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

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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
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Prior art keywords
conductive
glass
resin powder
conductive paste
powder
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PCT/JP2017/002480
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French (fr)
Japanese (ja)
Inventor
伸一 次本
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株式会社村田製作所
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Priority to JP2016055274 priority Critical
Priority to JP2016-055274 priority
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

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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C03C17/04Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01QANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00Details of, or arrangements associated with, antennas
    • H01Q1/27Adaptation for use in or on movable bodies
    • H01Q1/32Adaptation for use in or on road or rail vehicles
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern

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

Conductive paste, a method for forming a conductive pattern, and the glass article

The present invention is a method of forming a conductive paste, conductive patterns, and to a glass article, more particularly, electrically conductive to form a heat ray or an antenna pattern or the like of the anti-fogging annexed to vehicle glazing such as automobiles paste, a method for forming a conductive pattern using a conductive paste, and conductive Bae - relates to a glass article such as anti-fogging glass or glass with an antenna using strike.

Conventionally, the window glass of a vehicle such as an automobile, a glass article of glass with an antenna or the like for receiving radio waves from anti-fogging glass or exterior decor heat rays for defogging is used. These glass article, for example in anti-fogging glass, typically, to form a collecting pattern at both end portions of the circuit pattern to form a circuit pattern by applying a conductive paste on a glass substrate made of a material, and dried It has been prepared and fired processing after. A conductive film of a predetermined pattern causes fixed on a glass substrate by this, the connection terminal to the collector electrode formed on both end portions of the conductive film soldered, the connection terminal connected to the power supply terminal further via leads ing.

Then, this kind of the conductive paste is also conventionally have been actively studied and developed.

For example, Patent Document 1, the finely divided particles of conductive material, lead borate, lead silicate, silicate compounds such as lead borosilicate, oxides or oxide precursors and mixtures thereof of a metal an inorganic binder selected from the group consisting of, a conductive composition comprising a liquid vehicle to disperse them, total composition comprises solids of from 50 to 95 mass%, the inorganic binder, the less than 1.0% of the conductive composition of the total solids of the composition have been proposed.

Patent Document 1 includes 50 to 95 mass% solids, and by reducing the content of the inorganic binder (glass frit) to less than 1.0% of the total solids, crack enamel coating the substrate it is possible to maintain the adhesive force without even occurs, is set to thereby attempt is made to balance the conductivity and adhesion.

JP 2004-311438 JP (claim 2, paragraphs [0009], [0019] ~ [0021], Table 2, etc.)

In Patent Document 1, by reducing the content of the inorganic binder in the conductive composition in the specific resistance was low, and thereby improve the conductivity. However, the content of the inorganic binder is less and less than 1.0%, the poor adhesive force between Accordingly conductive film and the glass substrate.

The present invention has been made in view of such circumstances, a conductive paste, conductive paste capable of ensuring good bonding strength between the substrate while maintaining the desired low resistivity and to provide the method for forming a conductive pattern, and a glass article such as glass with anti-fogging glass or the antenna using the conductive paste.

Conductive paste used to make the glass article of anti-fogging glass or antenna with glass for a vehicle, usually, the conductive powder, glass frit, and contains an organic vehicle composed of an organic binder and an organic solvent there. Further, the glass article of this kind, as described in the Background of the Invention, although the conductive film and the collector electrode is made by baking of a conductive paste, such conductive paste, conductive and substrate fixing force against is requested to be good.

In order to obtain good electrical conductivity is as much as possible necessary to suppress the specific resistance of the conductive film, it is desirable to form a dense conductive film therefor.

The present inventors, using a conductive paste from such viewpoint a conductive film is formed on the glass substrate were intense study, decomposition gas of the organic binder generated during firing trapped inside conductive film, Furthermore this decomposition gas was found to form a cavity gathered interface of the conductive film and the glass substrate. As a result of cavity decomposition gas is filled is formed a large number at the interface between the glass substrate, a conductive film and reduces the contact area with the glass substrate, the fixing strength is decreased between Accordingly glass substrate and the conductive film it was found to be.

The present inventor has was further intensive studying has insoluble and resin powder destroyed by baking treatment (hereinafter, referred to as "insoluble resin powder".) To the organic vehicle is contained in the conductive paste by performing the calcination treatment Te, voids formed burned traces of insoluble resin powder functions as the ventilation hole of the cracked gas as described above, thereby it is possible to suppress the formation of cavities that are filled with cracked gas, It was obtained a finding that it is possible to improve the fixing strength between the substrate while ensuring a low specific resistance.

