリットを含有したセラミック材料を主成分とするセラミックペーストを第１のガラス基板１２上に塗布し、乾燥させる。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、その後、セラミックペーストと導電性ペーストとを同時焼成して導電膜１６を形成する。次いで、中間膜１４が第１のガラス基板１２と第２のガラス基板１３とが狭持されるように接着剤を介して貼付し、これによりアンテナ付きガラスが作製される。 That is, a ceramic paste mainly composed of a ceramic material containing glass frit is applied on the first glass substrate 12 and dried. Next, the conductive paste of the present invention is applied on the ceramic paste so as to have a predetermined antenna pattern, dried, and then the ceramic paste and the conductive paste are simultaneously fired to form the conductive film 16. Next, the intermediate film 14 is pasted through an adhesive so that the first glass substrate 12 and the second glass substrate 13 are sandwiched, thereby producing a glass with an antenna.
　このように本アンテナ付きガラスにおいても、本発明の導電性ペーストを使用して導電膜１６を形成することにより、第１の実施の形態と同様、低比抵抗を確保しつつ固着力が向上した良好な機械的強度を有するアンテナ付きガラスを得ることができる。 Thus, also in this glass with an antenna, by forming the conductive film 16 using the conductive paste of the present invention, as in the first embodiment, the fixing force was improved while ensuring a low specific resistance. An antenna-attached glass having good mechanical strength can be obtained.
　尚、本発明は上記実施の形態に限定されるものではない。上記導電パターンの形成方法では、基板としてガラス基板１を使用したが、セラミック基板等、その他の基板類についても適用可能であるのはいうまでもない。 The present invention is not limited to the above embodiment. In the method for forming a conductive pattern, the glass substrate 1 is used as a substrate, but it goes without saying that the present invention can also be applied to other substrates such as a ceramic substrate.
　また、防曇ガラスやアンテナ付きガラス等のガラス物品は、車両等のフロント部又はリア部に装備されることから、導電膜の形成部分を暗色に着色させて意匠的効果を発揮するケイ化モリブデンや防眩作用を有するクロム酸化物や銅酸化物等の黒色系顔料を導電性ペーストに添加するのも好ましい。 In addition, glass articles such as antifogging glass and glass with an antenna are mounted on the front or rear part of a vehicle or the like, so that the molybdenum silicide that exhibits a design effect by coloring the conductive film forming portion in a dark color. It is also preferable to add a black pigment such as chromium oxide or copper oxide having antiglare action to the conductive paste.
　また、本発明は、特性に影響を与えない範囲で、必要に応じ各種無機成分を含有していてもよい。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, the present invention may contain various inorganic components as necessary within a range not affecting the characteristics. For example, Zr, P, V, Ce, Nb, Ta, W, Pd, Ag, Ru, Sn, In, Y, Dy, La, or the like may be contained. In addition, the form of inclusion is not particularly limited, and is appropriately selected from oxides, hydroxides, peroxides, halides, carbonates, nitrates, phosphates, sulfates, fluorides, organometallic compounds, and the like. 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 di-2-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, etc. may be added.
　次に、本発明の実施例を具体的に説明する。 Next, specific examples of the present invention will be described.
〔試料の作製〕
　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系ガラスフリット、平均粒径が１μｍのケイ化モリブデン粉末、及び平均粒径が１～３０μｍのポリプロピレン樹脂粉末（不溶性樹脂粉末）を用意した。 [Sample preparation]
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-based glass frit, the average particle size of 1μm molybdenum silicide powder, and the average A polypropylene resin powder (insoluble resin powder) having a particle size of 1 to 30 μm was prepared.
　尚、平均粒径Ｄ50はレーザー回析式粒度分布測定器で測定した。 The average particle diameter D 50 was measured by a laser diffraction particle size distribution analyzer.
　また、有機ビヒクルを以下の方法で作製した。すなわち、有機バインダとしてのエチルセルロース樹脂が１０ｗｔ％、有機溶剤としてのα－ターピネオールが９０ｗｔ％となるようにエチルセルロース樹脂とα－ターピネオールとを混合し、有機ビヒクルを作製した。 Also, an organic vehicle was produced by the following method. That is, the organic cellulose was prepared by mixing the ethyl cellulose resin and α-terpineol so that the ethyl cellulose resin as the organic binder was 10 wt% and the α-terpineol as the organic solvent was 90 wt%.