The present invention was made based on such findings, the conductive paste according to the present invention, the conductive containing at least a conductive powder, a glass frit, an organic vehicle composed of an organic binder and an organic solvent a sexual paste is characterized in that it contains an insoluble resin powder to said organic vehicle is burned off in a and calcined insoluble.

Here, "having insoluble in organic vehicle", be stirred by adding a resin powder in an organic vehicle, it means that the solid undissolved which does not dissolve in the organic vehicle remains, organic not only do not completely insoluble in an organic solvent vehicle, including the case of poorly soluble solids undissolved those slightly soluble in organic solvent remains.

In the conductive paste of the present invention, the temperature at which the insoluble resin powder is burned is preferably 500 ~ 800 ° C..

In the conductive paste of the present invention, the insoluble resin powder is preferably an average particle diameter of 3 ~ 15 [mu] m.

In this case, by adjusting the content of the insoluble resin powder, the ratio can suppress an increase in resistance, thus to obtain a conductive paste adhesive force of the conductive and the substrate and has both effectively it can.

In the present invention, the average particle size cumulative cumulative distribution 50% particle size, i.e., a median diameter (hereinafter, referred to as "average particle diameter D 50".) Refers to.

The conductive paste of the present invention, the content of the insoluble resin powder, more preferably from 0.2 to 1 part by weight with respect to the 100 parts by weight of the conductive powder.

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 it is possible to obtain.

The conductive paste of the present invention, the insoluble resin powder, polyolefin, polymethacrylate, and contains at least one selected from the group of polyacrylic acid esters preferred.

Such insoluble resin powder from easily be destroyed by a and firing processes insoluble in the organic vehicle, it may be used in favor in the conductive paste of the present invention.

The conductive paste of the present invention, the conductive powder is, preferably has a main component Ag.

The formation method of the conductive pattern according to the present invention includes a conductive powder, burned down a glass frit, an organic vehicle composed of an organic binder and an organic solvent, at a and calcined insoluble against organic vehicle a step of applying a conductive paste containing a resin powder on a substrate, subjected to a firing treatment to the conductive paste coated on the substrate, wherein the simultaneously forming a conductive film in a predetermined pattern on a substrate resin powder is burned out, it is characterized by comprising a step of forming a through hole penetrating through the conductive film burned traces of the resin powder.

Thus since the through-holes for ventilating the decomposition gas of the organic binder is formed on the burned traces of insoluble resin powder, the through hole becomes the ventilation holes for the decomposition gas of the organic binder, the cavity in which the cracked gas is filled a substrate it can be suppressed from being formed between the conductive film. Thus, the blister between the substrate and the conductive film (swelling) without also being formed, since the contact area of ​​the interface is increased, thereby improving the fixing strength between the substrate and the conductive film.

The formation method of the conductive pattern of the present invention, the specific resistance of the conductive film after firing, preferably not more than 3.4μΩ · cm.

This makes it possible to obtain a good conductive layer of the conductive by becoming not low resistivity adhesive force only can the fixing strength and conductivity to obtain a desired conductive pattern compatible.

The glass article according to the present invention, is formed a conductive film on a glass substrate, a glass article connection terminal is joined on the conductive film, the conductive film is electrically conductive as described above either It is characterized in that it is formed of a sintered body of the paste.

Thereby fixing strength between the glass substrate and the conductive film while securing the conductivity obtain good various glass articles such as excellent anti-fogging glass or the antenna with glass in mechanical strength.

According to the conductive paste of the present invention comprises at least a conductive powder, a glass frit, a conductive paste containing an organic vehicle composed of an organic binder and an organic solvent, the insoluble in the organic vehicle and because it contains an insoluble resin powder destroyed by burning treatment, voids such as through-holes through the burned to trace the conductive film of the insoluble resin powder was destroyed by firing are formed. Then, the gap functions as the ventilation hole of the decomposition gas generated by thermal decomposition of the organic binder, and thereby possible to suppress the generation of the cavities at the interface due to the generation of the decomposed gas.

Thus, even if obtained by firing the conductive paste of the present invention, it is possible to suppress the generation of cavity decomposition gas of the organic binder is filled, it is possible to contact area with the substrate increases, the desired low resistivity it is possible to obtain a suitable conductive paste for making glass article fixing strength is improved between the substrate while securing the.