　次に、Ａｇ粉末：８０ｗｔ％、ガラスフリット５ｗｔ％、ケイ化モリブデン粉末：０．５ｗｔ％、有機ビヒクル：１４．５ｗｔ％となるように調合し、さらにＡｇ粉末１００重量部に対しポリプロピレン樹脂粉末が０～２重量部となるようにポリプロピレン樹脂粉末を添加し、プラネタリーミキサで混合した後に、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, Ag powder: 80 wt%, glass frit 5 wt%, molybdenum silicide powder: 0.5 wt%, organic vehicle: 14.5 wt%, and further, polypropylene resin powder is added to 100 parts by weight of Ag powder. Polypropylene resin powder was added so as to be 0-2 parts by weight, mixed with a planetary mixer, then dispersed with a three-roll mill and kneaded to prepare conductive pastes of sample numbers 1-9.
〔試料の評価〕
　縦：７６ｍｍ、横：２６ｍｍ、厚み：１．４ｍｍのスライドガラスを用意し、上記導電性ペーストを使用し、ライン全長Ｌ：１００ｍｍ、線幅Ｗ：０．５ｍｍとなるようにスクリーン印刷し、スライドガラス上に回路パターンを形成し、さらに両端部に縦：２ｍｍ、横：２ｍｍの集電用パターンを形成し、回路パターンと集電用パターンとからなる乾燥膜を得た。次いで、このスライドガラスを１５０℃の温度で１０分間乾燥した後、最高温度６００℃で５分間焼成し、乾燥膜を乾燥させてスライドガラスの表面に導電膜及び集電電極が形成された試料番号１～９の試料を作製した。 (Sample evaluation)
Prepare slide glass with length: 76 mm, width: 26 mm, thickness: 1.4 mm, use the above conductive paste, screen print so that line total length L: 100 mm, line width W: 0.5 mm, slide A circuit pattern was formed on the glass, and a current collecting pattern of 2 mm in length and 2 mm in width was formed on both ends to obtain a dry film comprising the circuit pattern and the current collecting pattern. Next, this slide glass was dried at a temperature of 150 ° C. for 10 minutes, then baked at a maximum temperature of 600 ° C. for 5 minutes, the dried film was dried, and a sample number in which a conductive film and a collecting electrode were formed on the surface of the slide glass Samples 1 to 9 were prepared.
　次に、導電膜の両端に形成された集電電極の抵抗値をデジタル抵抗計で測定した。次いで、導電膜の断面積を接触式表面粗さ計で測定し、該断面積とライン全長Ｌ（＝１００ｍｍ）とから比抵抗を算出した。 Next, the resistance value of the collecting electrode formed on both ends of the conductive film was measured with a digital resistance meter. Next, the cross-sectional area of the conductive film was measured with a contact-type surface roughness meter, and the specific resistance was calculated from the cross-sectional area and the line total length L (= 100 mm).
　また、ＳｎめっきされたＣｕ製のリード線を集電電極にはんだ付けして接合し、該リード線を一定速度で引っ張り、剥離するまでの最大荷重を測定し、電極の固着強度を求めた。 Also, a Sn-plated Cu lead wire was soldered and joined to the current collecting electrode, the lead wire was pulled at a constant speed, and the maximum load until peeling was measured to determine the fixing strength of the electrode.
　表１は、試料番号１～９で使用したポリプロピレン樹脂粉末の平均粒径、Ａｇ１００重量部に対する含有量、及び測定結果（比抵抗、固着強度）を示している。 Table 1 shows the average particle diameter of polypropylene resin powders used in sample numbers 1 to 9, the content with respect to 100 parts by weight of Ag, and the measurement results (specific resistance, adhesion strength).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　試料番号１は、導電性ペースト中にポリプロピレン樹脂粉末が含有されていないため、比抵抗は２．６μΩ・ｃｍと良好であるが、固着強度が１１Ｎと低く、スライドガラスと導電膜との間の固着力に劣ることが分かった。 Sample No. 1 does not contain polypropylene resin powder in the conductive paste, so the specific resistance is as good as 2.6 μΩ · cm, but the adhesion strength is as low as 11 N, and it is between the slide glass and the conductive film. It was found that the adhesive strength was inferior.
　これに対し試料番号２～９は、固着強度が１２Ｎ以上であり、試料番号１に比べて固着力が向上していることが分かった。 On the other hand, Sample Nos. 2 to 9 have an adhesion strength of 12 N or more, and it was found that the adhesion strength was improved compared to Sample No. 1.
　ただし、試料番号２は、試料番号１に比べると固着力は改善されているものの固着強度は１２Ｎであり、改善効果は小さかった。これはポリプロピレン樹脂粉末の平均粒径Ｄ50が１μｍと小さいため、ポリプロピレン樹脂粉末が焼成により焼失しても換気孔として機能するような大きな空隙を形成することができず、分解ガスが導電膜を若干押し上げ、導電膜とスライドガラスとの接触面積が減少したためと思われる。 However, Sample No. 2 had an improved fixing strength compared to Sample No. 1, but the fixing strength was 12 N, and the improvement effect was small. This is because the average particle diameter D 50 of the polypropylene resin powder as small as 1 [mu] m, it is impossible to polypropylene resin powder be removed by firing to form a large void that functions as a ventilation hole, decomposition gas conductive film This is probably because the contact area between the conductive film and the slide glass decreased.
　また、試料番号６は、固着強度が１６Ｎであり、２０Ｎ以下となって改善効果が小さかった。これはポリプロピレン樹脂粉末の平均粒径Ｄ50が３０μｍと大きいため、導電性ペースト中のポリプロピレン樹脂粉末の個数が少なく、焼成により、空隙が形成されても該空隙の存在密度が低下し、このため導電膜とスライドガラスとの接触面積が減少したためと思われる。 Sample No. 6 had a fixing strength of 16N and was less than 20N, and the improvement effect was small. This is because the average particle diameter D 50 of the polypropylene resin powder is as large as 30 μm, so the number of polypropylene resin powders in the conductive paste is small, and even if voids are formed by firing, the density of the voids decreases. This is probably because the contact area between the conductive film and the slide glass decreased.
　一方、試料番号９は、固着強度が２４Ｎと良好であったものの、比抵抗が４．３μΩ・ｃｍと大きくなった。これはポリプロピレン樹脂粉末の含有量がＡｇ１００重量部に対し２重量部と多く、このため導電性ペースト中のＡｇ粉末の含有量が相対的に少なくなり、比抵抗が増加したものと思われる。 On the other hand, Sample No. 9 had good adhesion strength of 24 N, but the specific resistance increased to 4.3 μΩ · cm. This is because the content of the polypropylene resin powder is as large as 2 parts by weight with respect to 100 parts by weight of Ag. Therefore, the content of Ag powder in the conductive paste is relatively decreased, and it is considered that the specific resistance is increased.
　これに対し試料番号３～５、７、８は、ポリプロピレン樹脂粉末の平均粒径Ｄ50が３～１５μｍ、その含有量もＡｇ粉末１００重量部に対し０．２～１．０重量部といずれも好ましい範囲にあるので、比抵抗は３．４μΩ・ｃｍ以下で固着強度は２０～２５Ｎとなり、比抵抗と固着力のいずれも良好な導電性ペーストが得られることが分かった。 In contrast, Sample Nos. 3 to 5, 7, and 8 have an average particle diameter D 50 of polypropylene resin powder of 3 to 15 μm and a content of 0.2 to 1.0 part by weight with respect to 100 parts by weight of Ag powder. Therefore, the specific resistance was 3.4 μΩ · cm or less, the fixing strength was 20 to 25 N, and it was found that a conductive paste with good specific resistance and fixing strength can be obtained.
　以上より所望の比抵抗を確保しつつ固着力を向上させるためには、有機ビヒクルに対し不溶性を有し焼成処理で焼失するポリプロピレン樹脂等の不溶性樹脂粉末を導電性ペースト中に含有させるのが重要であり、また、比抵抗（導電性）及び固着強度（固着力）が両立したより良好な特性を得るためには、不溶性樹脂粉末の平均粒径Ｄ50は３～１５μｍ、その含有量は導電性粉末１００重量部に対し０．２～１．０重量部とするのが効果的であることが分かった。 From the above, in order to improve the adhesion while securing the desired specific resistance, it is important to include insoluble resin powder such as polypropylene resin that is insoluble in the organic vehicle and burned off by the baking treatment in the conductive paste. In addition, in order to obtain better characteristics in which specific resistance (conductivity) and fixing strength (adhesion strength) are compatible, the average particle diameter D 50 of the insoluble resin powder is 3 to 15 μm, and the content thereof is conductive. It was found that 0.2 to 1.0 parts by weight is effective with respect to 100 parts by weight of the conductive powder.
　所望の比抵抗を確保しつつ基板との固着力が良好な車両用防曇ガラスやアンテナ付きガラス等のガラス物品に好適に利用できる導電性ペーストを実現する。 A conductive paste that can be suitably used for glass articles such as an anti-fogging glass for vehicles and a glass with an antenna having good adhesion to the substrate while ensuring a desired specific resistance is realized.
１　ガラス基板
２　導電膜
４　乾燥膜
５　導電性粉末
６　ガラスフリット
７　不溶性樹脂粉末
８　有機バインダ
１２　第１のガラス基板
１６　導電膜 DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Conductive film 4 Dry film 5 Conductive powder 6 Glass frit 7 Insoluble resin powder 8 Organic binder 12 First glass substrate 16 Conductive film