Further, according to the method for forming a conductive pattern of the present invention, the ventilation holes because the through hole for ventilating the decomposition gas of the organic binder is formed on the burned traces of insoluble resin powder, the through holes for the decomposition gas of the organic binder next, the cavity in which the cracked gas is filled can be prevented from being formed between the substrate and the conductive film. And consequently, the contact area between the substrate and the conductive film is increased, thereby improving the fixing strength between the substrate and the conductive film.

Further, according to the glass article of the present invention, is formed a conductive film on a glass substrate, a glass article connection terminal is joined on the conductive film, the conductive film, conductive any of the above-described because it is formed of a sintered body of sexual paste, while securing the conductivity can be improved fixing strength between the glass substrate and the conductive film, the tensile conductive film stress is loaded inhibited from breaking various glass articles such as anti-fogging glass or the antenna with glass having a good mechanical strength to be able to obtain.

An embodiment of the anti-fogging glass as a glass article which is manufactured using the conductive paste according to the present invention (first embodiment) is a front view showing. It is an A-A sectional view taken along line of FIG. An example of a dry film is a cross-sectional view schematically showing. An example of the sintered body is a sectional view schematically showing. Another example of a dry film is a cross-sectional view schematically showing. Another example of the sintered body is a sectional view schematically showing. The antenna with glass as a second embodiment of a glass article according to the present invention is a cross-sectional view schematically showing.

Then, detailing an embodiment of the present invention.

Figure 1 is a front view showing an embodiment of anti-fogging glass as a glass article produced by using the conductive paste according to the present invention, FIG 2 is A-A sectional view taken along line of FIG. 1 it is.

The anti-fogging glass, together with the conductive film 2 of the thinning-thinned linear with a predetermined interval on the surface of the glass substrate 1 is formed with a plurality of parallel shape, the both end portions of the conductive film 2 collecting denden poles 3a, 3b are formed, collector electrode 3a, the 3b are joined connection terminal (not shown) is soldered.

That is, the anti-fogging glass is at both ends of the circuit pattern with the circuit pattern electrically conductive paste on the glass substrate 1 is coated is formed is formed collector pattern, the conductive film 2 in a predetermined pattern by baking treatment and collector electrodes 3a, 3b are formed. Thus the conductive film 2 and the collector electrode 3a, 3b is formed by a sintered body of an electroconductive paste. Then, the conductive film 2 is fixed on the glass substrate 1, the collector electrode 3a, the 3b connection terminal (not shown) is soldered, and is connected to the lead wire through the connection terminal.

The anti-fogging glass is, for example, implemented as a front glass or a rear glass of a vehicle such as an automobile, collector electrodes 3a, through 3b is powered from the power supply terminal to the conductive film 2, the window glass by heating the conductive film 2 anti-fog can be carried out.

Next, it will be described in detail conductive paste for forming the above-mentioned conductive film 2 and the collector electrode 3a, the 3b.

This conductive paste is a conductive powder, a glass frit, and contains an organic vehicle. The organic vehicle is composed of an organic binder and an organic solvent, soluble organic binder is dissolved in an organic solvent in an organic solvent.

Further, this conductive paste, the organic vehicle to have an insoluble and are contained insoluble resin powder destroyed by calcination process, thereby the glass substrate 1 while maintaining a desired low resistivity conductive film thereby improving the adherence of two.

Here, "having insoluble in organic vehicle", be stirred by adding a resin powder in an organic vehicle, it means that the solid undissolved which does not dissolve in the organic vehicle remains, organic not only insoluble not at all dissolved in the vehicle, including the case of poorly soluble solids undissolved those slightly soluble in the organic vehicle remains.

After this kind of the conductive paste was applied and dried on a glass substrate 1, when the firing process, but the organic binder is burned off accompanied by pyrolysis, conduction low resistivity in order to ensure good electrical conductivity to obtain a film 2, it is necessary to densify the conductive film 2.

However, an attempt to form a dense conductive film 2, the decomposition gas of CO 2 or the like which is produced by pyrolysis of the organic binder is confined to the inside of the conductive film 2, and this decomposition gas and the glass substrate 1 conductive film concentrated on the interface between the 2, to form a cavity. Thus, at the interface increases occupation ratio of cavity decomposition gas is filled, and thus reduces the contact area between the glass substrate 1 and the conductive film 2, leads to a decrease in the fixing strength of the conductive film 2 to the glass substrate 1 fear there is.

Therefore, in this embodiment, the insoluble resin powder destroyed by a and firing processes insoluble in the organic vehicle is contained in the conductive paste, a void burned traces and thereby to burn off insoluble resin powder during firing formed, by functioning the void as the ventilation hole of the decomposition gas, cavity decomposition gas is filled is prevented from remaining in the interface between the glass substrate 1 and the conductive film 2.

Thus, the present conductive paste includes at least a conductive powder, a glass frit, a conductive paste containing an organic vehicle, an insoluble resin powder to said organic vehicle is burned off in a and calcined insoluble because it contains, the firing traces of insoluble resin powder was destroyed by firing voids such as through holes passing through the conductive film is formed. Then, the gap acts as a ventilation hole of the decomposition gas generated by thermal decomposition of the organic binder can suppress the formation of cavities at the interface of decomposition gas is filled. This increases the contact area between the glass substrate 1 and the conductive film 2, it is possible to improve the fixing strength between the glass substrate 1 while maintaining the desired resistivity. Therefore, it is possible to suppress the conductive film 2 and the collector electrode 3a, the tensile stress from the outside from the glass substrate be loaded 3b for peeling. Particularly collector electrodes 3a leads are connected through a connecting terminal, which is preferable tensile stress from the outside is easily loaded 3b.

Such insoluble resin powder has and firing processes insoluble in an organic vehicle as described above, i.e. the firing temperature (e.g., 500 ~ 800 ° C.) when the resin destroyed by, the present invention is not particularly limited no, but typically, polyolefins such as polypropylene, polymethacrylate, preferring resin powder containing at least one selected from the group of polyacrylic acid esters may be used.

Then, detailing the reasons for this conductive paste was contained insoluble resin powder.

Figure 3 is an example of a state before firing a cross-sectional view schematically showing Fig. 4, an example of a state after firing shows a cross-sectional view schematically showing.

In other words, before firing, as shown in FIG. 3, since the surface of the glass substrate 1 is a conductive paste is applied and dried, a dry film 4 is formed on the glass substrate 1. The dry film 4, the conductive powder 5, the glass frit 6, containing an insoluble resin powder 7, and an organic binder 8,.

Then, when subjected to a firing treatment on the dried film 4, as shown in FIG. 4, the glass frit 6 together with the conductive film 2 is formed to segregate at the interface between the glass substrate 1. Further, insoluble resin powder 7 burned by thermal decomposition, the burned traces insoluble resin powder 7 was present gap 9 is formed.

During the conductive film 2 voids 9 of different pore sizes depending on the size of the particle size of the insoluble resin powder 7 is formed, the gap 9 so as to penetrate the conductive film 2, i.e. through-holes 11 may also be formed. And these voids 9 acts as a ventilation hole. As a result, decomposition gases can without pushing up the conductive film 2 is filled between the glass substrate 1 and the conductive film 2, it is suppressed formation of blisters (swelling) to be described later, thereby the glass substrate 1 and the conductive film 2 it is possible to increase the contact area with the.

By thus containing the insoluble resin powder 7 in the conductive paste, it is possible to suppress the formation of blisters after firing result, to increase the contact area between the glass substrate 1 and the conductive film 2 possible and becomes, thereby making it possible to effectively improve the bonding strength between the glass substrate 1.

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.

Figure 5 is another example of a state before firing a cross-sectional view schematically showing, 6, another example of the state after the firing is a cross-sectional view schematically showing the mean particle insoluble resin powder diameter D 50 indicates the case where relatively small.

Before firing, as shown in FIG. 5, since the conductive paste on the surface of the glass substrate 1 is coated and dried on the glass substrate 1 is dry film 4 is formed. Thus, the dry film 4 is similar to FIG. 3, the conductive powder 5, the glass frit 6, containing an insoluble resin powder 7, and an organic binder 8,.

Then, when subjected to a firing treatment on the dried film 4, as shown in FIG. 6, the glass frit 6 together with the conductive film 2 is formed to segregate at the interface between the glass substrate 1. Also, similar to FIG. 4, an insoluble resin powder 7 burned by thermal decomposition, the burned traces insoluble resin powder 7 was present gap 9 is formed.

However, when the average particle diameter D 50 of the insoluble resin powder 7 is small, the gap 9 or lost due to densification of the conductive film 2, the glass frit 6 enters the air gap 9, also compared to the thickness of the conductive film 2 very small air gap 9 is formed Te, there may not sufficiently exhibit the function as the ventilation hole of the voids 9 are decomposed gas. As a result, as shown in FIG. 6, the conductive film 2 of the decomposition gas generated in the form a blister 10 pushes up the conductive film 2, a reduction in the contact area of ​​this for the glass substrate 1 and the conductive film 2 lead. Therefore, although the adhesive force is improved as compared to the case of not containing an insoluble resin powder 7, improvement is small.

On the other hand, when the average particle diameter D 50 of the insoluble resin powder 7 becomes excessively large, since the number of insoluble resin powder 7 in the conductive paste is relatively reduced, also reduced the number of voids 9 which functions as a ventilation hole the density of voids 9 drops Te, the effect of improving the anchoring force even in this case there is a small possibility.

That is, insoluble resin powder 7 in the conductive paste is long is contained, can be formed of the air gap 9 by baking treatment, although it is possible to improve the adhesive force, the more improvement in the effective adhesion force to obtain an average particle diameter D 50 of the insoluble resin powder 7 is present is preferably in the range.

Then, the average particle diameter D 50 of such a preferred range is 3 ~ 15 [mu] m. When the average particle diameter D 50 of greater than 3μm or less than 15μm, although the fixing strength is improved as compared with the case not containing the insoluble resin powder 7, improvement effect is small.

As for the content of the insoluble resin powder, since the insoluble resin powder by calcining treatment if insoluble resin powder is contained as described above to form a void and burned, but are not limited to, from the viewpoint of achieving both fixing force and resistivity, preferably 0.2-1 parts by weight per 100 parts by weight of the conductive powder.

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, it may not be obtained a sufficient effect of improving adhesive force. On the other hand, if the content of insoluble resin powder exceeds 1 parts by weight with respect to 100 parts by weight of the conductive powder, although sticking force increases, the insoluble resin powder 7 is relatively increased with respect to the conductive powder 5, there is a possibility that specific resistance lowers the conductivity increases.

Therefore, in order to both resistivity and adhesive force to those better an average particle diameter D 50 of 3 - 15 [mu] m insoluble resin powder, 0.2 ~ to 100 parts by weight of the conductive powder and the content preferably 1 part by weight.

That is, by employing such preferred range an average particle size D 50 and the content of the insoluble resin powder suitable for producing the anti-fogging glass, resistivity bonding strength is more than 12N below 3.4μΩ · cm conductive and the fixing force can be obtained both by conductive paste.

As the conductive powder, but are not particularly limited as long as it is a metal powder having good conductivity, is generally used prefer that the Ag powder main component (e.g., more than 50 wt%) be able to. For example, a main component of Ag powder, Pd, various noble metal powder such as Pt may be contained as an auxiliary component.

Shape of the conductive powder is also not particularly limited, for example, spherical, flat, amorphous shape, or may be a mixture powder thereof.

The average particle diameter D 50 of the conductive powder may include, but are not particularly limited, from the viewpoint of ensuring the mechanical strength and the like, the average particle size D 50 is preferably 0.1 ~ 5 [mu] m. The average particle diameter D 50 of the conductive powder is equal to or less than 0.1μm viscosity increases during the paste producing paste becomes difficult, while when the average particle diameter D 50 of the conductive powder exceeds 5 [mu] m, at the time of firing the presence of the desired grain growth crystal grains between the conductive powder is insufficient, which may cause a decrease in mechanical strength.

The content of the conductive powder may include, but are not particularly limited but is preferably 50 ~ 90 wt%. If the content of the conductive powder is less than 50 wt%, since the content of the glass frit is relatively increased, in order to secure the desired conductivity, or to widen the line width, thick conductive film It must be of, which may lead to high costs. On the other hand, if the content of the conductive powder exceeds 90 wt%, the conductive powder becomes excessive paste may become difficult. Accordingly, the content of the conductive powder, although not particularly limited, but is preferably 50 ~ 90 wt%.

The composition of the glass frit is not particularly limited, from the viewpoint of avoiding a sealing deficiency at the interface decreases and the conductive film 2 of the sintered density, and melt at the firing temperature is required to flow. Then, the glass article, such as anti-fogging glass, usually, preferably from being fired at a temperature of about 500 ~ 800 ° C., to use a glass frit having a softening point is a composition adjusted to about 350 ~ 600 ° C..

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 2 O, Li 2 O, Sb 2 O 3, FeO, from various oxides such as CuO, can be selected in consideration of the softening point and chemical durability.

The average particle diameter D 50 of the glass frit is also not particularly limited, from the viewpoint of sinterability of sessile or conductive paste between the glass substrate 1 and the conductive film 2 is preferably 0.1 ~ 5.0 .mu.m .

The content of the glass frit is also not particularly limited, considering the solderability of the sticking resistance and lead between the glass substrate 1 and the conductive film 2, is preferably 1.5 ~ 6.0 wt%.

The ratio between the organic binder and organic solvent constituting the organic vehicle also is not particularly limited, usually, for example volume ratio, 1 to 3: are prepared so that 7-9. As the organic binder, for example, can be used ethyl cellulose resin, nitrocellulose resins, acrylic resins, alkyd resins, or a combination thereof. As the organic solvent, alpha-terpineol, xylene, toluene, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate alone or can be used in combination.

Next, explaining the method of producing the anti-fogging glass including a method of forming a conductive pattern of the present invention.

First, a conductive powder such as Ag powder, Bi-B-Si-based, such as glass frit, prepared the insoluble resin powder polypropylene resin or the like which burn off at a and firing processes insoluble in an organic vehicle.

Further, an organic solvent such as an organic binder and α- terpineol such as soluble cellulose resin in an organic solvent are blended in a predetermined ratio to prepare an organic vehicle.

Then, conductive powder, glass frit, and was charged insoluble resin powder in an organic vehicle, and dispersed and kneaded by using a three-roll mill, thereby preparing a conductive paste.

Then, by using a printing method such as screen printing, a conductive paste on the glass substrate 1 was coated, a predetermined time at a temperature of about 120 ~ 170 ° C. (e.g., 10 minutes) and dried to give a dry film 4.

Then, the dry film 4 to 500 ~ 800 ° C. of about sintering temperature for a predetermined time (e.g., 5 minutes) the firing process is performed. Then insoluble resin powder is burned, the burned traces of insoluble resin powder with voids containing a through hole is formed, the conductive film 2 and the collector electrode 3a ~ 3b having a predetermined pattern is formed on the glass substrate 1 , thereby anti-fogging glass is produced.

Method of forming such a Honshirubeden pattern includes a conductive powder, a glass frit, an insoluble resin powder destroyed by having and baking treatment with an organic vehicle composed of an organic binder and an organic solvent, the insoluble in the organic vehicle preparing a preparative, coating the conductive powder, the glass frit and the insoluble resin powder the by kneading with an organic vehicle to make a paste, a step of preparing a conductive paste, the conductive paste on a substrate and then drying, a process of forming a dry film, the dry film to baking treatment performed, when forming a conductive film in a predetermined pattern on the substrate to burn off the insoluble resin powder simultaneously, the decomposition gas of the organic binder since the air gap to ventilate comprising the step of forming the burned traces of the insoluble resin powder, the gap becomes a ventilation hole for the decomposition gas of the organic binder, the Can cavity solutions gas is filled is prevented from being formed between the substrate and the conductive film. And consequently, the contact area between the glass substrate 1 and the conductive film 2 is increased, thereby improving the fixing strength between the substrate and the conductive film.

Thus since the improved fixing strength between the glass substrate 1 and the conductive film 2, good defogging mechanical strength conductive film 2 and the terminal electrodes 3a, the tensile stress 3b does not break as easily be loaded it is possible to obtain a glass.

Figure 7 is a fragmentary cross-sectional view showing an example of an antenna with a glass of a second embodiment of a glass article according to the present invention.

The antenna with glass, the intermediate film 14 made of a polyvinyl alcohol resin or the like between the plurality of glass substrates (first and second glass substrates 12 and 13) is a laminated glass was interposed, considering impact resistance structure It has become.

Then, the surface of the first glass substrate 12 ceramic layer 15 is formed, a receiving unit composed of a single wire or a plurality of wires having an antenna function is further surface of the ceramic layer 15, which is connected to the receiver the conductive film 16 and a soldering portion of the rectangular shape is formed. The receiving unit is connected to the connection terminal via the soldered portion, and the connection terminal is connected to the lead wire. Then, the antenna with glass, like anti-fogging glass, for example, be implemented as a vehicle window glass such as an automobile, receives radio waves from outside the vehicle, is subjected to radio and television.

The antenna attached glass is produced as follows.

That is, the ceramic paste mainly composed of ceramic material containing glass frit is coated on the first glass substrate 12 and dried. Then, this on the ceramic paste a conductive paste of the present invention to have a predetermined antenna pattern is applied, dried, then, a conductive film 16 by co-firing the ceramic paste and conductive paste. Then, the intermediate film 14 and the first glass substrate 12 and the second glass substrate 13 are attached via an adhesive to be clamped, thereby the antenna with glass is prepared.

In this way, the glass with the antenna, by forming a conductive film 16 using a conductive paste of the present invention, like the first embodiment, adhesive force is improved while ensuring a low resistivity it is possible to obtain a glass with an antenna having a good mechanical strength.

The present invention is not limited to the above embodiment. In the method of forming the conductive pattern, but using a glass substrate 1 as a substrate, a ceramic substrate, or the like, it is needless to say also be applied to other substrates such.

The glass articles such as anti-fogging glass or the antenna with the glass, since it is mounted on the front portion or rear portion of a vehicle or the like, molybdenum silicide to exert design effect by coloring the formation portions of the conductive film in dark also preferred to add a black pigment such as chromium oxide or copper oxide with or anti-glare effect in the conductive paste.

Further, the present invention is within a range that does not affect the characteristics, may contain various inorganic components needed. For example, Zr, P, V, Ce, Nb, Ta, W, Pd, Ag, Ru, Sn, In, Y, Dy, may contain La or the like. Also, there are no particular limitation on containing forms, oxides, hydroxides, peroxides, halides, carbonates, nitrates, phosphates, sulfates, fluorides, organometallic compounds, etc., suitably selected can do.

Further, the present conductive paste, if necessary, di-2-ethylhexyl phthalate, also preferable to add one or a combination of these plasticizers such as dibutyl phthalate. Also preferable to add a rheology modifier such as a fatty acid amide or fatty acid, more thixotropic agents, thickening agents, may be added a dispersant.

Next, a description will be given of an embodiment of the present invention in detail.

Preparation of sample]
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 particle size were prepared polypropylene resin powder 1 ~ 30 [mu] m (insoluble resin powder).

The average particle diameter D 50 was measured by a laser diffraction particle size distribution analyzer.

Further, to produce an organic vehicle in the following manner. That is, ethyl cellulose resin is 10 wt% of organic binder, the α- terpineol as an organic solvent were mixed and ethylcellulose resin and α- terpineol so that 90 wt%, to prepare an organic vehicle.

Next, Ag powder: 80 wt%, the glass frit 5 wt%, molybdenum silicide powder: 0.5 wt%, the organic vehicle: were blended to a 14.5 wt%, the polypropylene resin powder to further Ag powder 100 parts by weight 0 was added a polypropylene resin powder as a to 2 parts by weight, were mixed in a planetary mixer, and dispersed with a three-roll mill were kneaded, to prepare a conductive paste of sample No. 1-9.

[Evaluation of the sample]
Vertical: 76 mm, Horizontal: 26 mm, thickness: providing a 1.4mm glass slide, using the above conductive paste, the line total length L: 100 mm, line width W: screen printing so as to 0.5 mm, slide forming a circuit pattern on the glass, further longitudinally opposite ends: 2 mm, lateral: 2 mm of forming a current collecting pattern to obtain a dry film comprising a circuit pattern and the collector pattern. Then, the slide glass was dried for 10 minutes at a temperature of 0.99 ° C., and calcined for 5 minutes at a maximum temperature 600 ° C., dry film conductive film on the surface of the slide glass and dried and sample numbers collector electrode is formed a sample of 1 to 9 were produced.

Then, the resistance was measured in the collector electrodes formed on both ends of the conductive film with a digital ohmmeter. Then, the cross-sectional area of ​​the conductive film was measured with a contact-type surface roughness meter was calculated color resistivity between the cross area and the line total length L (= 100mm).

Further, joining by soldering the lead wire made of Cu which is Sn-plated in the collecting electrode, pulling the lead wire at a constant rate, measuring the maximum load until the peeling was determined fixing strength of the electrode.

Table 1 shows the average particle size of the polypropylene resin powder used in Sample No. 1-9, the amount of content for Ag100 parts, and the measurement results (resistivity, adhesion strength).

Figure JPOXMLDOC01-appb-T000001

Sample No. 1, since the polypropylene resin powder in the conductive paste is not contained, but the specific resistance is good and 2.6μΩ · cm, the bonding strength is as low as 11N, between the slide glass and the conductive film It was found to be inferior to the adhesive force.

In contrast Sample No. 2-9, the bonding strength is at 12N or more, it was found that fixing strength as compared with Sample No. 1 is improved.

However, Sample No. 2, the fixing strength of what is improved fixing strength as compared to Sample No. 1 is 12N, improvement 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 pushed slightly, the contact area between the conductive film and the slide glass is believed to be due to decreased.

Further, Sample No. 6, the fixing strength is 16N, it was small improvement becomes 20N or less. Since this large average particle diameter D 50 of the polypropylene resin powder and 30 [mu] m, less the number of the polypropylene resin powder in the conductive paste, by baking, is formed voids is decreased the density of voids also Therefore contact area between the conductive film and the slide glass is believed to be due to decreased.

On the other hand, Sample No. 9, although the fixing strength was good and 24N, the resistivity is increased as 4.3μΩ · cm. This content of the polypropylene resin powder lot and 2 parts by weight to Ag100 parts, the content of Ag powder in this order conductive paste becomes relatively small, specific resistance seems to have increased.

Sample Nos. 3 to 5, 7 and 8 In contrast, the average particle diameter D 50 of 3 to 15 [mu] m polypropylene resin powder, either 0.2 to 1.0 part by weight relative to the content of even Ag powder 100 parts by weight since also the preferred ranges, the resistivity bond strength below 3.4μΩ · cm was found to be 20 ~ 25 N, and the none of the specific resistance and the adhesive force good conductivity paste is obtained.

The important that contain an insoluble resin powder polypropylene resins burned off in the firing process has a insoluble in the organic vehicle in the conductive paste to improve the fixing strength while maintaining the desired resistivity than higher , and the addition, in order to obtain good properties than the resistivity (conductivity) and bonding strength (adhesive force) is incompatible, the average particle diameter D 50 of the insoluble resin powder 3 ~ 15 [mu] m, the content thereof is conductive is 0.2 to 1.0 part by weight was found to be effective against sex powder 100 parts by weight.

Realizing suitably available conductive paste glass articles such as adhesive force is excellent anti-fogging glass or an antenna with a glass for a vehicle with the substrate while maintaining the desired resistivity.

1 glass substrate 2 conductive film 4 dry film 5 conductive powder 6 glass frit 7 insoluble resin powder 8 organic binder 12 the first glass substrate 16 a conductive film

Claims (9)

  1. At least a conductive powder, a glass frit, a conductive paste containing an organic vehicle composed of an organic binder and an organic solvent,
    Conductive paste characterized by containing a resin powder which burned at a and firing processes insoluble in the organic vehicle.
  2. Temperature the resin powder is burned is 500 ~ 800 ° C. in a claim 1, wherein the conductive paste
  3. The resin powder, according to claim 1 or claim 2, wherein the conductive paste, wherein the average particle diameter of 3 ~ 15 [mu] m.
  4. The content of the resin powder, the conductive paste according to any one of claims 1 to 3, characterized in that relative to the 100 parts by weight of the conductive powder is 0.2 to 1 parts by weight.
  5. The resin powder, polyolefin, polymethacrylate, and claims 1 to 4 of any one of the description of the conductive paste, characterized in that it comprises at least one selected from the group of polyacrylic acid ester.
  6. Wherein the conductive powder, conductive paste according to any one of claims 1 to 5, characterized in that it is mainly composed of Ag.
  7. A conductive powder, a glass frit, an organic vehicle composed of an organic binder and an organic solvent, a conductive paste comprising a resin powder which burned at a and calcined insoluble on the substrate with respect to the organic vehicle coating a step of,
    Subjected to firing treatment to the conductive paste coated on the substrate, to burn off the resin powder and at the same time to form a conductive film in a predetermined pattern on the substrate, a through hole penetrating through the conductive layer of the resin powder method of forming a conductive pattern which comprises a step of forming a burned mark.
  8. Specific resistance of the conductive film after firing, a method of forming the conductive pattern according to claim 7, wherein a is less 3.4μΩ · cm.
  9. Conductive film is formed on a glass substrate, a glass article connection terminal is joined on the conductive film,
    The conductive film is a glass article, characterized by being formed by a sintered body of a conductive paste according to any one of claims 1 to 6.
PCT/JP2017/002480 2016-03-18 2017-01-25 Conductive paste, method for forming conductive pattern, and glass article WO2017159055A1 (en)

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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, the electrode circuit, and a 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, the electrode circuit, and a plasma display panel
WO2010116851A1 (en) * 2009-04-10 2010-10-14 株式会社村田製作所 Charged powder

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