Claims (9)

  1. 　少なくとも導電性粉末と、ガラスフリットと、有機バインダと有機溶剤とからなる有機ビヒクルとを含有した導電性ペーストであって、
    　前記有機ビヒクルに対し不溶性を有しかつ焼成処理で焼失する樹脂粉末を含有していることを特徴とする導電性ペースト。     A conductive paste containing at least a conductive powder, a glass frit, an organic vehicle composed of an organic binder and an organic solvent,
    A conductive paste characterized by containing a resin powder that is insoluble in the organic vehicle and burns away by a baking treatment.
  2. 　前記樹脂粉末が焼失する温度は５００～８００℃である請求項１記載の導電性ペースト The conductive paste according to claim 1, wherein a temperature at which the resin powder burns out is 500 to 800 ° C.
  3. 　前記樹脂粉末は、平均粒径が３～１５μｍであることを特徴とする請求項１又は請求項２記載の導電性ペースト。 3. The conductive paste according to claim 1, wherein the resin powder has an average particle size of 3 to 15 μm.
  4. 　前記樹脂粉末の含有量は、前記導電性粉末１００重量部に対し０．２～１重量部であることを特徴とする請求項１乃至請求項３のいずれかに記載の導電性ペースト。 4. The conductive paste according to claim 1, wherein the content of the resin powder is 0.2 to 1 part by weight with respect to 100 parts by weight of the conductive powder.
  5. 　前記樹脂粉末は、ポリオレフィン、ポリメタクリル酸エステル、及びポリアクリル酸エステルの群から選択された少なくとも１種を含むことを特徴とする請求項１乃至請求項４のいずれかに記載の導電性ペースト。 The conductive paste according to any one of claims 1 to 4, wherein the resin powder includes at least one selected from the group consisting of polyolefin, polymethacrylic acid ester, and polyacrylic acid ester.
  6. 　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乃至請求項５のいずれかに記載の導電性ペースト。 6. The conductive paste according to claim 1, wherein the conductive powder contains Ag as a main component.
  7. 　導電性粉末と、ガラスフリットと、有機バインダと有機溶剤とからなる有機ビヒクルと、該有機ビヒクルに対して不溶性を有しかつ焼成処理で焼失する樹脂粉末とを含む導電性ペーストを基板上に塗布する工程と、
    　前記基板上に塗布された前記導電性ペーストに焼成処理を施し、前記基板上に所定パターンの導電膜を形成すると同時に前記樹脂粉末を焼失させ、前記導電膜を貫通する貫通孔を前記樹脂粉末の焼失跡に形成する工程とを含むことを特徴とする導電パターンの形成方法。     A conductive paste including a conductive powder, a glass frit, an organic vehicle composed of an organic binder and an organic solvent, and a resin powder that is insoluble in the organic vehicle and burns away by a baking treatment is applied onto a substrate. And a process of
    The conductive paste applied on the substrate is baked to form a conductive film having a predetermined pattern on the substrate, and at the same time, the resin powder is burned off, and a through-hole penetrating the conductive film is formed in the resin powder. And a step of forming a burnt trace.
  8. 　焼成後の前記導電膜の比抵抗が、３．４μΩ・ｃｍ以下であることを特徴とする請求項７記載の導電パターンの形成方法。 The method for forming a conductive pattern according to claim 7, wherein the specific resistance of the conductive film after firing is 3.4 μΩ · cm or less.
  9. 　ガラス基板上に導電膜が形成され、導電膜上に接続端子が接合されるガラス物品であって、
    　前記導電膜は、請求項１乃至請求項６のいずれかに記載の導電性ペーストの焼結体で形成されていることを特徴とするガラス物品。     A glass article in which a conductive film is formed on a glass substrate and a connection terminal is bonded on the conductive film,
    The said electrically conductive film is formed with the sintered compact of the electrically conductive paste in any one of Claims 1 thru | or 6. The glass article characterized by the above-mentioned.
PCT/JP2017/002480 2016-03-18 2017-01-25 Conductive paste, method for forming conductive pattern, and glass article WO2017159055A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016055274 2016-03-18
JP2016-055274 2016-03-18

Publications (1)

Publication Number Publication Date
WO2017159055A1 true WO2017159055A1 (en) 2017-09-21

Family

ID=59850656

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/002480 WO2017159055A1 (en) 2016-03-18 2017-01-25 Conductive paste, method for forming conductive pattern, and glass article

Country Status (1)

Country Link
WO (1) WO2017159055A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113873788A (en) * 2021-10-09 2021-12-31 深圳市百柔新材料技术有限公司 Preparation method of multilayer glass substrate, glass substrate and Mini-LED glass substrate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10172345A (en) * 1996-12-04 1998-06-26 Murata Mfg Co Ltd Conductive paste and manufacture of ceramic substrate using the same
WO2005048667A1 (en) * 2003-11-14 2005-05-26 Murata Manufacturing Co., Ltd. Conductive paste and multilayer ceramic substrate
JP2005191310A (en) * 2003-12-25 2005-07-14 Kyocera Corp Conductive paste for forming via conductor and manufacturing method of circuit board
JP2009245704A (en) * 2008-03-31 2009-10-22 Toray Ind Inc Photosensitive conductive paste composition, electrode circuit, and plasma display panel
WO2010116851A1 (en) * 2009-04-10 2010-10-14 株式会社村田製作所 Charged powder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10172345A (en) * 1996-12-04 1998-06-26 Murata Mfg Co Ltd Conductive paste and manufacture of ceramic substrate using the same
WO2005048667A1 (en) * 2003-11-14 2005-05-26 Murata Manufacturing Co., Ltd. Conductive paste and multilayer ceramic substrate
JP2005191310A (en) * 2003-12-25 2005-07-14 Kyocera Corp Conductive paste for forming via conductor and manufacturing method of circuit board
JP2009245704A (en) * 2008-03-31 2009-10-22 Toray Ind Inc Photosensitive conductive paste composition, electrode circuit, and plasma display panel
WO2010116851A1 (en) * 2009-04-10 2010-10-14 株式会社村田製作所 Charged powder

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113873788A (en) * 2021-10-09 2021-12-31 深圳市百柔新材料技术有限公司 Preparation method of multilayer glass substrate, glass substrate and Mini-LED glass substrate

Similar Documents

Publication Publication Date Title
KR100798255B1 (en) Electroconductive thick film composition, electrode, and solar cell formed therefrom
EP3026674B1 (en) Composition for forming solar cell electrode, and electrode produced from composition
KR20130109071A (en) Low silver content paste composition and method of making a conductive film therefrom
CN109844871B (en) Resistor paste, resistor, electronic component, and method for producing lead-free resistor
KR20120032568A (en) Paste composition and solar cell element using same
US10052690B2 (en) Conductive paste and glass article
US20130327394A1 (en) Electroconductive Paste and Solar Cell
WO2017159055A1 (en) Conductive paste, method for forming conductive pattern, and glass article
KR101138246B1 (en) Manufacturing method of paste composition having low temperature coefficient resistance for resistor, thick film resistor and manufacturing method of the resistor
JP6260882B2 (en) Conductive paste and glass article
JP2011233548A (en) Conductive paste and solar cell
JP2013243279A (en) Conductive paste for forming solar cell electrode
KR20130107767A (en) Electrode paste for solar cell
JP5215914B2 (en) Resistor film manufacturing method, resistor film, and resistor
WO2022255117A1 (en) Electrically conductive paste and glass article
JP6200128B2 (en) Conductive paste for solar cell electrode formation
WO2019064738A1 (en) Conductive paste, glass article, and method for producing glass article
WO2017006714A1 (en) Electroconductive paste, and glass article
WO2019073637A1 (en) Conductive paste, glass article, and method for manufacturing glass article
KR20200123643A (en) Glass frit composition for forming solar cell electrode, and paste composition including the same
KR101166709B1 (en) Manufacturing method of paste composite for resistor, thick film resistor and manufacturing method of the resistor
JPH03176905A (en) Conductive paste
WO2021221175A1 (en) Thick film resistor paste, thick film resistor, and electronic component
WO2021221174A1 (en) Thick film resistor paste, thick film resistor, and electronic component
JP6338200B2 (en) Conductive paste and pattern forming method

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17766063

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17766063

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP