JP2021147263A - Paste of glass composition, and sealing structure and electric/electronic component including the glass composition - Google Patents

Abstract

To provide a paste of a lead-free, low-melting-point glass composition that allows use of an aqueous solvent while maintaining a softening temperature comparable to that of the conventional lead-free, low-melting-point glass composition, and a sealing structure and an electric/electronic component including the glass composition paste.SOLUTION: A glass composition paste has powder of a lead-free glass composition and a solvent. The glass composition has V2O5 and Ag2O when its components are expressed in terms of oxide. The mol% content of V2O5 and the mol% content of Ag2O satisfy the relation (1): 1/3×[V2O5]≤[Ag2O]≤2×[V2O5]. The solvent is an aqueous solvent.SELECTED DRAWING: Figure 2

Description

The present invention relates to a technique for a lead-free low melting point glass composition, and more particularly to a glass composition paste containing an aqueous solvent, a sealing structure manufactured by using the glass composition paste, and electrical and electronic parts.

Sealing / bonding technology using glass for the purpose of airtight sealing (also called sealing) between constituent base materials and electrical insulation fixing is used in a wide range of fields and products. For example, vacuum insulated double glazing panels in the field of housing parts, image display devices in the field of electrical and electronic parts, crystal oscillators, integrated circuit packages, semiconductor sensors, multilayer circuit boards, solar cell panels and the like can be mentioned. Further, in the field of electrical and electronic parts, a material obtained by mixing a glass composition powder and a metal powder is printed on a base material and fired to pattern an electrode and / or a wiring (hereinafter referred to as an electrode / wiring). It may also be used to form a heat conductive bonding layer.

In glass sealing / bonding technology, lowering the softening flow temperature of the glass composition and thermal / chemical stability are extremely important properties. Until around 2000, lead glass compositions that softened and flowed at relatively low temperatures and were thermally and chemically stable (glass containing lead oxide (PbO) as the main component) were widely used as glass compositions.

However, since the beginning of the 21st century, the trend of green procurement and green design has intensified worldwide, and safer materials have been required. For example, in the European Union (EU), the European Union Directive (RoHS Directive) on restrictions on the use of specified hazardous substances in electronic and electrical equipment came into effect on July 1, 2006, and Pb, mercury (Hg), and cadmium. (Cd), hexavalent chromium (Cr ⁶⁺ ), etc. are designated as prohibited substances.

Therefore, the development of low melting point glass (lead-free low melting point glass composition) containing no Pb has been promoted. For example, Patent Document 1 (Japanese Patent Laid-Open No. 2013-032255) describes a lead-free glass composition in which 10 to 60% by mass of Ag ₂ O and 5 to 65% by mass of Ag 2 O when the components are represented by oxides. and V ₂ O _5, contains and TeO ₂ of 15 to 50 wt%, the total content of Ag ₂ O and V ₂ O ₅ and TeO ₂ is less than 75 mass% to 100 mass%, P as the balance _{It is characterized by containing one or more of 2} O ₅ , BaO, K ₂ O, WO ₃ , Fe ₂ O ₃ , MnO ₂ , Sb ₂ O ₃ , and Zn O in an amount of more than 0% by mass and not more than 25% by mass. The glass composition to be used is disclosed.

Patent Document 2 (Japanese Unexamined Patent Publication No. 2016-050135) describes a lead-free low melting point glass composition containing vanadium oxide, tellurium oxide and silver oxide, and further comprises one or more of yttrium and lanthanoid oxides as additional components. A lead-free low melting point glass composition containing, and characterized in that the content of the additional component is 0.1 to 3.0 mol% in terms of oxide, is disclosed.

Patent Document 3 (Japanese Patent Laid-Open No. 2016-050136) describes a lead-free low melting point glass composition containing vanadium oxide, tellurium oxide, and silver oxide, which is V ₂ O ₅ , TeO _2, and Ag ₂ O in terms of the following oxides. The total content of _{TeO 2} and Ag ₂ O is 1 to 2 times that of the content of _{V 2} O _{5 , respectively, and BaO, WO 3} and A lead-free low melting point characterized by containing 0 to 13 mol% of any one or more of P ₂ O ₅ and 0.1 to 3.0 mol% of any one or more of oxides of Group 13 of the periodic table as an additional component. The glass composition, is disclosed.

According to Patent Document 1, it is possible to provide a lead-free glass composition that softens and flows at a firing temperature equal to or lower than that of a low melting point lead glass composition, and has both good thermal stability and chemical stability. ing. Further, according to Patent Documents 2 to 3, a _{lead-free low-melting-point glass composition which suppresses or prevents crystallization of an Ag 2} OV ₂ O _5- TeO _2- based lead-free low-melting-point glass composition and improves softening fluidity at low temperatures. It is said that it can provide.

Japanese Unexamined Patent Publication No. 2013-032255 Japanese Unexamined Patent Publication No. 2016-050135 Japanese Unexamined Patent Publication No. 2016-050136

In the glass sealing / bonding technology, the glass composition powder, the resin binder, and the solvent are mixed from the viewpoint of workability (for example, to facilitate application to the material to be sealed or the base material to be bonded). Glass paste is often used. Further, a thermal expansion adjusting filler powder (for example, a powder of a low thermal expansion filler) is mixed with the glass paste so that the thermal expansion / thermal shrinkage of the substrate to be sealed or the substrate to be bonded and the glass composition are matched. Sometimes.

In general, the lower the characteristic temperature (transition point, yield point, softening point, etc.) of the glass composition, the better the softening fluidity during heating. On the other hand, a glass composition having a lower characteristic temperature tends to have poorer chemical stability (water resistance, moisture resistance) with respect to water. In particular, when mixed with water in a frit state (powder state, state with a large specific surface area), unwanted adsorption and unwanted chemical bonds between the surface of glass particles and water molecules occur, resulting in softening fluidity during heating. Problems such as deterioration and generation of unwanted bubbles during the softening flow are likely to occur.

For this reason, conventionally, it has been considered that the low melting point glass composition powder should be handled so as to avoid adverse effects due to water content, and even in Patent Documents 1 to 3, the solvent used for the low melting point glass paste contains water as much as possible. No organic solvent (non-aqueous solvent) is selected.

In the glass sealing / bonding process using the glass composition paste, the solvent of the applied paste is usually heated after the step of applying the glass composition paste to the desired portion of the material to be sealed or the base material to be bonded. A drying step is performed. In this solvent heating / drying step, since the solvent is an organic solvent, an explosion-proof heating / drying machine, an abatement device, or the like is required from the viewpoint of ensuring work safety and protecting the global environment. In other words, those safety equipment costs have been considered inevitable manufacturing costs.

In recent years, the demand for green procurement and green design for industrial products has been increasing, and the cost of safety equipment is on the rise. On the other hand, the demand for cost reduction for housing parts and electrical and electronic parts is increasing.

As one of the solutions satisfying these conflicting requirements, aqueous solventization of the solvent in the low melting point glass composition paste can be considered. If an aqueous solvent can be used instead of an organic solvent, it will be possible to reduce costs by simplifying safety equipment that was previously considered essential (for example, explosion-proof heat dryers, abatement devices, explosion-proof storage equipment, etc.). become. That is, the realization of a lead-free low melting point glass composition paste using an aqueous solvent is expected.

Therefore, the primary object of the present invention is a lead-free low-melting-point glass composition that makes it possible to use an aqueous solvent while maintaining a softening temperature (for example, 400 ° C. or lower) equivalent to that of a conventional lead-free low-melting-point glass composition. The purpose is to provide a paste of things. Another object of the present invention is to provide a sealing structure and an electric / electronic component manufactured by using the glass composition paste.

(I) One aspect of the present invention is a glass composition paste containing a lead-free glass composition powder and a solvent.
_{The glass composition contains V 2} O ₅ (vanadium oxide) and Ag ₂ O (silver oxide) when the components are expressed as oxides.
The molar% content of V ₂ O _{5 and} the molar% content of Ag ₂ O are
Relational expression (1): 1/3 × [V ₂ O ₅ ] ≤ [Ag ₂ O] ≤ 2 × [V ₂ O ₅ ],
The filling,
The solvent provides a glass composition paste, which is characterized by being an aqueous solvent.
In the present invention, [component X] represents the molar% content of component X in the glass composition.

(II) Another aspect of the present invention is a glass composition paste containing a lead-free glass composition powder and a solvent.
_{The glass composition contains V 2} O ₅ and Ag ₂ O when the components are represented by oxides.
The solvent is an aqueous solvent and
In the radial structure function obtained by Fourier transforming the wide-area X-ray absorption fine structure near the K absorption edge of the vanadium component, the peak top intensity of the first coordination sphere in the glass composition is V ₂ O _{5 of a single substance.} Provided is a glass composition paste, which is characterized in that it is larger than the peak top intensity of the first coordination sphere in a crystal.

(III) Yet another aspect of the present invention is a lead-free glass composition.
When the components are expressed as oxides, they consist of three or more types of oxides.
_{Contains V 2} O ₅ and Ag ₂ O as the main ingredients,
_{Containing Te O 2} (tellurium oxide) and / or Li ₂ O (lithium oxide) as the first optional component,
_{A group consisting of K 2} O (potassium oxide), MgO (magnesium oxide), P ₂ O ₅ (phosphorus oxide), BaO (barium oxide), ZnO (zinc oxide), and WO ₃ (tungsten trioxide) as the second optional component. Contains more than one of
As the third optional component, Al ₂ O ₃ (aluminum oxide), Fe ₂ O ₃ (iron oxide), Y ₂ O ₃ (yttrium oxide), La ₂ O ₃ (lanthanum oxide), CeO ₂ (cerium oxide), Er ₂ Contains one or more of the group consisting of O ₃ (erbium oxide) and Yb ₂ O _{3 (yttrium oxide).}
The molar% content of the main component is
Relational expression (1): 1/3 × [V ₂ O ₅ ] ≤ [Ag ₂ O] ≤ 2 × [V ₂ O ₅ ],
The filling,
When the first optional component is contained, the molar% content of the first optional component is
Relational expression (2): [V ₂ O ₅ ] + [Ag ₂ O] + [TeO ₂ ] ≧ 73,
Relational expression (3): [Li ₂ O] ≤ 1/2 x [Ag ₂ O],
Relational expression (4): [Ag ₂ O] + [Li ₂ O] ≤ 2 × [V ₂ O ₅ ],
Relational expression (5): 20 ≤ [V ₂ O ₅ ] ≤ 45,
Relational expression (6): 12 ≤ [Ag ₂ O] ≤ 45,
Relational expression (7): 25 ≤ [TeO ₂ ] ≤ 47, and relational expression (8): 0 <[Li ₂ O] ≤ 15,
The filling,
When the second optional component is contained, the molar% content of the second optional component is
Relational expression (9): 0 <[K ₂ O] + [MgO] + [P ₂ O ₅ ] + [BaO] + [WO ₃ ] + [ZnO] ≤ 17,
The filling,
When the third optional component is contained, the molar% content of the third optional component is
Relational expression (10): 0.3 ≤ [Al ₂ O ₃ ] + [Fe ₂ O ₃ ] + [Y ₂ O ₃ ] + [La ₂ O ₃ ] + [CeO ₂ ] + [Er ₂ O ₃ ] + [Yb ₂ O ₃ ] ≤ 7.5,
Provided is a glass composition, which is characterized by satisfying.

(IV) Yet another aspect of the present invention is a sealing structure having a sealing portion made of a glass material.
Provided is a sealing structure, characterized in that the glass material comprises the glass composition according to the present invention.

(V) Yet another aspect of the present invention is an electrical and electronic component having electrodes / wiring or heat conductive bonding layers made of glass material.
Provided is an electrical / electronic component, characterized in that the glass material comprises the glass composition according to the present invention.

According to the present invention, a paste of a lead-free low melting point glass composition that makes it possible to use an aqueous solvent while maintaining a softening temperature (for example, 400 ° C. or lower) equivalent to that of a conventional lead-free low melting point glass composition, the glass composition. It is possible to provide a sealing structure and an electric / electronic component manufactured by using a physical paste. By using the glass composition paste of the aqueous solvent, it is possible to reduce the manufacturing cost (that is, the cost reduction) of the sealed structure and the electric / electronic parts.

This is a typical example of a chart obtained during the heating process of differential thermal analysis (DTA) on a glass composition. The first coordination sphere of the radial structure function obtained by Fourier transforming the wide-area X-ray absorption fine structure near the K-edge of the vanadium component in the glass compositions GA-1 to GA-3 and GB-1 to GB-6. It is a graph which shows the area. It is a schematic schematic diagram which shows the manufacturing method of the joint body which becomes the joint part evaluation sample. It is a graph which shows the relationship between the volume ratio of "Ag powder / GE-39 powder" in the paste, and the connection resistance of various joints in the glass composition paste which mixed the glass composition GE-39 powder and Ag powder. .. It is a graph which shows the relationship between the volume ratio of "Cu powder / GE-39 powder" in the paste, and the connection resistance of various joints in the glass composition paste which mixed the glass composition GE-39 powder and Cu powder. .. In a graph showing the relationship between the volume ratio of "Al powder / GE-02 powder powder" in the paste and the connection resistance of various conjugates in the glass composition paste in which the glass composition GE-02 powder and Al powder are mixed. be. In a graph showing the relationship between the volume ratio of "Sn powder / GE-02 powder powder" in the paste and the connection resistance of various conjugates in the glass composition paste in which the glass composition GE-02 powder and Sn powder are mixed. be. A graph showing the relationship between the volume ratio of "Ag powder / GE-60 powder powder" in the paste and the wiring resistance of each electrode / wiring in the glass composition paste in which the glass composition GE-60 powder and Ag powder are mixed. Is. It is a plan schematic diagram of the produced vacuum insulation double glazing panel, and is the enlarged sectional sectional schematic diagram along the line AA. It is a plan schematic diagram which shows the state which the sealing part and the spacer are formed on one glass substrate which constitutes a vacuum insulation double glazing panel, and is the enlarged sectional sectional schematic diagram along line BB. It is an enlarged sectional schematic diagram which shows the outline of the vacuum sealing process of the vacuum insulation multi-layer glass panel. This is an example of a firing temperature profile in the vacuum sealing process of a vacuum-insulated double glazing panel. It is a plan view of the produced organic light emitting diode display panel, and is an enlarged sectional schematic view along line CC. It is a plan view of the light receiving surface of the produced solar cell panel, the plan view of the back surface, and the cross-sectional schematic view along the DD line. It is sectional drawing which shows the example of the manufacturing process of the crystal oscillator package which concerns on this invention.

The present invention can make the following improvements and modifications to the above-mentioned glass composition paste (I) according to the present invention.
(I) The glass composition further contains _{TeO 2} when the components are expressed as oxides, and _{the molar% content of V 2} O _{5 and} the molar% content of Ag ₂ O and the Te O ₂ The molar% content is
Relational expression (2): [V ₂ O ₅ ] + [Ag ₂ O] + [TeO ₂ ] ≧ 73,
Meet.
(Ii) The glass composition further contains _{Li 2} O when the components are expressed as oxides, and _{the molar% content of V 2} O _{5 and} the molar% content of Ag ₂ O and the Li ₂ The molar% content of O is
Relational expression (3): [Li ₂ O] ≤ 1/2 × [Ag ₂ O], and relational expression (4): [Ag ₂ O] + [Li ₂ O] ≤ 2 × [V ₂ O ₅ ],
Meet.
(Iii) _{The mol% content of V 2} O ₅ , the mol% content of Ag ₂ O, and the molar% content of Te O ₂ are
Relational expression (5): 20 ≤ [V ₂ O ₅ ] ≤ 45,
Relational expression (6): 12 ≤ [Ag ₂ O] ≤ 45, and relational expression (7): 25 ≤ [TeO ₂ ] ≤ 47,
Meet.
(Iv) _{The mol% content of V 2} O ₅ , the mol% content of Ag ₂ O, the molar% content of Te O ₂ , and the molar% content of Li ₂ O are
Relational expression (5): 20 ≤ [V ₂ O ₅ ] ≤ 45,
Relational expression (6): 12 ≤ [Ag ₂ O] ≤ 45,
Relational expression (7): 25 ≤ [TeO ₂ ] ≤ 47, and relational expression (8): 0 <[Li ₂ O] ≤ 15,
Meet.
(V) The glass composition further contains one or more of the group consisting _{of K 2} O, MgO, P ₂ O ₅ , BaO, ZnO, and WO ₃ when the components are represented by oxides.
The molar% content of the components that make up the group
Relational expression (9): 0 <[K ₂ O] + [MgO] + [P ₂ O ₅ ] + [BaO] + [WO ₃ ] + [ZnO] ≤ 17,
Meet.
(Vi) The glass composition has Al ₂ O ₃ , Fe ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Er ₂ O ₃ , and Yb ₂ O when the components are expressed as oxides. Further containing one or more of the group consisting of ₃
The molar% content of the components that make up the group
Relational expression (10): 0.3 ≤ [Al ₂ O ₃ ] + [Fe ₂ O ₃ ] + [Y ₂ O ₃ ] + [La ₂ O ₃ ] + [CeO ₂ ] + [Er ₂ O ₃ ] + [Yb ₂ O ₃ ] ≤ 7.5,
Meet.

The present invention can make the following improvements and modifications to the above-mentioned glass composition paste (II) according to the present invention.
(Vii) The peak top intensity of the glass composition is 1.2 times or more the _{peak top intensity of the single V 2} O _{5 crystal.}

The present invention can be improved or modified as follows in the above-mentioned glass composition pastes (I) and (II) according to the present invention.
(Viii) The transition point of the glass composition is 260 ° C. or lower.
(Ix) The liquid property of the glass composition paste is neutral or alkaline.
(X) The glass composition paste further contains a nonionic water-soluble thermoplastic resin as a resin binder.
(Xi) The water-soluble thermoplastic resin is polyethylene oxide.
(Xii) The weight average molecular weight of the polyethylene oxide is 3,500,000 or more.
(Xiii) The glass composition paste further contains a thermal expansion adjusting filler powder.
(Xiv) The thermal expansion adjusting filler powder is Zr ₂ (WO ₄ ) (PO ₄ ) ₂ (zirconium tungstate phosphate), Li ₂ O ・ Al ₂ O ₃・ 2SiO ₂ (β-eucryptite), 2MgO. _{· 2Al 2 O 3 · 5SiO 2} ( _{cordierite), 3Al 2 O 3 · 2SiO} 2 ( mullite), SiO ₂ (silica), Nb ₂ O ₅ (niobium oxide), and Si of the group consisting of (silicon) Any one or more powders.
(Xv) The volume content of the thermal expansion adjusting filler powder is 2.5 times or less the volume content of the glass composition.
(Xvi) The glass composition paste further comprises a metal powder.
(Xvii) The metal powder is one or more of the group consisting of Ag, Ag alloy, Cu (copper), Cu alloy, Al, Al alloy, Sn (tin), Sn alloy, Fe, and Fe alloy. It is a powder.
(Xviii) The volume content of the metal powder is 9 times or less the volume content of the glass composition.

The present invention can be improved or modified as follows in the above-mentioned glass composition (III) according to the present invention.
(Xix) In the radial structure function obtained by Fourier transforming the wide-area X-ray absorption fine structure at the K-edge of the vanadium component, the peak top intensity of the first coordination sphere in the glass composition is V _{2 of a single substance.} It is larger than the peak top intensity of the first coordination sphere in the _{O 5 crystal.}
(Xx) The peak top intensity of the glass composition is 1.2 times or more the _{peak top intensity of the single V 2} O _{5 crystal.}
(Xxi) The transition point of the glass composition is 260 ° C. or lower.
(Xxii) The glass composition further comprises a thermal expansion adjusting filler powder.
(Xxiii) said thermal expansion adjustment filler _{powder, Zr 2 (WO 4) (} PO 4) 2, Li 2 O · Al 2 O 3 · 2SiO 2, 2MgO · 2Al 2 O 3 · 5SiO 2, 3Al 2 O 3 · A powder of any one or more of the group consisting of 2SiO ₂ , SiO ₂ , Nb ₂ O _{5, and Si.}
(Xxiv) The volume content of the thermal expansion adjusting filler powder is 2.5 times or less the volume content of the glass phase in the glass composition.
(Xxv) The glass composition further comprises a metal powder.
(Xxvi) The metal powder is any one or more powders in the group consisting of Ag, Ag alloys, Cu, Cu alloys, Al, Al alloys, Sn, Sn alloys, Fe, and Fe alloys.
(Xxxvii) The volume content of the metal powder is 9 times or less the volume content of the glass phase in the glass composition.

(Basic idea of the present invention)
As described above, in the conventional lead-free low melting point glass composition paste, an organic solvent (non-aqueous solvent) containing as little water as possible has been used as a solvent in order to avoid adverse effects of water on the glass composition powder. The present inventors have studied and investigated the composition of the lead-free low-melting-point glass composition in more detail than before in order to develop a paste of the lead-free low-melting-point glass composition that makes it possible to use an aqueous solvent. As a result, in a limited composition, a glass composition that does not cause any problems even when an aqueous solvent which was conventionally considered to be inappropriate is used, but rather exhibits a softening fluidity superior to that when an organic solvent is used. We have found that a paste can be obtained.

In order to study the glass structure of this characteristic glass composition, a wide-area X-ray absorption fine structure near the K-absorbing edge of the vanadium (V) component, which is considered to be the skeleton-forming component (mesh-forming component) of the glass composition. The radial structure function obtained by Fourier transforming (EXAFS) was investigated. As a result, in the glass composition according to the present invention, an extremely specific phenomenon is observed in which the peak top intensity of the V component in the first coordination sphere is _{larger than the peak top intensity of the simple V 2} O _{5 crystal.} rice field. This means that the coordination number of the V component is larger than that in _{a single V 2} O _{5 crystal.}

In addition, the glass composition according to the present invention exhibits extremely excellent softening fluidity, and as a result, the content of the glass composition in the glass composition paste can be reduced as compared with that of the conventional glass paste. (In other words, the content of the thermal expansion adjusting filler powder and / or the metal powder can be increased more than that of the conventional glass paste). This contributes to improving the characteristics and reducing the cost of the sealing glass material, the electrode / wiring glass material, and the heat conductive glass bonding material.

The present invention has been completed based on the above-mentioned characteristic phenomena and findings.

Hereinafter, embodiments of the present invention will be specifically described with reference to the drawings. However, the present invention is not limited to the embodiments taken up here, and can be appropriately combined with a known technique or improved based on the known technique without departing from the technical idea of the invention. be.

(Glass composition and its paste)
As described above, the present invention provides a lead-free low-melting-point glass composition paste that makes it possible to use an aqueous solvent while maintaining a softening temperature (for example, 400 ° C. or lower) equivalent to that of a conventional lead-free low-melting-point glass composition. It is to provide. That is, the glass composition paste according to the present invention contains a powder of a lead-free low melting point glass composition and an aqueous solvent (does not contain an organic solvent).

First, the characteristic temperatures (transition point, yield point, softening point, crystallization temperature) of the glass composition will be briefly described.

The characteristic temperature of the glass composition is often measured by differential thermal analysis (DTA). FIG. 1 is a typical example of a chart obtained in the process of raising the temperature of DTA with respect to the glass composition. As shown in FIG. 1, the start temperature of the first heat absorption peak _{is defined as the transition point T g} (corresponding to viscosity = 10 ^13.3 poise), and the peak temperature of the first heat absorption peak is the yield point T _d (viscosity = 10). ^11.0 poise equivalent) and is defined, the peak temperature of the second endothermic peak is defined as a softening point T _s (corresponding to a viscosity = 10 ^7.65 poise), the starting temperature of the first exothermic peak is defined as the crystallization temperature T _cry , The peak temperature of the first exothermic peak is defined as the _{crystallization peak temperature T cry-p.} Each temperature is the temperature obtained by the tangent method. Each characteristic temperature in the present invention is based on the above definition.

Ease of crystallization of the glass composition (corresponding to the calorific value) from the difference (absolute value) between the softening point T _s and the crystallization temperature T _{cry in the glass composition and the height of the exothermic peak due to crystallization (corresponding to the calorific value).} (Called crystallization tendency) can be estimated. If the temperature difference between the softening point T _s and the crystallization temperature T _cry is large, the glass can be softened and flowed in a wide temperature range of _{T s} or more and _{less than T cry, and workability such as glass sealing is improved.} In addition, if the calorific value during crystallization is small, even if the working temperature _{reaches T cry} , the rapid temperature rise caused by the heat generated by crystallization is suppressed, and the crystals accompanying the temperature rise are suppressed. Since the crystallization progresses slowly, there is an advantage that the temperature can be controlled in a timely manner.

Next, the chemical composition of the glass composition will be described.

The glass composition used in the present invention contains V ₂ O ₅ and Ag ₂ O when the components are expressed as oxides, and contains the mol% content of the _{V 2} O _{5 and the mol% of the Ag 2} O. The rate is
Relational expression (1): 1/3 × [V ₂ O ₅ ] ≤ [Ag ₂ O] ≤ 2 × [V ₂ O ₅ ],
It is preferable to satisfy. In the present invention, [component X] of each relational expression represents the molar% content of component X in the glass composition. Both V ₂ O ₅ and Ag ₂ O are melting point lowering components for obtaining low melting point glass, and by mixing them in a predetermined ratio, both low temperature and water resistance can be achieved at the same time.

The glass composition preferably further contains _{Te O 2} and / or Li ₂ O as the first optional component. In the present invention, the optional component means a component that may or may not be contained. TeO ₂ is a low melting point component like _{V 2} O ₅ and Ag _{2 O.} Li ₂ O is a vitrification component that contributes to the improvement of adhesiveness and adhesion to the material to be sealed and the material to be bonded.

When the first optional component is contained, the molar% content of the first optional component is
Relational expression (2): [V ₂ O ₅ ] + [Ag ₂ O] + [TeO ₂ ] ≧ 73,
Relational expression (3): [Li ₂ O] ≤ 1/2 x [Ag ₂ O],
Relational expression (4): [Ag ₂ O] + [Li ₂ O] ≤ 2 × [V ₂ O ₅ ],
Relational expression (5): 20 ≤ [V ₂ O ₅ ] ≤ 45,
Relational expression (6): 12 ≤ [Ag ₂ O] ≤ 45,
Relational expression (7): 25 ≤ [TeO ₂ ] ≤ 47, and relational expression (8): 0 <[Li ₂ O] ≤ 15,
It is preferable to satisfy. When _{only one of TeO 2} and Li ₂ O is contained, the relational expression related to the component can be ignored.

The glass composition preferably further contains at least one of the group consisting _{of K 2} O, MgO, P ₂ O ₅ , BaO, ZnO, and WO ₃ as the second optional component. These second optional components are components that contribute to the reduction of the crystallization tendency.

When the second optional component is contained, the molar% content of the second optional component is
Relational expression (9): 0 <[K ₂ O] + [MgO] + [P ₂ O ₅ ] + [BaO] + [WO ₃ ] + [ZnO] ≤ 17,
It is preferable to satisfy. For the component not to be contained in the group of the second optional component, the mol% content of the component in the relational expression (9) may be set to "0 mol%".

This glass composition is in the group consisting _{of Al 2} O ₃ , Fe ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Er ₂ O ₃ , and Yb ₂ O _{3 as the third optional component.} It is preferable to contain one or more. These third optional components are components that contribute to the reduction of crystallization tendency and the improvement of water resistance (including moisture resistance).

When the third optional component is contained, the molar% content of the third optional component is
Relational expression (10): 0.3 ≤ [Al ₂ O ₃ ] + [Fe ₂ O ₃ ] + [Y ₂ O ₃ ] + [La ₂ O ₃ ] + [CeO ₂ ] + [Er ₂ O ₃ ] + [Yb ₂ O ₃ ] ≤ 7.5,
It is preferable to satisfy. For the component not to be contained in the group of the third optional component, the mol% content of the component in the relational expression (10) may be set to "0 mol%".

A glass composition satisfying the above composition exhibits excellent low-temperature softening characteristics with a _{transition point T g} of 260 ° C. or lower and a softening point T _{s of 330 ° C. or lower.} Details of the specific example will be described later.

The glass composition paste of the present invention is characterized in that it uses an aqueous solvent instead of an organic solvent. The liquid property of the aqueous solvent used (the glass composition paste using the same) is preferably neutral or alkaline. In other words, the pH of the aqueous solvent and the paste using the same is preferably 7 or more, more preferably 7.5 or more and 13 or less, and further preferably 8 or more and 12 or less. If the liquidity of the aqueous solvent is acidic, _{the stability of V 2} O ₅ which is a main component of the glass composition and the resin binder described later may be impaired.

When the glass composition paste of the present invention contains a resin binder for adjusting the viscosity of the paste, it is preferable to use a nonionic water-soluble thermoplastic resin as the resin binder. By using a non-ionic water-soluble thermoplastic resin, defects in the glass phase (for example, matting, generation of bubbles) that may occur due to an undesired chemical reaction during the heating and softening flow of the glass composition can be caused. It can be suppressed.

As a nonionic water-soluble thermoplastic resin, polyethylene oxide (PEO) can be mentioned as a typical example. The softer fluidity of the glass composition tends to be better as PEO having a larger weight average molecular weight is used, and it is particularly preferable that the weight average molecular weight is 3,500,000 or more. Since non-ionic water-soluble thermoplastic resins are generally easily decomposed in an acidic aqueous solution and tend to have a small molecular weight, it is preferable to keep the aqueous solvent of the paste neutral or alkaline.

When manufacturing a sealing structure having a glass sealing portion using a glass composition paste or a bonded body having a glass bonding layer, thermal expansion of the material to be sealed or the base material to be bonded and the glass composition / It is preferable that the glass composition paste is mixed with the thermal expansion adjusting filler powder so that the thermal shrinkage is consistent. Examples of the thermal expansion adjusting filler powder to be mixed include Zr ₂ (WO ₄ ) (PO ₄ ) ₂ (zirconium tungstate phosphate), Li ₂ O · Al ₂ O ₃ · 2SiO ₂ (β-eucryptite), and so on. _{2MgO · 2Al 2 O 3 · 5SiO} 2 ( _{cordierite), 3Al 2 O 3 · 2SiO} 2 ( mullite), SiO ₂ (silica), Nb ₂ O ₅ (niobium oxide), and among the group consisting of Si (silicon) Any one or more of the powders can be preferably used.

When the thermal expansion adjusting filler powder is mixed with the glass composition paste, the volume content of the thermal expansion adjusting filler powder is preferably 2.5 times or less with respect to the volume content of the glass composition. When the volume content of the thermal expansion adjusting filler powder is more than 2.5 times that of the glass composition, the softening flow during heating is hindered, and good adhesion and adhesion to the material to be sealed and the material to be bonded are obtained. It becomes difficult to obtain.

Further, when manufacturing an electric / electronic component having an electrode / wiring or a heat conductive bonding layer using a glass composition paste, good conductivity and heat conductivity are ensured in the electrode / wiring and the heat conductive bonding layer to be formed. Therefore, it is preferable that the metal powder is mixed with the glass composition paste. As the metal powder to be mixed, any one or more powders in the group consisting of Ag, Ag alloy, Cu, Cu alloy, Al, Al alloy, Sn, Sn alloy, Fe, and Fe alloy can be preferably used.

When the metal powder is mixed with the glass composition paste, the volume content of the metal powder is preferably 9 times or less the volume content of the glass composition. If the volume content of the metal powder is more than 9 times that of the glass composition, the amount of the glass composition will be insufficient, resulting in the formation of dense electrodes / wiring, adhesion to the substrate to be bonded, and the bonding layer itself. The mechanical strength of the glass becomes insufficient.

As a matter of course, the glass composition paste of the present invention may contain the thermal expansion adjusting filler powder and the metal powder at the same time.

(About the structure of the glass composition)
The glass composition used in the present invention has an extremely attractive property that an aqueous solvent can be used as a paste solvent while having a softening temperature (for example, 400 ° C. or lower) equivalent to that of a conventional lead-free low melting point glass composition. show. In investigating the cause of this property, it is of great interest whether there is a difference in the glass structure between the glass composition of the present invention and the conventional lead-free low melting point glass composition.

Here, a general feature of glass is that it is amorphous, unlike crystalline substances such as metals and minerals. One of the structural classifications of glass is a short-range structure (for example, the coordination number of cations, the bond distance between cations and anions, and the type of second proximity cation). Amorphous glass generally has an increased average bond distance between constituent atoms and a decreased coordination number of cations as compared with a crystalline substance having the same cation component.

In the present invention, in order to investigate the coordination number of the vanadium (V) component, which is considered to be the skeleton component (mesh forming component) of the glass composition, the wide-area X-ray absorption fine structure near the K absorption edge of the V component ( The radial structure function obtained by Fourier transforming EXAFS) was investigated. As a result, in the glass composition according to the present invention, the peak top intensity in the first coordination sphere of the radial structure function of the V component is extremely larger than _{the peak top intensity in the simple V 2} O _{5 crystal.} A peculiar phenomenon was seen. This means that the coordination number of the V component is larger than that in _{a single V 2} O _{5 crystal.}

Unfortunately, in the glass composition of the present invention, _{the mechanism that the coordination number of the V component is larger than that in the simple V 2} O ₅ crystal and the mechanism that the aqueous solvent can be used as the solvent for the paste can still be elucidated. Not. However, an increase in the coordination number of the V component means a decrease in the unbonded hands (empty sites that are not involved in the chemical bond) of the V atom, so that the adsorption sites and bond sites of water molecules are reduced and the water resistance is reduced. A model that improves sex is conceivable. Based on this model, it is preferable that the coordination number of the V component increases. Specifically, the peak top intensity in the first coordination sphere in the radial structure function of the V component is more preferably 1.1 times or more, more preferably 1.2 times or more, as compared with that _{of a simple V 2} O _{5 crystal.} More preferred.

Conventional technical knowledge / common general knowledge is that an increase in the coordination number of cations in glass significantly increases the characteristic temperature (transition point, yield point, softening point, etc.) of the glass composition. On the other hand, in the glass composition according to the present invention, although the coordination number of the V component _{is larger than that in the simple V 2} O ₅ crystal, the characteristic temperature is equal to or lower than the conventional one (for example, 260 ° C or lower). It has a transition point T _{g and a softening point T s} ) of 330 ° C or lower. Details of the specific example will be described later.

(Sealing structure)
The glass composition according to the present invention is applicable to various sealing structures. Suitable sealing structures include, for example, vacuum insulated double glazing panels in the field of housing parts, image display devices (flat panel displays, vacuum fluorescent displays, etc.) in the field of electrical and electronic parts, crystal oscillators, integrated circuit packages, and microscopic components. Examples include electromechanical systems (MEMS).

In the production of a sealed structure using a glass composition paste, the glass composition is roughly applied to a desired portion of the material to be sealed or the base material to be bonded by a coating method (for example, a screen printing method, a dispenser method, etc.). After applying the product paste, the solvent of the applied paste is heated and dried. Next, the glass composition is _{fired at a temperature about 20 to 50 ° C. higher than the softening point T s} of the contained glass composition to sufficiently soften and flow the glass composition so that it adheres to the substrate to be sealed or the substrate to be bonded. As a result, a sealed structure is manufactured.

Here, since the glass composition paste of the present invention uses an aqueous solvent, safety equipment (for example,, for example,) as in the case of a conventional glass composition paste using an organic solvent during the heating and drying step of the solvent. Explosion-proof heating / drying machine, abatement device, etc.) can be greatly simplified, and there is an advantage that the manufacturing cost of the sealed structure can be greatly reduced. That is, a low-cost sealing structure can be obtained.

(Electrical and electronic parts)
The glass composition according to the present invention can also be applied to electrodes / wirings and heat conductive bonding layers in various electrical and electronic components. Examples of electrical and electronic components having electrodes / wiring made of glass material and a heat conductive junction layer include solar cells, image display devices, multilayer capacitors, inductors, crystal oscillators, light emitting diodes (LEDs), multilayer circuit boards, and semiconductor modules. Can be mentioned.

In the production of an electric / electronic component having an electrode / wiring or a heat conductive bonding layer using a glass composition paste, it is desired to form an electrode / wiring or a heat conductive bonding layer as in the case of the above-mentioned sealing structure. After applying the glass composition paste to the base material / location of the above by a coating method (for example, screen printing method, dispenser method, etc.), the solvent of the applied paste is heated and dried. _{Next, firing is performed at a temperature about 20 to 50 ° C. higher than the softening point T s} of the contained glass composition to sufficiently soften and flow the glass composition to form an electrode / wiring or a heat conductive bonding layer. Electrical and electronic parts are manufactured by adhering to the base material / location. When the metal powder contained in the glass composition paste is a metal that easily oxidizes, it is desirable to set the firing atmosphere to an inert gas or vacuum in order to prevent the metal powder from oxidizing.

Hereinafter, the present invention will be described in detail based on specific examples and comparative examples. However, the present invention is not limited to the examples taken up here, and includes variations thereof.

[Experiment 1]
In Experiment 1, a glass composition paste was prepared using the powder of the low melting point glass composition shown in Table 1 described later and the solvent shown in Table 2, and the effect of the solvent on the glass composition paste (softening fluidity, aging). Stability) was examined.

As a starting material for each of the glass compositions GA-01 to GA-03 and GB-01 to GB-06, the commercially available reagents of the oxide powders shown in Table 1 (each having a purity of 99.9%) or the oxides shown in Table 1 are used. Commercially available reagents (each with a purity of 99.9%) of carbonate powder of the cation of the above were used. First, each starting material was weighed and mixed so as to obtain a desired glass composition, and a mixed raw material powder (about 200 g) was prepared. As can be estimated from the purity of the starting material, the glass composition in the present invention contains unavoidable impurities.

For the glass compositions GB-07 and GB-08, _{commercially available Bi 2} O ₃ glass compositions and Pb O glass compositions were prepared (commercially available products have a component ratio not disclosed).

A quartz glass crucible containing the mixed raw material powder is placed in a glass melting furnace and heated to 700 to 800 ° C at a heating rate of 10 ° C / min to melt the mixed raw material powder, and the melt in the quartz glass crucible is melted. It was held for 1 hour while stirring with an alumina rod to make the composition uniform. Then, the quartz glass crucible was taken out from the glass melting furnace, and the melt was poured into a stainless steel mold to prepare a bulk of the glass composition.

The bulk of the prepared glass composition was pulverized using a stamp mill and a jet mill to obtain a powder of a low melting point glass composition (D ₉₀ diameter = 45 μm, D ₅₀ = 10 to 15 μm).

Next, the low melting point glass composition powder and the solvent were mixed and kneaded in the mass ratio of "low melting point glass composition powder: solvent = 7: 3 to 8: 2" to prepare a glass composition paste.

In order to investigate the softening fluidity and the stability over time of the glass composition paste, the glass composition paste prepared above was stored at room temperature for a predetermined period (1 hour, 7, 30 days, 60 days). The glass composition paste after storage is applied on a quartz glass substrate in a predetermined size, and the solvent is heated and dried at 150 to 180 ° C. in the air, and then the temperature rise rate is 5 ° C./min in the air. , The glass composition was held at a temperature at which it sufficiently softened and flowed for 30 minutes) to prepare an evaluation sample.

The evaluation of the softening fluidity was based on the softening fluidity of the glass composition alone that was not mixed with the solvent. Specifically, the glass composition powder alone was placed on a quartz glass substrate so that the amount of the glass composition powder was the same as that of the evaluation sample and the size was the same, and the low melting point obtained under the same firing conditions as above was obtained. The state of the glass layer was used as a reference.

If the softening fluidity of the glass composition paste is higher than that of the glass composition alone, the size of the low melting point glass layer (eg, projected area) after firing of the evaluation sample should be larger than that of the reference sample. .. Therefore, compared to the size of the low melting point glass layer after firing of the reference sample, less than ± 5% is judged as "equivalent", + 5% or more is judged as "good", and -5% or less is judged as "bad". Judged. In addition, the surface condition (gloss, presence or absence of air bubbles) of the low melting point glass layer after firing was visually determined.

When the softening fluidity is "good" and the surface of the low melting point glass layer is "glossy", the sample is evaluated as "excellent", and the softening fluidity is "equivalent" and the surface of the low melting point glass layer is "glossy". If the sample is evaluated as "Passed" and the softening fluidity is "poor" and / or the surface of the low melting point glass layer is "matte" or "air bubbles are present". The sample was evaluated as "Failed". The evaluation results are summarized in Tables 3 and 4.

As shown in Tables 1 to 3, the glass compositions GA-01 to GA-03 are glass compositions according to the present invention, and are organic solvents SB-01 (ethanol) and SB-03 (α-terpineol). , SB-04 (dihydroterpineol) mixed paste, each rated "pass" for all 1 to 60 day storage. In addition, the paste obtained by mixing the glass compositions GA-01 to GA-03 and the organic solvent SB-02 (butyl carbitol acetate) was "passed" for only 1 hour, and "failed" for storage for 7 to 60 days. ".

On the other hand, the glass compositions GA-01 to GA-03 were evaluated as "excellent" in the paste mixed with the aqueous solvent SA-01 (pure water) in all of the storage for 1 hour to 60 days. It is confirmed that the softening fluidity and the stability over time are very excellent. In other words, it can be seen that the paste obtained by mixing the glass compositions GA-01 to GA-03 and the aqueous solvent SA-01 exhibits better softening fluidity than the paste mixed with the organic solvent.

On the other hand, the glass compositions GB-01 to GB-06 contain V ₂ O ₅ as a main component, but are glass compositions that deviate from the provisions of the present invention. The glass compositions GB-07 and GB-08 are commercially available Bi ₂ O ₃ based glass compositions and Pb O based glass compositions, respectively. The firing temperature of the glass compositions GB-05 to GB-08 had to be higher than those of the glass compositions GA-01 to GA-03.

As shown in Tables 1, 2 and 4, the glass composition GB-01 was "passed" in all combinations of organic solvents SB-03 to SB-04 for 1 hour to 60 days, respectively. It has been evaluated. However, the glass composition GB-01 was "passed" for only 1 hour each in combination with the aqueous solvent SA-01 and the organic solvents SB-01 to SB-02, and "failed" for storage for 7 to 60 days. Is.

The glass composition GB-02 was evaluated as "passed" in all combinations of the organic solvents SB-02 and SB-04 for 1 hour to 60 days, respectively. However, the glass composition GB-02 was "passed" for only 1 hour each in combination with the aqueous solvent SA-01, organic solvent SB-01 and SB-03, and was "failed" for storage for 7 to 60 days. Is.

The glass composition GB-03 was evaluated as "passed" in all combinations of the organic solvents SB-02 to SB-04 for 1 hour to 60 days, respectively. However, the glass composition GB-03, in combination with the aqueous solvent SA-01 and the organic solvent SB-01, each "failed" after storage for 1 hour to 60 days.

The glass compositions GB-04 to GB-06 were evaluated as "passed" in all of the 1 hour to 60 day storage in combination with the organic solvents SB-02 and SB-04, respectively. However, the glass composition GB-04 is "failed" in all of the 1 hour to 60 day storage in combination with the aqueous solvent SA-01, the organic solvent SB-01 and SB-03, respectively.

The glass compositions GB-07 to GB-08 were rated "passed" in all combinations of organic solvents SB-02 to SB-04 for 1 hour to 60 days, respectively. However, the glass composition GB-07 was "failed" in all 1 hour to 60 day storage in combination with the organic solvent SB-01, and was "failed" in combination with the aqueous solvent SA-01 for only 1 hour. With "pass", storage for 7 to 60 days is "fail".

Here, assuming the industrial production (mass production) of a sealing structure and electrical and electronic parts using the glass composition paste, it is considered that the glass composition paste needs to be stable over time for at least 7 days. Looking at the above results from this point of view, the softening fluidity of the combination of the glass compositions GB-01 to GB-08 and the aqueous solvent SA-01 was not "passed" or "excellent", and the combination with the aqueous solvent SA-01 was not found. Possible glass compositions (having stability over time for 7 days or more) are GA-01 to GA-03, and it can be seen that the softening fluidity is "excellent".

[Experiment 2]
In Experiment 2, the extended X-ray absorption fine structure (EXAFS) was measured for the glass compositions GA-01 to GA-03 and GB-01 to GB-06, for which a clear difference was observed in Experiment 1, and the glass was measured. The structure was investigated. Specifically, the EXAFS near the K-edge of the V component, which is considered to be the skeleton-forming component (mesh-forming component) of the glass compositions GA-01 to GA-03 and GB-01 to GB-06, is Fourier transformed. In the obtained radial structure function, the peak top intensity of the V component in the first coordination sphere was investigated. The peak top intensity _{of a single V 2} O ₅ crystal as a reference sample was also investigated. The EXAFS was measured using the large synchrotron radiation facility SPring-8.

FIG. 2 shows the radial structure obtained by Fourier transforming EXAFS near the K absorption edge of the V component in the glass compositions GA-01 to GA-03 and GB-01 to GB-06 and the elemental V ₂ O _{5 crystal.} It is a graph which shows the first coordination sphere region of a function. As shown in FIG. 2, the glass compositions GA-01 to GA-03 in which the aqueous solvent SA-01 can be used have a peak top in the first coordination sphere of the V component rather than _{a single V 2} O _{5 crystal.} It can be seen that the strength is high. This means that the coordination number of the V component is larger than that in _{a single V 2} O _{5 crystal.} On the other hand, it can be seen that the glass compositions GB-01 to GB-06, in which the aqueous solvent SA-01 cannot be used, have a smaller peak top intensity in the first coordination sphere of the V component than the _{simple V 2} O _{5 crystals.} ..

Amorphous glass generally has an increased average bond distance between constituent atoms and a reduced cation coordination number as compared to simple oxide crystals of constituent cation components. In the glass compositions GB-01 to GB-06, the peak top intensity of the V component in the first coordination sphere _{is smaller than that of the simple V 2} O ₅ crystal, which is as per the conventional technical wisdom. Results have been obtained.

On the other hand, in the glass compositions GA-01 to GA-03, the peak top intensity of the V component in the first coordination sphere _{is larger than that of the simple V 2} O ₅ crystal (coordination number of the V component). Is larger than that in a single V ₂ O ₅ crystal)), which is a very specific phenomenon. The detailed mechanism by which such a peculiar phenomenon occurs has not yet been elucidated, but it is thought that it is related to the coexistence of _{Ag 2 O, another major component, in a predetermined ratio.} An increase in the coordination number of the V component means a decrease in unbonded hands (empty sites that are not involved in chemical bonding) of the V atom. A model that makes it possible to use it is conceivable.

The increase in the coordination number of the network-forming component in glass is accompanied by an increase in the characteristic temperature (for example, transition point and softening point), but the glass composition of the present invention is another main component, Ag _2. It is considered that O contributes to lowering the characteristic temperature.

[Experiment 3]
In Experiment 3, based on the results of Experiments 1 and 2, the balance of the constituent components of the glass composition was examined.

Powders of glass compositions GC-01 to GC-15 were prepared in the same manner as in Experiment 1 so as to have the compositions shown in Table 5 described later, and the properties of the obtained glass compositions were investigated. The properties investigated were the characteristic temperature of the glass, the peak top intensity ratio of the vanadium radial structural function, and the compatibility with the aqueous solvent SA-01. The glass composition GC-14 in Table 5 means 63 _{V 2} O _{5 -37P 2} O ₅ , and the glass composition GC-15 means 50 V ₂ O ₅ -50 PbO.

The characteristic temperature of each glass composition was determined by DTA measurement. As the DTA measurement conditions, α-alumina was used as the reference sample, the mass of the reference sample and the measurement sample was 500 mg each, and the temperature rise rate was 5 ° C./min in the atmosphere. From the chart obtained by DTA measurement, the characteristic temperature was determined by the same definition as in FIG.

The peak top intensity ratio of the vanadium radial structure function of each glass composition is the first coordination zone in the radial structure function obtained by Fourier transforming EXAFS near the K absorption edge of the V component in the same manner as in Experiment 2. The peak top intensity of the glass composition was measured and used as the ratio of the peak top intensity of the glass composition to the peak top intensity of _{the single V 2} O _{5 crystal measured in Experiment 2.}

The compatibility of each glass composition with the aqueous solvent SA-01 is the same as in Experiment 1, after mixing and kneading with the aqueous solvent SA-01 to prepare a glass composition paste and storing it at room temperature for 7 days. An evaluation sample was prepared by firing at a temperature 20 to 30 ° C higher than the softening point T _{s, and the softening fluidity and surface condition were investigated.} The judgment / evaluation criteria were the same as in Experiment 1.

Table 6 summarizes the properties of the glass compositions GC-01 to GC-15.

As shown in Tables 5 to 6, the glass compositions GC-01 to GC-10 can measure their respective characteristic temperatures (T _g , T _d , T _s , T _cry ), and "T _g ≤ 223 ° C". , Has excellent softening properties of "T _s ≤ 270 ° C". On the other hand, the glass compositions GC-11 to GC-12 were easy to crystallize and could not measure _{clear T s.} From this, it can be seen that _{the molar ratio of V 2} O ₅ to Ag ₂ O in the glass composition is preferably "[Ag ₂ O] / [V ₂ O ₅ ] ≤ 2.0".

The peak top intensity ratio of the vanadium radial structure function obtained by performing the same EXAFS measurement as in Experiment 2 for the glass compositions GC-01 to GC-10 shows that V ₂ O ₅ and Ag ₂ O in the glass composition. It can be seen that the peak top intensity ratio of the vanadium radial structure function tends to increase as the molar ratio “[Ag ₂ O] / [V ₂ O _{5]” increases.} It can also be seen that the peak top intensity ratio of the vanadium radial structure function is greater than 1.00 when "1/3 ≤ [Ag ₂ O] / [V ₂ O _5]".

The peak top intensity ratio of the vanadium radial structure function of the glass compositions GC-13 to GC-14 containing no Ag _{2 O is less than 1.00.} On the other hand, the glass composition GC-15 containing PbO in place of Ag ₂ O is a peak top intensity ratio of vanadium radial structure function is 1.00 greater, since it contains PbO, green procurement Green Design Does not fit the concept.

Regarding compatibility with the aqueous solvent SA-01, the glass compositions GC-02 to GC-10 having a peak top intensity ratio of the vanadium radial structure function of more than 1.00 are "excellent" as in the results of Experiments 1 and 2. However, it can be seen that the glass composition GC-01 having the peak top intensity ratio of less than 1.00 is "failed".

From the above, it can be seen that _{the molar ratio of V 2} O ₅ to Ag ₂ O in the glass composition is preferably "1/3 ≤ [Ag ₂ O] / [V ₂ O ₅ ] ≤ 2.0". In other words,
Relational expression (1): 1/3 × [V ₂ O ₅ ] ≤ [Ag ₂ O] ≤ 2 × [V ₂ O ₅ ],
Is established.
Further, regarding the peak top intensity ratio of the vanadium radial structure function, it can be seen that the peak top intensity ratio exceeding 1.00 is preferable.

[Experiment 4]
In Experiment 4, based on the results of Experiments 1 to 3, the constituent components of the glass composition and their balance were further investigated.

Powders of glass compositions GD-01 to GD-18 were prepared in the same manner as in Experiment 1 so as to have the compositions shown in Table 7, and the properties of each glass composition obtained in the same manner as in Experiment 3 were investigated. .. The properties investigated were the characteristic temperature of the glass, the peak top intensity ratio of the vanadium radial structural function, and the compatibility with the aqueous solvent SA-01.

In the compatibility test with the aqueous solvent SA-01, the softening fluidity and stability over time were investigated using the glass composition paste stored for 100 days. As a result, the softening fluidity by firing was "good". When the surface of the low melting point glass layer was "glossy", the sample was evaluated as "highest: Brilliant".

Table 8 summarizes the properties of the glass compositions GD-01 to GD-18.

As shown in Tables 7 to 8, the glass compositions GD-01 to GD-16 can measure their respective characteristic temperatures (T _g , T _d , T _s , T _cry ), and "T _g ≤ 219 ° C". , Has excellent softening properties of "T _s ≤ 263 ° C". On the other hand, the glass compositions GD-17 to GD-18 were easy to crystallize and could not _{clearly measure T s. From this, the molar ratio of V 2} O ₅ and Ag ₂ O to Li ₂ O in the glass composition is "([Ag ₂ O] + [Li ₂ O]) / [V ₂ O ₅ ] ≤ 2.0". It turns out that is preferable. From this result, it is considered that Ag and Li bind to the same site for V in the glass structure.

The peak top intensity ratio of the vanadium radial structure function obtained by performing the same EXAFS measurement as in Experiment 2 for the glass compositions GD-01 to GD-16 shows that V _{2 in the glass composition is the same as in Experiment 3.} As the molar ratio of _{O 5} to Ag _{2 O "[Ag 2} O] / [V ₂ O ₅ ]" increases, the peak top intensity ratio of the vanadium radial structure function tends to increase, and "1/3 ≤" It can be seen that "[Ag ₂ O] / [V ₂ O _{5]" is preferable.}

However, when the molar ratio "[Li ₂ O] / [Ag _{2 O]" of Ag 2} O and Li ₂ O in the glass composition approaches 1, the peak top intensity ratio becomes less than 1.00. It can be seen that the peak top intensity ratio is larger than 1.00 when "[Li ₂ O] / [Ag ₂ O] ≤ 1/2".

Regarding compatibility with the aqueous solvent SA-01, similar to the results of Experiments 1 to 3, the glass compositions GC-02, GC-13 to GC-, in which the peak top intensity ratio of the vanadium radial structure function is less than 1.00. 14 is "failed", but the glass compositions GC-01, GC-03 to GC-12, and GC-15 to GC-16 having the peak top intensity ratio of more than 1.00 are "excellent" or "highest". It turns out that. In particular, when the peak top intensity ratio is 1.20 or more, it can be seen that the "highest" evaluation is shown.

From the above, _{the balance between V 2} O ₅ and Ag ₂ O and Li ₂ O in the glass composition is "1/3 ≤ [Ag ₂ O] / [V ₂ O ₅ ]", "( It can be seen that [Ag ₂ O] + [Li ₂ O]) / [V ₂ O ₅ ] ≤ 2.0 "and" [Li ₂ O] / [Ag ₂ O] ≤ 1/2 "are preferable. In other words,
Relational expression (1): 1/3 × [V ₂ O ₅ ] ≤ [Ag ₂ O] ≤ 2 × [V ₂ O ₅ ],
Relational expression (3): [Li ₂ O] ≤ 1/2 × [Ag ₂ O], and relational expression (4): [Ag ₂ O] + [Li ₂ O] ≤ 2 × [V ₂ O ₅ ],
Is established.
Further, regarding the peak top intensity ratio of the vanadium radial structure function, it can be seen that the peak top intensity ratio of more than 1.00 is preferable, and 1.20 or more is more preferable.

[Experiment 5]
In Experiment 5, based on the results of Experiments 1 to 4, the constituent components of the glass composition and their balance were examined in more detail.

Powders of glass compositions GE-01 to GE-71 and GF-01 to GF-16 were prepared in the same manner as in Experiment 1 so as to have the compositions shown in Tables 9 to 12, and the obtained glass compositions were prepared. The properties were investigated. The properties investigated were the characteristic temperature of the glass, the coefficient of thermal expansion, the density, and the compatibility with the aqueous solvent SA-01. The investigation of the characteristic temperature and compatibility with the aqueous solvent SA-01 was carried out in the same manner as in Experiment 3.

Density measurement was performed on each of the prepared glass composition powders by a pycnometer method in helium gas.

In the measurement of the coefficient of thermal expansion, first, a pressure powder molded product is formed using each of the prepared glass composition powders, and fired at a temperature 20 to 30 ° C. higher than _{the softening point T s of the glass composition, and then fired.} , A measurement sample was prepared by grinding into a prismatic shape (4 mm × 4 mm × 20 mm). Next, each measurement sample was determined by measuring the thermal expansion curve at a heating rate of 5 ° C./min in the atmosphere using a thermal expansion meter. The measurement temperature range of the coefficient of thermal expansion was set to a temperature from 30 ° C. to less than the _{transition point T g of the glass composition.}

Tables 13 to 16 summarize the component balance and property survey results of the glass compositions GE-01 to GE-71 and GF-01 to GF-16.

As shown in Tables 9 to 16, the glass compositions GE-01 to GE-71 can measure their respective characteristic temperatures (T _g , T _d , T _s , T _cry ), and "T _g ≤ 256 ° C". , Has excellent softening properties of "T _s ≤ 320 ° C". In addition, it can be seen that the glass compositions GE-01 to GE-71 are all evaluated as "excellent" in terms of compatibility with the aqueous solvent SA-01.

On the other hand, the glass compositions GF-01 to GF-16 can measure their respective characteristic temperatures (T _g , T _d , T _s , T _cry ) in the same manner as the glass compositions GE-01 to GE-71. It _{exhibits excellent softening characteristics of "T g} ≤ 242 ° C" and "T _s ≤ 300 ° C". However, it can be seen that all the glass compositions GF-01 to GF-16 are evaluated as "failed" in terms of compatibility with the aqueous solvent SA-01.

Therefore, when the component balance of the glass compositions GE-01 to GE-71 was examined closely, it was confirmed that the following relational expression was satisfied.
Relational expression (1): 1/3 × [V ₂ O ₅ ] ≤ [Ag ₂ O] ≤ 2 × [V ₂ O ₅ ],
Relational expression (2): [V ₂ O ₅ ] + [Ag ₂ O] + [TeO ₂ ] ≧ 73,
Relational expression (3): [Li ₂ O] ≤ 1/2 × [Ag ₂ O], and relational expression (4): [Ag ₂ O] + [Li ₂ O] ≤ 2 × [V ₂ O ₅ ],
Is established.
In the _{glass compositions GE-01 to GE-14 containing no Li 2} O, the relational expressions (3) to (4) are ignored.

Regarding the second optional component (one or more of the group consisting of _{K 2} O, MgO, P ₂ O ₅ , BaO, ZnO, and WO ₃₎
Relational expression (9): 0 <[K ₂ O] + [MgO] + [P ₂ O ₅ ] + [BaO] + [WO ₃ ] + [ZnO] ≤ 17,
Is established. For the component not to be contained in the group of the second optional component, the mol% content of the component in the relational expression (9) is calculated as "0 mol%".

For the third optional component (one or more of the group consisting of _{Al 2} O ₃ , Fe ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Er ₂ O ₃ , and Yb ₂ O ₃₎
Relational expression (10): 0.3 ≤ [Al ₂ O ₃ ] + [Fe ₂ O ₃ ] + [Y ₂ O ₃ ] + [La ₂ O ₃ ] + [CeO ₂ ] + [Er ₂ O ₃ ] + [Yb ₂ O ₃ ] ≤ 7.5,
Is established. For the component not to be contained in the group of the third optional component, the mol% content of the component in the relational expression (10) is calculated as "0 mol%".

Furthermore, when the results of the previous experiments 3 to 4 are combined and examined closely,
Relational expression (5): 20 ≤ [V ₂ O ₅ ] ≤ 45,
Relational expression (6): 12 ≤ [Ag ₂ O] ≤ 45,
Relational expression (7): 25 ≤ [TeO ₂ ] ≤ 47, and relational expression (8): 0 <[Li ₂ O] ≤ 15,
It turns out that is established. In _{the case of a glass composition containing no Li 2} O, the relational expression (8) is ignored.

The glass compositions GF-01 to GF-16 whose compatibility with the aqueous solvent SA-01 is "failed" must not satisfy any one or more of the above relational formulas (1) to (8). It is confirmed.

[Experiment 6]
In the glass composition paste, a resin binder is often mixed with the paste as a viscosity modifier for facilitating application to the substrate to be sealed or the substrate to be bonded. In Experiment 6, a water-soluble resin binder suitable for using an aqueous solvent as the paste solvent was examined.

Table 17 shows the water-soluble resin binder used in the study. BA-01 to BA-02 are non-ionic water-soluble thermoplastic resins, and BB-01 to BB-07 are ionic (cationic or anionic) water-soluble thermoplastic resins.

A 3% by mass resin binder aqueous solution was prepared by dissolving the water-soluble resin binders BA-01 to BA-02 and BB-01 to BB-07 in the aqueous solvent SA-01, respectively. If necessary, it was dissolved by heating so that no undissolved substance remained (for example, stirring and dissolving at 50 ° C.).

Next, the glass composition powder prepared in Experiment 5 and the resin binder aqueous solution were mixed and kneaded in the range of "glass composition powder: resin binder aqueous solution = 7: 3 to 8: 2" to prepare a glass composition paste. .. Glass composition powders include GE-02, GE-11, GE-34, GE-35, GE-40, GE-46, GE-51, GE-54, GE-60, GE-61, GE-62. , And GE-68 were used.

For these 12 types of glass composition powders, the same EXAFS measurement as in Experiment 2 was performed to determine the peak top intensity ratio of the vanadium radial structure function. As a result, 1.32, 1.20, 1.24, 1.29, 1.33, respectively. It was 1.30, 1.22, 1.24, 1.30, 1.32, 1.23, and 1.24, and it was confirmed that all of them were 1.20 or higher.

Next, each of the prepared glass composition pastes was stored at room temperature for 7 days, then coated on a quartz glass substrate in a predetermined size, and under predetermined conditions (in the air, no heat-drying step, 5 ° C./min rise). An evaluation sample was prepared by firing at a temperature rate (held at a temperature 20 to 30 ° C. higher than the softening point T _{s of the glass composition for 30 minutes).} The softening fluidity and surface condition of the evaluation sample were investigated according to the same judgment / evaluation criteria as in Experiment 1. The evaluation results are summarized in Table 18.

As shown in Table 18, the glass composition paste using the ionic water-soluble resin binders BB-01 to BB-07 was evaluated as "failed" in combination with any of the glass compositions. .. On the other hand, the glass composition paste using the non-ionic water-soluble resin binders BA-01 to BA-02 was evaluated as "passed" in combination with any of the glass compositions.

When the softening fluidity of the glass composition paste using the nonionic water-soluble resin binders BA-01 to BA-02 was observed in more detail, the glass composition paste using BA-01 was used rather than BA-02. Showed higher softening fluidity.

From the above results, it can be seen that in the glass composition paste of the present invention using an aqueous solvent, a nonionic water-soluble thermoplastic resin is preferable as the resin binder. The detailed mechanism by which the glass composition paste with the ionic water-soluble resin binder was "failed" has not yet been fully elucidated, but for example, during storage and / or firing of the glass composition paste. It is possible that the ions dissociated in the resin binder aqueous solution are corroding the glass composition in the paste.

[Experiment 7]
As described above, in Experiment 6, the glass composition paste using the water-soluble resin binder BA-01 showed higher softening fluidity than the one using BA-02. In Experiment 7, the effect of the weight average molecular weight of BA-01 (polyethylene oxide) on the softening fluidity of the glass composition paste was investigated.

Using the polyethylene oxide resin binders BA-01a to BA-01h shown in Table 19, an aqueous resin binder solution was prepared so as to have the resin binder concentration in the table. At this time, it was dissolved by heating as necessary so that no undissolved substance remained (for example, stirring and dissolving at 50 ° C.). The BA-01 used in Experiment 6 corresponds to BA-01d in Experiment 7.

Next, in the same manner as in Experiment 6, the glass composition powder and the resin binder aqueous solution are mixed and kneaded in the range of "glass composition powder: resin binder aqueous solution = 7: 3 to 8: 2" to prepare a glass composition paste. Made. An evaluation sample for evaluation of softening fluidity was prepared using each of the prepared glass composition pastes, and the softening fluidity and surface state of the evaluation sample were investigated. The evaluation results are summarized in Table 20.

As shown in Table 20, the glass composition pastes using the resin binders BA-01a to BA-01h were evaluated as "passed" or higher in combination with any of the glass compositions, but the weight average molecular weight of the resin was evaluated. The larger the value, the more the softening fluidity of the glass composition paste tends to improve. In particular, in a glass composition paste using a resin binder having a weight average molecular weight of 3,500,000 or more, the softening fluidity is evaluated as "excellent".

When the stability over time was investigated in the glass composition paste evaluated as "excellent" in the same manner as in Experiment 1, it was separately confirmed that the glass composition paste was evaluated as "excellent" even after storage for 60 days.

From the results of Experiments 6 to 7, the resin binder used in the glass composition paste of the present invention is more preferably polyethylene oxide, which is a nonionic water-soluble thermoplastic resin, and further preferably polyethylene oxide having a weight average molecular weight of 3,500,000 or more. It can be said that.

[Experiment 8]
In Experiment 7, it was observed that the glass composition paste stored for 60 days and the paste using a glass composition other than GE-02 and GE-11 tended to have improved softening fluidity as compared with the glass composition paste stored for 7 days. Was done. In Experiment 8, the factors were investigated.

In addition to the glass composition paste prepared in Experiment 7 (containing resin binder BA-01f, stored for 60 days), a new glass composition paste containing resin binder BA-01f and stored for 1 hour was newly prepared, and the liquid property of the paste was prepared. (PH) was measured and compared.

As a result, the paste using the glass composition of GE-02 and GE-11 was neutral (pH = 7) with no change in liquid property between 1 hour storage and 60 days storage. On the other hand, in the pastes using other glass compositions, the liquid property of the paste stored for 1 hour is neutral (pH = 7), and the liquid property of the paste stored for 60 days is clearly alkaline (pH> 7). ).

Comparing the chemical compositions of the glass compositions used in Experiment 7 (see Tables 9 to 12), the difference between GE-02 and GE-11 and the others was considered to be "presence or absence of _{Li 2 O component".} For pastes using glass compositions other than GE-02 and GE-11, it is possible that some Li ions were eluted from the glass composition during storage and the liquid nature of the paste changed to alkaline. rice field.

In order to investigate the effect of the liquid property of the paste on the softening fluidity, lithium hydroxide (LiOH) was added and dissolved in the paste using the glass composition GE-02 (containing resin binder BA-01f, stored for 1 hour). Then, a glass composition paste was prepared in which the liquid property of the paste was intentionally adjusted to be alkaline. Next, using the glass composition paste, an evaluation sample for evaluation of softening fluidity was prepared in the same manner as in Experiment 6, and the softening fluidity and surface state of the evaluation sample were investigated.

As a result, the evaluation sample prepared from the glass composition paste whose liquid property is intentionally adjusted to be alkaline may have improved softening fluidity as compared with the evaluation sample prepared from the glass composition paste having neutral liquid property. confirmed. From the results of this experiment, it was found that the liquid property of the glass composition paste is preferably "pH ≥ 7" and more preferably "pH> 7".

[Experiment 9]
When sealing or bonding with a glass composition paste, a thermal expansion adjusting filler powder is often mixed with the paste in order to match the thermal expansion / contraction with the material to be sealed or the base material to be bonded. In Experiment 9, a glass composition paste containing a thermal expansion adjusting filler powder and bonding using the paste were examined.

Table 21 shows the thermal expansion adjusting filler powder used in the study. F-01 to F-02 are materials with a negative coefficient of thermal expansion, F-03 to F-04 are materials with a coefficient of thermal expansion close to "0", and F-05 to F-07 are common. It is a material that is said to have a small coefficient of thermal expansion. Filler powders F-01 to F-07 having an average particle size (D ₅₀ ) in the range of 10 to 50 μm were used.

First, a resin binder aqueous solution in which 1% by mass of a water-soluble resin binder BA-01f was dissolved in an aqueous solvent SA-01 was prepared. Next, the glass composition powder, the thermal expansion adjusting filler powder, and the resin binder aqueous solution were mixed and kneaded at a predetermined ratio to prepare a glass composition paste.

As the glass composition powder, three types of GE-34, GE-51, and GE-61 prepared in Experiment 5 were used. The volume content of the heat expansion adjusting filler powder to be mixed was 0.5 to 3 times the volume content of the glass composition powder. The total mass content of the glass composition powder and the thermal expansion adjusting filler powder was 75% by mass, and the mass content of the resin binder aqueous solution was 25% by mass.

Using each of the prepared glass composition pastes, a bonded body (joint evaluation sample) in which the same types of base materials to be bonded were bonded to each other was prepared, and the breaking stress in the shearing direction at the joint was measured to evaluate the bondability. .. Table 22 shows the base materials to be bonded used in the experiment.

FIG. 3 is a schematic schematic diagram showing a method for producing a joint body as a joint portion evaluation sample.

FIG. 3A: A columnar base material 11 (diameter 3 mm × thickness 2 mm) having a circular joint surface 12 is prepared. FIG. 3B: A glass composition paste is applied to the circular bonding surface 12 of the columnar base material 11 to form a coating film 13. FIG. 3C: The solvent contained in the coating film 13 is heat-dried (for example, held at 60 ° C. for 20 minutes in the air) to form a dry coating film 14. FIG. 3 (d): A plate-shaped base material 15 (thickness 1 to 3 mm) to be paired with the bonded body is prepared, and a dry coating film 14 of the columnar base material 11 is applied on the main surface of the plate-shaped base material 15. established by contact, and a cylindrical base member 11 and the plate-shaped substrates 15 are clipped heat-resistant, a predetermined condition (e.g., in the atmosphere, about 30 to 50 ° C. higher than the softening point T _s of the glass composition Heat at a heating rate of 5 ° C./min to a temperature and hold for 30 minutes) to bake to prepare the bonded body 10.

As a reference sample for determining the bondability at the joint, a Cu / Cu junction in which Cu base materials of the same size as the joint evaluation sample were bonded using lead-free tin solder was separately prepared. Cu base material and lead-free tin solder are examples that are generally considered to be a combination that provides good bonding. The breaking stress in the shearing direction at the joint of the reference sample was measured and found to be 20 to 30 MPa. Therefore, when the breaking stress in the joint evaluation sample is less than 20 MPa, it is evaluated as "failed", when the breaking stress is 20 MPa or more and 30 MPa or less, it is evaluated as "passed", and the breaking stress is more than 30 MPa. The case was evaluated as "excellent".

Table 23 shows the evaluation results of bondability in the bonded body of Ni substrates.

As shown in Table 23, all the measured joints were evaluated as "excellent". From this, it can be seen that the glass composition paste of the present invention containing the thermal expansion adjusting filler powder exhibits excellent bondability in low temperature bonding between Ni substrates.

Next, Table 24 shows the evaluation results of the bondability of the bonded body of Fe base materials.

As shown in Table 24, all the measured joints were evaluated as "excellent". From this, it can be seen that the glass composition paste of the present invention containing the thermal expansion adjusting filler powder exhibits excellent bondability in low temperature bonding between Fe substrates.

Next, Table 25 shows the evaluation results of the bondability of the soda lime glass base materials in a bonded body.

As shown in Table 25, a bonded body having a volume ratio of “filler powder / glass composition powder” of 2.5 or less in the glass composition paste is evaluated as “excellent” or “passed”. From this, it can be seen that the glass composition paste of the present invention containing the thermal expansion adjusting filler powder exhibits excellent bondability in low temperature bonding between soda lime glass substrates.

Next, Table 26 shows the evaluation results of the bondability of the borosilicate glass substrates to each other.

As shown in Table 26, a bonded body having a volume ratio of “filler powder / glass composition powder” of 2.5 or less in the glass composition paste is evaluated as “excellent” or “passed”. From this, it can be seen that the glass composition paste of the present invention containing the thermal expansion adjusting filler powder exhibits excellent bondability in low temperature bonding between borosilicate glass substrates.

Next, Table 27 shows the evaluation results of the bondability of the bonded body of the alumina base materials.

As shown in Table 27, a bonded body having a volume ratio of “filler powder / glass composition powder” of 2.5 or less in the glass composition paste is evaluated as “excellent” or “passed”. From this, it can be seen that the glass composition paste of the present invention containing the thermal expansion adjusting filler powder exhibits excellent bondability in low temperature bonding between alumina base materials.

Next, Table 28 shows the evaluation results of the bondability of the silicon nitride base materials in the bonded body.

As shown in Table 28, a bonded body having a volume ratio of “filler powder / glass composition powder” of 2.5 or less in the glass composition paste is evaluated as “excellent” or “passed”. From this, it can be seen that the glass composition paste of the present invention containing the thermal expansion adjusting filler powder exhibits excellent bondability in low temperature bonding between silicon nitride substrates.

Next, Table 29 shows the evaluation results of the bondability of the bonded body of the silicon base materials.

As shown in Table 29, a bonded body having a volume ratio of “filler powder / glass composition powder” of 2.5 or less in the glass composition paste is evaluated as “excellent” or “passed”. From this, it can be seen that the glass composition paste of the present invention containing the thermal expansion adjusting filler powder exhibits excellent bondability in low temperature bonding between silicon substrates.

From the above results, it was confirmed that the glass composition paste of the present invention exhibits excellent bondability in low temperature bonding of various substrates by containing the thermal expansion adjusting filler powder. Further, it was confirmed that the volume ratio of "filler powder / glass composition powder" in the glass composition paste is preferably 2.5 or less. In Experiment 9, the thermal expansion adjusting filler powders F-01 to F-07 were used for investigation, but the present invention is not limited thereto.

[Experiment 10]
When forming electrodes / wirings, conducting conductive bonding or thermally conductive bonding using a glass composition paste, metal powder is often mixed with the paste in order to ensure conductivity and heat transfer. In Experiment 10, a glass composition paste containing a metal powder and bonding using the paste were examined.

As metal powder, Ag powder (spherical particles, average particle size (D ₅₀ ) 2 μm), Cu powder (spherical particles, average particle size (D ₅₀ ) 15 μm), Al powder (spherical particles, average particle size (D ₅₀ ) 3 μm) ) And Sn powder (spherical particles, average particle size (D ₅₀ ) 20 μm) were prepared. As the glass composition powder, the glass compositions GE-02 and GE-39 (average particle size (D ₅₀ ) 3 μm, respectively) prepared in Experiment 5 were used.

In preparing the glass composition paste, first, an aqueous resin binder solution prepared by dissolving 0.6% by mass of the water-soluble resin binder BA-01h in the aqueous solvent SA-01 was prepared. Next, the glass composition powder, the metal powder, and the resin binder aqueous solution were mixed and kneaded at a predetermined ratio to prepare a glass composition paste. At this time, the volume content of the metal powder to be mixed was set to 1 to 9 times the volume content of the glass composition powder. The total mass content of the glass composition powder and the metal powder was 75% by mass, and the mass content of the resin binder aqueous solution was 25% by mass.

Using each of the prepared glass composition pastes, a bonded body (joint evaluation sample) in which the same or different types of substrates to be bonded are bonded to each other is prepared, and the connection resistance at the junction (electrical resistance between the substrates to be bonded). Was measured by the four-terminal method to evaluate the bondability.

Specifically, Al, Cu, Ni, and Fe are used as the base material to be bonded, and the combination of Al base materials (Al / Al junction) and the combination of Al base material and Cu base material are used as the joint evaluation sample. (Al / Cu bonded body), a combination of an Al base material and a Ni base material (Al / Cu bonded body), and a combination of an Al base material and a Fe base material (Al / Fe bonded body) were prepared.

The joint body to be the joint portion evaluation sample is basically produced according to FIG.

Specifically, as in Experiment 9, FIG. 3A: a columnar base material 11 (diameter 3 mm × thickness 2 mm) having a circular joint surface 12 is prepared. FIG. 3B: A glass composition paste is applied to the circular bonding surface 12 of the columnar base material 11 to form a coating film 13. FIG. 3 (c): The columnar base material 11 on which the coating film 13 is formed is raised to a temperature of about 30 to 50 ° C. higher than _{the softening point T s of the glass composition under predetermined conditions (for example, 5 ° C./min).} (Heating at a temperature rate and holding for 10 minutes) is fired to form a fired coating film 14'. FIG. 3 (d): A plate-shaped base material 15 (thickness 1 to 3 mm) to be paired with the joint is prepared, and the fired coating film 14'of the columnar base material 11 is placed on the main surface of the plate-shaped base material 15. The columnar base material 11 and the plate-like base under predetermined conditions (for example, applied pressure 14 to 21 MPa, applied current 5 kA, applied time 100 to 200 msec) using a resistance welder. Weld the material 15 to make a joint 10'.

Further, as in Experiment 9, as a reference sample for determining the connection resistance at the joint, a Cu / Cu junction in which Cu base materials of the same size as the joint evaluation sample are bonded using lead-free tin solder is used. (Cu / Cu standard sample) was prepared separately.

Further, an Al / Al comparison sample, an Al / Cu comparison sample, an Al / Ni comparison sample, and an Al / Fe comparison sample were separately prepared as comparison samples of the connection resistance at the junction. The bonding in the comparative sample was carried out by sandwiching lead-free tin solder between the substrates and performing predetermined firing (holding in argon gas at 250 ° C. for 10 minutes) while pressing the solder. Since the Al base material is inferior in solder wettability, it was joined by the method (pinching, pressing, firing).

Table 30 shows the connection resistances of the prepared reference sample and comparative sample.

As shown in Table 30, the Cu / Cu reference sample shows a ^{very low connection resistance on the order of 10 -6} Ω / mm ² , while the Al / Al comparison sample, Al / Cu comparison sample, and Al / Ni comparison. It can be seen that the connection resistance of the sample and the Al / Fe comparison sample is on the ^{order of 10 -3} Ω / mm ² and is more than 3 orders of magnitude higher than that of the Cu / Cu standard sample. The high connection resistance of the comparative sample is considered to be due to the chemically stable natural oxide film formed on the surface of the Al base material, in which at least one of the base materials to be bonded is an Al base material.

FIG. 4 shows the relationship between the volume ratio of "Ag powder / GE-39 powder" in the paste and the connection resistance of various conjugates in the glass composition paste in which the glass composition GE-39 powder and Ag powder are mixed. It is a graph which shows.

^{As shown in FIG. 4, the present glass composition paste is 10 -6} Ω / mm in any of the Al / Al conjugate, the Al / Cu conjugate, the Al / Cu conjugate, and the Al / Fe conjugate. ^It can be seen that a very low connection resistance of 2 orders can be achieved. The connection resistance on the order of 10 ^-6 Ω / mm ² is equivalent to the connection resistance of the Cu / Cu reference sample, and is about 3 orders of magnitude lower than the connection resistance of each comparison sample.

In addition, in the volume ratio of "Ag powder / GE-39 powder", the connection resistance of the bonded body tends to decrease as the volume ratio increases, and a very stable connection resistance is obtained especially in the range of volume ratio 4 to 9. It turns out that it will be done.

The following model can be considered as a factor for obtaining such a low connection resistance in the bonded body containing the Al base material.

In the glass composition / glass composition paste of the present invention, the main component V ₂ O ₅ combines with the natural oxide film on the surface of the Al substrate during heat softening and flow to remove the oxide film, thereby removing the Al substrate. In addition to reducing the electrical resistivity of the surface, Ag metal particles are more likely to precipitate from the Ag ₂ O component, which is another major component, as _{the V 2} O _{5 component in the glass structure is consumed, and the precipitated Ag particles are separated from each other.} A model is conceivable in which the conductivity of the bonding layer is improved by growing so as to be connected.

FIG. 5 shows the relationship between the volume ratio of "Cu powder / GE-39 powder" in the paste and the connection resistance of various conjugates in the glass composition paste in which the glass composition GE-39 powder and Cu powder are mixed. It is a graph which shows. ^{As shown in FIG. 5, this glass composition paste also has 10 -6} Ω / mm ^{2 in} any of the Al / Al conjugate, the Al / Cu conjugate, the Al / Cu conjugate, and the Al / Fe conjugate. It turns out that very low connection resistance on the order can be achieved.

FIG. 6 shows the relationship between the volume ratio of “Al powder / GE-02 powder powder” in the paste and the connection resistance of various conjugates in the glass composition paste obtained by mixing the glass composition GE-02 powder and the Al powder. It is a graph which shows. ^{As shown in FIG. 6, this glass composition paste also has 10 -6} Ω / mm ^{2 in} any of the Al / Al conjugate, the Al / Cu conjugate, the Al / Cu conjugate, and the Al / Fe conjugate. It turns out that very low connection resistance on the order can be achieved.

FIG. 7 shows the relationship between the volume ratio of “Sn powder / GE-02 powder powder” in the paste and the connection resistance of various conjugates in the glass composition paste in which the glass composition GE-02 powder and Sn powder are mixed. It is a graph which shows. ^{As shown in FIG. 7, this glass composition paste also has 10 -6} Ω / mm ^{2 in} any of the Al / Al conjugate, Al / Cu conjugate, Al / Cu conjugate, and Al / Fe conjugate. It turns out that very low connection resistance on the order can be achieved.

From the above results, it was confirmed that the glass composition paste of the present invention exhibits a very low connection resistance in low temperature bonding of various substrates by containing a metal powder. Further, it was confirmed that the volume ratio of "metal powder / glass composition powder" in the glass composition paste is preferably in the range of 1 to 9. In addition, since there is a high correlation between conductivity and thermal conductivity, the glass composition paste of the present invention containing a metal powder can be expected to have the same effect in thermal conductive bonding.

In Experiment 10, Ag powder, Cu powder, Al powder, and Sn powder were used as the metal powder for investigation, but the present invention is not limited thereto, and examples thereof include Au powder and Fe powder. In addition, Al / Al conjugates, Al / Cu conjugates, Al / Cu conjugates, and Al / Fe conjugates have been examined as applicable conjugates, but the present invention is not limited thereto, and for example, one of them is used. Examples thereof include a bonded body made of an Mg base material and a bonded body made of a Ti base material on one side.

[Experiment 11]
In Experiment 11, the formation of the electrode / wiring using the glass composition paste containing the metal powder and the properties of the electrode / wiring were examined.

Ag powder (spherical particles, average particle size (D ₅₀ ) 1.5 μm) was used as the metal powder, and the glass composition GE-60 (average particle size (D ₅₀ ) 1 μm) prepared in Experiment 5 was used as the glass composition powder. Was used.

In preparing the glass composition paste, first, an aqueous resin binder solution prepared by dissolving 0.8% by mass of the water-soluble resin binder BA-01g in the aqueous solvent SA-01 was prepared. Next, the glass composition GE-60 powder, Ag powder, and the resin binder aqueous solution were mixed and kneaded at a predetermined ratio to prepare a glass composition paste. At this time, the volume content of the Ag powder to be mixed was set to 1 to 9 times the volume content of the glass composition GE-60 powder. The total mass content of the glass composition GE-60 powder and Ag powder was 75% by mass, and the mass content of the resin binder aqueous solution was 25% by mass.

Using each of the prepared glass composition pastes, a wiring board (wiring evaluation sample) in which electrodes / wirings are formed on various substratess is prepared, and the electrical resistance (wiring resistance) of the electrodes / wirings is measured. , The adhesion of the electrode / wiring to the substrate was evaluated. As the substrate, an alumina substrate, a borosilicate glass substrate, a silicon substrate, a ferrite substrate, and a polyimide substrate were used.

The wiring board used as the wiring evaluation sample was prepared as follows. First, seven strip-shaped patterns (2 mm × 40 mm each) were applied onto various substrates by a screen printing method using each of the prepared glass composition pastes. Next, for each substrate coated with the strip-shaped pattern, the temperature is raised to 5 ° C./min to a temperature about 40 to 50 ° C. higher than _{the softening point T s of the glass composition GE-60 in the air.} A wiring board was prepared by firing and baking at a temperature rate (heated at a temperature rate and held for 10 minutes).

The breakdown of the seven electrode wirings was "1, 2, 3, 4, 5, 6, 9" in the volume ratio of "Ag powder / GE-60 powder" in the paste. The electrical resistance of each electrode / wiring formed on the substrate was measured by the four-terminal method. In addition, the adhesion test of each electrode / wiring to the substrate was carried out by a peeling test.

FIG. 8 shows the volume ratio of “Ag powder / GE-60 powder powder” in the paste and the wiring resistance of each electrode / wiring in the glass composition paste obtained by mixing the glass composition GE-60 powder and Ag powder. It is a graph which shows the relationship.

As shown in FIG. 8, as the volume ratio of "Ag powder / GE-60 powder powder" increases, the wiring resistance of the electrode / wiring tends to decrease. In particular, ^{it can be seen that a very low wiring resistance on the order of 10 -6} Ω / mm ² can be achieved in the range of volume ratio 3 to 9, and a very stable wiring resistance can be obtained in the range of volume ratio 4 to 9. Moreover, it can be said that there is no particular difference depending on the type of substrate.

As described above, the adhesion test of each electrode / wiring to the substrate was performed by a peeling test. When a commercially available peeling tape is attached to each electrode / wiring and then the peeling tape is peeled off, the electrode / wiring peeling from the substrate and the electrode / wiring disconnection are not visually observed as "passed". Evaluation was performed, and those in which peeling of the electrode / wiring from the substrate and / or disconnection of the electrode / wiring were visually observed were evaluated as "failed". As a result, all electrodes / wirings and all substrates were evaluated as "passed".

From the above results, it was confirmed that the glass composition paste of the present invention can form electrodes / wirings having very low wiring resistance on various substrates by low-temperature firing by containing metal powder. Further, it was confirmed that the formed electrodes / wirings showed sufficient adhesion to various substrates.

In Experiment 11, GE-60 powder was used as the glass composition powder and Ag powder was used as the metal powder, but the present invention is not limited thereto. For example, Experiment 1 as a glass composition powder. The GA series and GC to GE series described in ~ 5 can be appropriately used, and Cu powder, Al powder, Sn powder, Au powder and Fe powder can be appropriately used as the metal powder. Further, as the substrate, a glass substrate, a ceramic substrate, or a heat-resistant resin substrate other than the above can be appropriately used.

[Experiment 12]
In Experiment 12, a vacuum-insulated double glazing panel, which is an example of a sealing structure produced by using the glass composition paste according to the present invention, will be described. A vacuum-insulated double glazing panel is one in which a vacuum-insulated layer is provided between two glass substrates, and it is necessary to airtightly seal (seal) the periphery of the glass substrate in order to maintain the vacuum-insulated layer. be.

Vacuum-insulated double glazing panels are applied to windowpanes for building materials, windowpanes for vehicles, doors of commercial refrigerators and freezers, and the like. The vacuum-insulated double glazing panel used for windows and doors is generally large, and a soda lime glass substrate is often used as the glass substrate from the viewpoint of cost.

However, since soda lime glass has low thermal conductivity and is easily broken, it cannot be rapidly heated or rapidly cooled when the heat treatment for airtight sealing is performed, and it is necessary to perform slow heating or slow cooling. This means that the work time of the heat treatment process is lengthened, which causes an increase in manufacturing cost. In other words, in order to reduce the manufacturing cost (improve the productivity), it is desired that the airtight seal can be sealed at the lowest possible temperature.

FIG. 9 is a schematic plan view of the produced vacuum-insulated double glazing panel and a schematic enlarged cross-sectional view taken along the line AA. As shown in FIG. 9, the vacuum-insulated double glazing panel 20 includes two glass substrates 21a and 21b, a sealing portion 22 provided on the periphery of the glass substrate between the glass substrates 21a and 21b, and the glass. It has a plurality of spacers 23 that are two-dimensionally and evenly arranged inside the sealing portion 22 between the substrates 21a and 21b. Further, the vacuum-insulated double glazing panel 20 has an exhaust hole 24 and a cap 25 on one of the glass substrates 21b.

The spacer 23 is for maintaining the thickness of the space 26 between the two glass substrates 21a and 21b at an appropriate value. In order to make the distance between the glass substrates 21a and 21b equal to the thickness of the space portion 26 in the sealing portion 22 region, spherical beads 27 having a uniform particle size may be arranged in the sealing portion 22. In order to further improve the heat insulating property of the double glazing panel, a heat ray reflecting film 28 may be formed on the inner surface of one of the glass substrates 21a.

The sealed space 26 between the two glass substrates 21a and 21b can be evacuated from the exhaust hole 24 using a vacuum pump or the like. By attaching the cap 25, the space 26 can be evacuated. The vacuum state can be maintained. Further, even after the vacuum-insulated double glazing panel 20 is installed, the cap 25 is removed and the space portion 26 is exhausted as necessary (for example, when the degree of vacuum of the space portion 27 decreases). It is possible to improve the degree of vacuum of the space 26.

In order to realize the airtight sealing heat treatment at a low temperature, it is preferable to form the sealing portion 22 using the glass composition paste of the present invention. Further, in order to match the coefficient of thermal expansion of the glass substrates 21a and 21b to be used, it is preferable to add the thermal expansion adjusting filler powder to the glass composition paste.

In Experiment 12, soda lime glass substrates (900 mm × 600 mm × 3 mm each) were used as the glass substrates 21a and 21b. A glass substrate 21a having a heat ray reflecting film 28 formed therein was prepared, and a glass substrate 21b having an exhaust hole 24 formed therein was prepared. In order to set the distance between the two glass substrates 21a and 21b (thickness of the space 26) to 0.2 mm, the columnar spacer 23 (made of polyimide resin, height 0.2 mm) and the sealing portion 22 are arranged. Spherical beads 27 (made of soda lime glass, diameter 0.19 mm) were prepared.

As the glass composition paste for forming the sealing portion 22, the glass composition powder GE-54 (D ₅₀ = 15 μm), the thermal expansion adjusting filler powder F-02 (D ₅₀ = 15 μm), and the aqueous solvent SA A resin binder aqueous solution prepared by dissolving 0.6% by mass of the water-soluble resin binder BA-01h in -01 was mixed and kneaded.

The volume mixing ratio of the thermal expansion adjusting filler powder F-02 in the glass composition paste was 0.8 times that of the glass composition powder GE-54. The total content of the glass composition powder GE-54 and the thermal expansion adjusting filler powder F-02 in the paste was 75% by mass, and the content of the resin binder aqueous solution was 25% by mass. Regarding the addition ratio of the spherical beads 27, when the total of the glass composition powder GE-54 and the thermal expansion adjusting filler powder F-02 was 100 parts by volume, the addition ratio of the spherical beads 27 was 0.5 parts by volume.

Next, a method for manufacturing the vacuum-insulated double glazing panel 20 will be briefly described.

FIG. 10 is a schematic plan view showing a state in which a sealing portion and a spacer are formed on one of the glass substrates constituting the vacuum-insulated double glazing panel, and a schematic enlarged cross-sectional view along the line BB. As shown in FIG. 10, the prepared glass composition paste is applied to the peripheral edge of the glass substrate 21b by a coating method such as a dispenser method, and then the solvent of the paste is dried (for example, 50 to 60 ° C. in the air). (Hold for 20-30 minutes) to form a dry coating of the paste on the glass substrate 21b. Further, the spacer 23 is arranged at a predetermined position on the glass substrate 21b. The order of forming the dry coating film and arranging the spacer 23 is not limited.

FIG. 11 is an enlarged cross-sectional schematic view showing an outline of the vacuum sealing process of the vacuum insulated double glazing panel, and FIG. 12 is an example of a firing temperature profile in the vacuum sealing process of the vacuum insulated double glazing panel.

As shown in FIG. 11, the glass substrate 21b on which the dry coating film and the spacer 23 of the sealing portion 22 are formed and the glass substrate 21a on which the heat ray reflecting film 28 is formed are aligned and arranged to face each other to withstand heat resistance. Fix with a sex clip (not shown). Next, a heat treatment is performed to soften and flow the glass composition in the dry coating film while evacuating. As an example of the heat treatment conditions, as shown in FIG. 12, the glass composition GE-54 is _{heated to the vicinity of the softening point T s} at a heating rate of 5 ° C./min in the air, held for 30 minutes, and then evacuated. While heating at a heating rate of 5 ° C / min to a temperature 30 to 50 ° C higher than the _{softening point T s, hold for 30 minutes.}

The heat treatment in the vacuum sealing step softens and flows the glass composition in the dry coating film, the sealing portion 22 is crushed by the weight of the glass substrate and the pressing by the heat-resistant clip, and the intervals specified by the spherical beads 27 and the spacer 23. The two glass substrates 21a and 21b are sealed while maintaining the above. After that, when the cap 25 is attached to the exhaust hole 24 in the environment where the vacuum state is maintained, the vacuum insulation double glazing panel 20 is completed.

In Experiment 12, 10 vacuum-insulated double glazing panels 20 were produced. As a result of visual inspection of the 10 vacuum-insulated double glazing panels 20 produced, no visual defects (for example, cracks or cracks in the glass substrates 21a and 21b) were observed. The total thickness of the two sealed glass substrates 21a and 21b was even over the entire surface of the glass substrate. This means that the sealing portion 22 including the spherical beads 27 and the spacer 23 kept the distance between the two glass substrates 21a and 21b (the height of the space portion 26) evenly.

As a result of conducting a helium leak test using 4 of the 10 prepared vacuum-insulated double glazing panels 20, the sealing portion 22 on the periphery of the glass substrate was airtightly sealed in all the test samples. It was confirmed.

In order to confirm the water resistance reliability of the sealing portion 22, a hot water immersion test (50 ° C., 30 days) was performed using three vacuum-insulated double glazing panels 20 out of the ten sheets produced. It was confirmed that the sealing portion 22 had sufficient water resistance reliability without water entering the inside of any of the test samples.

In addition, in order to confirm the temperature cycle durability of the sealing portion 22, a temperature cycle test (-50 ° C ⇔ + 100 ° C, 1000 cycles) using 3 out of 10 vacuum-insulated double glazing panels 20. As a result, it was confirmed that the vacuum of the space portion 26 was maintained in all the test samples, and that the sealing portion 22 had sufficient temperature cycle durability.

From the results of Experiment 12, the vacuum-insulated double glazing panel 20 according to the present invention has high heat insulating properties and high overall temperature cycle durability because the sealing portion 22 exhibits high airtightness, high water resistance reliability, and high temperature cycle durability. It can be said that it has long-term reliability. Further, in the vacuum-insulated double glazing panel 20 according to the present invention, an inexpensive soda lime glass substrate can be used as the glass substrate, and the sealing temperature can be remarkably lowered, so that the productivity of the vacuum-insulated double glazing panel is improved. Contributes to (reduction of manufacturing cost).

[Experiment 13]
In Experiment 13, an example of a vacuum-insulated double glazing panel produced by using a glass composition paste containing a metal powder instead of the glass composition paste containing the thermal expansion adjusting filler powder used in the experiment 12 will be described.

The glass composition paste for forming the sealing portion includes glass composition powder GE-60 (D ₅₀ = 15 μm), Sn powder (D ₅₀ = 25 μm), and a water-soluble resin binder in the aqueous solvent SA-01. A mixture and kneading of a resin binder aqueous solution in which BA-01f was dissolved in 1% by mass was used.

The volume mixing ratio of Sn powder in the glass composition paste was 1.5 times that of the glass composition powder GE-60. The total content of the glass composition powder GE-60 and Sn powder in the paste was 80% by mass, and the content of the resin binder aqueous solution was 20% by mass. Regarding the addition ratio of the spherical beads 27, when the total of the glass composition powder GE-54 and the thermal expansion adjusting filler powder F-02 was 100 parts by volume, the addition ratio of the spherical beads was 1 part by volume.

In the same manner as in Experiment 12, 10 vacuum-insulated multi-layer glass panels were prepared. Similar to Experiment 12, visual inspection, helium leak test, hot water immersion test, and temperature cycle test were performed, and all the tests were equivalent to Experiment 12.

From this result, in the sealing / bonding using the glass composition paste, the glass composition paste contains a thermal expansion adjusting filler powder for matching the thermal expansion / contraction with the material to be sealed or the base material to be bonded. It was confirmed that airtight sealing is possible by including a soft metal powder instead of the thermal expansion adjusting filler powder. It is considered that this is because the metal powder plays a role of relaxing the thermal stress.

[Experiment 14]
In Experiment 14, an organic light emitting diode (OLED) display panel, which is an example of a sealing structure produced by using the glass composition paste according to the present invention, will be described. An OLED display panel is a display panel in which a large number of OLEDs are built-in and formed between two glass substrates.

FIG. 13 is a schematic plan view of the produced OLED display panel and a schematic enlarged cross-sectional view taken along the line CC. As shown in FIG. 13, the OLED display panel 30 includes two glass substrates 31a and 31b, a sealing portion 32 provided on the periphery of the glass substrate between the glass substrates 31a and 31b, and the glass substrate 31a, It has an OLED 33 arranged inside the sealing portion 32 between 31b.

In the OLED display panel 30, a non-alkali borosilicate glass substrate is usually used as the glass substrates 31a and 31b. Since the OLED 33 is easily deteriorated by moisture and oxygen, it is important to hermetically seal it with the sealing portion 32. Further, for the formation of the sealing portion 32, it is preferable to use the glass composition paste of the present invention in order to realize the airtight sealing heat treatment at a low temperature, and in particular, it is consistent with the coefficient of thermal expansion of the glass substrates 31a and 31b to be used. Therefore, it is preferable to use a mixture containing a thermal expansion adjusting filler powder having a small coefficient of thermal expansion.

The glass composition paste for forming the sealing portion 22 includes glass composition powder GE-56 (D ₅₀ = 1.5 μm), thermal expansion adjusting filler powder F-02 (D ₅₀ = 3 μm), and an aqueous solvent. A resin binder aqueous solution prepared by dissolving 0.6% by mass of a water-soluble resin binder BA-01h in SA-01 was mixed and kneaded.

The volume-blending ratio of the thermal expansion adjusting filler powder F-02 in the glass composition paste was double that of the glass composition powder GE-56. The total content of the glass composition powder GE-56 and the thermal expansion adjusting filler powder F-02 in the paste was 75% by mass, and the content of the resin binder aqueous solution was 25% by mass.

Next, a method for manufacturing the OLED display panel 30 will be briefly described.

Prepare two non-alkali borosilicate glass substrates as glass substrates 31a and 31b. An OLED 33 corresponding to a predetermined number of pixels is formed on one of the glass substrates 31b. After applying the prepared glass composition paste to the peripheral edge of the other glass substrate 31a by a coating method such as a dispenser method, the glass composition GE- A fired coating of the paste (eg, line width 2 mm, thickness 15 μm) is formed on the glass substrate 31a by heating to a temperature 30-50 ° C higher than the softening point T _{s of 56 and holding for 30 minutes.}

The glass substrate 31a on which the fired coating film of the sealing portion 32 is formed and the glass substrate 31b on which the OLED 33 is formed are aligned and arranged to face each other, and fixed with a heat-resistant clip or the like (not shown). Next, under a reduced pressure atmosphere, laser light irradiation (for example, scanning speed 10 mm / sec) is performed from the back surface side (the surface side on which the fired coating film is not formed) of the glass substrate 31a toward the fired coating film. The glass composition of the fired coating is heated, softened and flowed. As a result, the peripheral edges of the glass substrates 31a and 31b are sealed, and the OLED display panel 30 is completed.

The reason why the laser beam is used for heating the fired coating film is to prevent thermal damage to the OLED 33 and improve the productivity. The laser light to be used is preferably one that is efficiently absorbed by the glass composition of the fired coating film, and for example, a red semiconductor laser having a wavelength of 805 nm can be preferably used.

In Experiment 14, five OLED display panels 30 were produced. As a result of visual inspection and lighting test of the five OLED display panels 30 produced, no defects in appearance (for example, cracks and cracks in the glass substrates 21a and 21b) were observed, and all of them were lit without any problem. It was confirmed.

The five OLED display panels 30 produced were subjected to high-temperature and high-humidity tests (saturated pressure cooker test, temperature 120 ° C, relative humidity 100%, pressure 202 kPa) held for 1 day, 3 days and 7 days. After that, a lighting test was conducted. For comparison, an OLED display panel (line width 5 mm, thickness 15 μm of the sealing part) sealed only with resin instead of glass composition paste was separately prepared and the same test was conducted.

In the high temperature and high humidity test held for 1 day, all OLED display panels turned on without any problem. However, in the resin-sealed OLED display panel, the lighting of the sample after holding for 3 days was significantly deteriorated. It is probable that this is because moisture and oxygen invaded the inside of the OLED display panel from the resin sealing part and the OLED 33 deteriorated.

On the other hand, in the OLED display panel according to the present invention, no deterioration was observed in the lighting of the OLED even in the high temperature and high humidity test held for 7 days, and good test results were obtained. This strongly suggests that high airtightness is maintained in the sealing portion 32.

In Experiment 14, an example of an OLED display panel was described as a sealing structure produced using a glass composition paste. It has been confirmed that the glass composition paste of the present invention can form a sealing portion exhibiting high airtightness and high water resistance reliability, and can provide a good OLED display panel.

Further, from the results of Experiment 14, the glass composition paste of the present invention uses, in addition to the OLED display panel, a sealing structure that is susceptible to thermal damage (for example, a flat panel lighting fixture, an organic solar cell, and an organic element). It can be said that it can be effectively applied to the MEMS sensor that was used.

[Experiment 15]
In Experiment 15, an electrode / wiring of a solar cell panel, which is an example of an electric / electronic component manufactured by using the glass composition paste according to the present invention, particularly a solar cell panel using a Si crystal substrate will be described.

FIG. 14 is a schematic plan view of the light receiving surface of the Si crystal substrate solar cell panel, a schematic plan view of the back surface, and a schematic cross-sectional view along the DD line. As shown in FIG. 14, in the solar cell panel 40, a pn junction surface 46 is formed on one surface side of the Si crystal substrate 41, and that surface serves as a light receiving surface. A light receiving surface electrode / wiring 42 and an antireflection film 43 are formed on the light receiving surface. The other surface of the Si crystal substrate 41 is referred to as a back surface, and a current collecting electrode / wiring 44 and an output electrode / wiring 45 are formed on the back surface. Conventionally, a glass composition paste has been used for forming the light receiving surface electrode / wiring 42, the current collecting electrode / wiring 44, and the output electrode / wiring 45.

However, the electrode / wiring of the conventional Si crystal substrate solar cell panel is an organic solvent-based glass composition containing a leaded glass composition powder and Ag powder in forming the light receiving surface electrode / wiring 42 and the output electrode / wiring 45. A paste was used, and an organic solvent-based glass composition paste containing a leaded glass composition powder and an Al powder was used for forming the current collecting electrode / wiring 44.

These organic solvent-based glass composition pastes were applied on a Si crystal substrate 41 and then fired in the air at 600 to 900 ° C. In this case, the lead component and the organic solvent in the glass composition paste pose a safety and environmental problem. Further, since the firing temperature for forming the electrodes / wiring is high, there is a problem that the solar cell panel is greatly warped and easily damaged.

On the other hand, in the solar cell panel 40 according to the present invention, the light receiving surface electrode / wiring 42, the current collecting electrode / wiring 44, and the output electrode / wiring 45 are formed by the glass composition paste of the present invention. In Experiment 15, the Si crystal substrate 41 was a Si single crystal substrate for solar cells (150 mm × 150 mm × 0.2 mm), and an antireflection film 43 (thickness 100 nm) made of SiN (silicon nitride) was formed on the light receiving surface. I used the one that has been used.

The glass composition paste for forming the light receiving surface electrode / wiring 42 and the output electrode / wiring 45 includes glass composition powder GE-58 (D ₅₀ = 1 μm) and Ag powder (D ₅₀ = 1.5 μm). SA-01 was mixed and kneaded with an aqueous resin binder solution in which 0.6% by mass of the water-soluble resin binder BA-01h was dissolved.

The volume mixing ratio of Ag powder in the glass composition paste for the light receiving surface electrode / wiring 42 and the output electrode / wiring 45 was 6 times that of the glass composition powder GE-58. The total content of the glass composition powder GE-58 and Ag powder in the paste was 75% by mass, and the content of the resin binder aqueous solution was 25% by mass.

The glass composition paste for forming the current collecting electrode / wiring 44 includes glass composition powder GE-70 (D ₅₀ = 1 μm), Al powder (D ₅₀ = 3 μm), and SA-01 with a water-soluble resin. A mixture and kneading of a resin binder aqueous solution in which 1% by mass of binder BA-01f was dissolved was used.

The volume mixing ratio of the Al powder in the glass composition paste for the current collecting electrode / wiring 44 was 9 times that of the glass composition powder GE-70. The total content of the glass composition powder GE-70 and the Al powder in the paste was 75% by mass, and the content of the resin binder aqueous solution was 25% by mass.

Next, a method for manufacturing the solar cell panel 40 will be briefly described.

The prepared glass composition paste for the light receiving surface electrode / wiring 42 is applied to the light receiving surface side of the Si crystal substrate 41 by a coating method such as a screen printing method. Next, firing under predetermined conditions (for example, heating to a temperature 30 to 50 ° C higher than _{the softening point T s} of the glass composition GE-58 at a heating rate of 10 ° C / min in the air and holding for 30 minutes). As a result, the glass composition in the paste softens and flows to form the light receiving surface electrode / wiring 42, and at the same time, it adheres to the light receiving surface of the Si crystal substrate 41.

Next, the prepared glass composition paste for the output electrode / wiring 45 is applied to the back surface side of the Si crystal substrate 41 by a coating method such as a screen printing method, and then the paste solvent is dried (for example, in the air). (Hold at 50-60 ° C. for 20-30 minutes) to form a dry coating of the paste. Next, the prepared glass composition paste for the current collecting electrode / wiring 44 is applied by a coating method such as a screen printing method. Then, by firing under predetermined conditions (for example, heating to a temperature 30 to 50 ° C higher than _{the softening point T s} of the glass composition GE-70 at a heating rate of 10 ° C / min in the air and holding for 30 minutes). The glass composition in both pastes softens and flows to form the output electrode / wiring 45 and the current collecting electrode / wiring 44, and is fixed to the back surface of the Si crystal substrate 41 to complete the solar cell panel 40.

The light receiving surface electrode / wiring 42 is fired twice, which improves the electrical connection between the light receiving surface electrode / wiring 42 and the light receiving surface of the Si crystal substrate 41.

In Experiment 15, 10 solar cell panels 40 were produced. As a result of visual inspection of the 10 solar cell panels 40 produced, defects in appearance (for example, cracks and cracks in the light receiving surface electrode / wiring 42, the current collecting electrode / wiring 44 and the output electrode / wiring 45, and the solar cell No warpage of panel 40, etc.) was observed. It is considered that this is due to the fact that the water-based glass composition paste of the present invention was able to significantly lower the formation temperature of various electrodes / wirings.

As a result of investigating the electrical connection (current-voltage characteristics) between each electrode / wiring and the Si crystal substrate 41 for the 10 solar cell panels 40 produced, ohmic contact was obtained for each sample, and good electricity was obtained. It was confirmed that the target connection was established.

As a result of measuring the conversion efficiency of the 10 solar cell panels 40 produced by a solar simulator, the conversion efficiency was equivalent to that of the conventional solar cell panel, even though the formation temperature of each electrode / wiring was significantly lowered. It was confirmed that (about 18%) was obtained.

In order to confirm the water resistance reliability of each electrode / wiring, a hot water immersion test (50 ° C., 5 days) was performed using 3 of the 10 solar cell panels 40 produced, and then a solar simulator was used. The conversion efficiency was measured. For comparison, a conventional solar cell panel in which electrodes / wirings are formed using an organic solvent-based glass composition paste containing a leaded glass composition instead of the glass composition paste of the present invention is separately prepared and the same test is performed. Was done.

As a result, in the conventional solar cell panel, corrosion occurred in each electrode / wiring, and the power generation efficiency deteriorated to about 12 to 13%. On the other hand, in the solar cell panel according to the present invention, corrosion did not occur in each electrode / wiring, and no deterioration in conversion efficiency was observed. From this test, it was confirmed that the solar cell panel according to the present invention exhibits high water resistance reliability.

In addition, when the overlapping portion of the current collecting electrode / wiring 44 and the output electrode / wiring 45 formed on the back surface was disassembled and confirmed, an unwanted chemical reaction (formation of a brittle intermetallic compound) between Ag and Al was observed. I couldn't. It is considered possible that the interaction between the glass composition of the present invention and Ag particles or Al particles suppresses an unwanted chemical reaction between Ag and Al. This is considered to be one of the special effects of the glass composition of the present invention.

In Experiment 15, examples of a solar cell panel and its electrodes / wiring were described as electrical and electronic components manufactured using the glass composition paste. However, the glass composition paste of the present invention is not limited to application to solar cell panels, and can be effectively applied to electrodes / wiring of various electrical and electronic components, improving reliability and productivity of electrical and electronic components. It contributes to improvement and cost reduction.

[Experiment 16]
In Experiment 16, a crystal oscillator package, which is an example of an electric / electronic component manufactured by using the glass composition paste according to the present invention, particularly a conductive joint portion and a sealing portion of the package will be described.

FIG. 15 is a schematic cross-sectional view showing an example of a process for manufacturing a crystal oscillator package according to the present invention. A method for manufacturing the crystal oscillator package 50 will be briefly described with reference to FIG.

A glass composition paste containing metal powder is applied onto the wiring 52 built into the ceramic substrate 51 by a coating method such as a dispenser method, and then the paste solvent is dried (for example, in the air at 50 to 60 ° C.). (Hold for 20-30 minutes) to form a paste-dry coating 53.

Next, the crystal transducer 54 is arranged so as to be in contact with the paste-dried coating film 53, and the glass in the paste-drying coating film 53 is placed under predetermined conditions (for example, in an inert gas at a heating rate of 10 ° C./min). The glass composition is softened and flowed by heating at a temperature 30 to 50 ° C. higher than the softening point T _{s of the composition and held for 10 minutes) to electrically join the crystal transducer 54 and the wiring 52.}

A crystal oscillator 55 having a paste-fired coating film 56 formed on the outer periphery of the cap is separately prepared. The paste-baked coating film 56 is formed under predetermined conditions (for example, in the air, at 10 ° C./) after applying a glass composition paste containing a thermal expansion adjusting filler powder to the outer peripheral portion of the cap by a coating method such as a dispenser method. Bake at a heating rate of 30 to 50 ° C higher than _{the softening point T s} of the glass composition in the paste and hold for 10 minutes).

Next, the paste firing coating film 56 of the ceramic cap 55 and the ceramic substrate 51 are aligned and arranged, and paste firing is performed under predetermined conditions (for example, in a vacuum at a heating rate of 10 ° C./min) while applying a load. The glass composition in the coating film 56 is _{heated to a temperature 30 to 50 ° C higher than the softening point T s and} held for 10 minutes) to soften and flow the glass composition, and the ceramic cap 55 and the ceramic substrate 51 are sealed. Stop. This completes the crystal oscillator package 50.

In the above manufacturing process, it is important to prevent the electrical connection between the crystal oscillator 54 and the wiring 52 from peeling off during the firing step of sealing the ceramic cap 55 and the ceramic substrate 51. From this point of view, the softening point T _s of the glass composition used for the sealing between the ceramic cap 55 and the ceramic substrate 51, the softening point T _s of the glass composition used for electrical connection between the crystal resonator 54 and the wiring 52 It is desirable to select each glass composition so that the amount is also low.

In Experiment 16, the ceramic substrate 51 and the ceramic cap 55 were made of alumina. The glass composition paste used for electrical bonding between the crystal transducer 54 and the wiring 52 includes glass composition powder GE-11 (D ₅₀ = 1 μm), Ag powder (D ₅₀ = 1.5 μm), and an aqueous solvent SA. A mixture and kneading of a resin binder aqueous solution in which 1% by mass of a water-soluble resin binder BA-01f was dissolved in -01 was used.

The volume mixing ratio of Ag powder in the glass composition paste was 7 times that of the glass composition powder GE-11. The total content of the glass composition powder GE-11 and Ag powder in the paste was 75% by mass, and the content of the resin binder aqueous solution was 25% by mass.

The glass composition paste used for sealing the ceramic cap 55 and the ceramic substrate 51 includes glass composition powder GE-63 (D ₅₀ = 5 μm) and thermal expansion adjusting filler powder F-02 (D ₅₀ = 5 μm). , A resin binder aqueous solution in which 0.6% by mass of the water-soluble resin binder BA-01h was dissolved in the aqueous solvent SA-01 was mixed and kneaded.

The volume-blending ratio of the thermal expansion adjusting filler powder F-02 in the glass composition paste was set to 1 times that of the glass composition powder GE-63. The total content of the glass composition powder GE-63 and the thermal expansion adjusting filler powder F-02 in the paste was 75% by mass, and the content of the resin binder aqueous solution was 25% by mass.

The glass composition GE-11 of the paste used for electrical bonding between the crystal transducer 54 and the wiring 52 has a softening point T _s = 313 ° C, and the paste used for sealing the ceramic cap 55 and the ceramic substrate 51. The glass composition of GE-63 has a softening point T _s = 244 ° C. That is, the difference between the two is 69 ° C.

In Experiment 16, 24 crystal oscillator packages 50 were produced as described above. As a result of performing a visual inspection of the produced 24 crystal oscillator packages 50 with a stereomicroscope, problems with appearance (for example, misalignment between the ceramic cap 55 and the ceramic substrate 51, cracks and cracks in the glass sealing portion, etc.) ) Was not observed.

A continuity test was conducted to investigate whether the electrical connection between the crystal unit 54 inside the crystal unit package 50 and the wiring 52 was normal. As a result, it was confirmed that the crystal oscillator works in all the manufactured crystal oscillator packages 50.

As a result of a helium leak test using 5 of the 24 crystal oscillator packages 50 produced, it was confirmed that the ceramic cap 55 and the ceramic substrate 51 were hermetically sealed in each test sample. bottom.

A high-temperature and high-humidity test (saturated pressure cooker test, temperature 120 ° C, relative humidity 100%, pressure 202 kPa, holding for 3 days) was performed on 5 of the 24 crystal oscillator packages produced. Later, a helium leak test was performed. As a result, it was confirmed that the airtight seal between the ceramic cap 55 and the ceramic substrate 51 was maintained in all the test samples.

In Experiment 16, examples of a crystal oscillator package, its electrical bonding, and airtight sealing have been described as electrical and electronic components produced using the glass composition paste. However, the glass composition paste of the present invention is not limited to application to a crystal unit package, and can be applied to electrical bonding and airtight sealing of various electrical and electronic components.

The above-described embodiments and experimental examples have been described for the purpose of assisting the understanding of the present invention, and the present invention is not limited to the specific configurations described. For example, it is possible to replace a part of the configuration of the embodiment with the configuration of the common general technical knowledge of those skilled in the art, and it is also possible to add the configuration of the common general technical knowledge of the person skilled in the art to the configuration of the embodiment. That is, the present invention may delete, replace with another configuration, or add another configuration to a part of the configurations of the embodiments and experimental examples of the present specification without departing from the technical idea of the invention. It is possible.

10, 10'... Join,
11 ... Cylindrical substrate, 12 ... Circular joint surface, 13 ... Coating film, 14, 14'... Dry coating film, 15 ... Plate-like substrate,
20 ... Vacuum insulated double glazing panel,
21a, 21b ... glass substrate, 22 ... sealing part, 23 ... spacer, 24 ... exhaust hole, 25 ... cap,
26 ... Space, 27 ... Spherical beads, 28 ... Heat-reflecting film,
30 ... OLED display panel,
31a, 31b ... glass substrate, 32 ... sealing part, 33 ... OLED,
40 ... Solar panel,
41 ... Si crystal substrate, 42 ... Light receiving surface electrode / wiring, 43 ... Antireflection film, 44 ... Current collecting electrode / wiring,
45 ... Output electrode / wiring, 46 ... pn junction surface,
50 ... Crystal oscillator package,
51 ... Ceramic substrate, 52 ... Wiring, 53 ... Paste dry coating, 54 ... Crystal oscillator,
55 ... Ceramic cap, 56 ... Paste fired coating.

Claims (43)

A glass composition paste containing a lead-free glass composition powder and a solvent.
_{The glass composition contains V 2} O ₅ and Ag ₂ O when the components are represented by oxides.
The molar% content of V ₂ O _{5 and} the molar% content of Ag ₂ O are
Relational expression (1): 1/3 × [V ₂ O ₅ ] ≤ [Ag ₂ O] ≤ 2 × [V ₂ O ₅ ],
The filling,
The solvent is a glass composition paste, which is an aqueous solvent. In the glass composition paste according to claim 1,
The glass composition further contains _{TeO 2} when the components are represented by oxides.
The mol% content of V ₂ O _5, the mol% content of Ag ₂ O, and the molar% content of Te O ₂ are
Relational expression (2): [V ₂ O ₅ ] + [Ag ₂ O] + [TeO ₂ ] ≧ 73,
A glass composition paste characterized by satisfying. In the glass composition paste according to claim 2.
The glass composition further contains _{Li 2} O when the components are represented by oxides.
The molar% content of V ₂ O _5, the molar% content of Ag ₂ O, and the molar% content of Li ₂ O are
Relational expression (3): [Li ₂ O] ≤ 1/2 × [Ag ₂ O], and relational expression (4): [Ag ₂ O] + [Li ₂ O] ≤ 2 × [V ₂ O ₅ ],
A glass composition paste characterized by satisfying. In the glass composition paste according to claim 2.
Mole% content and the Ag ₂ O mol% content of the mole% content of the TeO ₂ of the V ₂ O ₅ is, equation (5): 20 ≦ [V 2 O 5] ≦ 45,
Relational expression (6): 12 ≤ [Ag ₂ O] ≤ 45, and relational expression (7): 25 ≤ [TeO ₂ ] ≤ 47,
A glass composition paste characterized by satisfying. In the glass composition paste according to claim 3,
The molar% content of V ₂ O _5, the molar% content of Ag ₂ O, the molar% content of Te O _{2 and} the molar% content of Li ₂ O are
Relational expression (5): 20 ≤ [V ₂ O ₅ ] ≤ 45,
Relational expression (6): 12 ≤ [Ag ₂ O] ≤ 45,
Relational expression (7): 25 ≤ [TeO ₂ ] ≤ 47, and relational expression (8): 0 <[Li ₂ O] ≤ 15,
A glass composition paste characterized by satisfying. In the glass composition paste according to any one of claims 1 to 5.
The glass composition further contains any one or more of the group consisting _{of K 2} O, MgO, P ₂ O ₅ , BaO, ZnO, and WO ₃ when the components are expressed as oxides.
The molar% content of the components that make up the group
Relational expression (9): 0 <[K ₂ O] + [MgO] + [P ₂ O ₅ ] + [BaO] + [WO ₃ ] + [ZnO] ≤ 17,
A glass composition paste characterized by satisfying. The glass composition paste according to any one of claims 1 to 6.
_{The glass composition comprises Al 2} O ₃ , Fe ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Er ₂ O ₃ , and Yb ₂ O ₃ when the components are represented by oxides. Further containing any one or more of the group,
The molar% content of the components that make up the group
Relational expression (10): 0.3 ≤ [Al ₂ O ₃ ] + [Fe ₂ O ₃ ] + [Y ₂ O ₃ ] + [La ₂ O ₃ ] + [CeO ₂ ] + [Er ₂ O ₃ ] + [Yb ₂ O ₃ ] ≤ 7.5,
A glass composition paste characterized by satisfying. In the glass composition paste according to any one of claims 1 to 7.
A glass composition paste characterized in that the transition point of the glass composition is 260 ° C. or lower. In the glass composition paste according to any one of claims 1 to 8.
A glass composition paste characterized in that the liquid property of the glass composition paste is neutral or alkaline. In the glass composition paste according to any one of claims 1 to 9.
The glass composition paste is a glass composition paste further containing a nonionic water-soluble thermoplastic resin as a resin binder. In the glass composition paste according to claim 10.
A glass composition paste, wherein the water-soluble thermoplastic resin is polyethylene oxide. In the glass composition paste according to claim 11,
A glass composition paste characterized by having a weight average molecular weight of the polyethylene oxide of 3,500,000 or more. The glass composition paste according to any one of claims 1 to 12.
The glass composition paste is a glass composition paste further containing a thermal expansion adjusting filler powder. In the glass composition paste according to claim 13,
Said thermal expansion adjustment filler _{powder, Zr 2 (WO 4) (} PO 4) 2, Li 2 O · Al 2 O 3 · 2SiO 2, 2MgO · 2Al 2 O 3 · 5SiO 2, 3Al 2 O 3 · 2SiO 2, A glass composition paste characterized by being one or more powders in the group consisting of SiO ₂ , Nb ₂ O _{5, and Si.} In the glass composition paste according to claim 13 or 14.
A glass composition paste characterized in that the volume content of the thermal expansion adjusting filler powder is 2.5 times or less the volume content of the glass composition. The glass composition paste according to any one of claims 1 to 12.
The glass composition paste is a glass composition paste further containing a metal powder. In the glass composition paste according to claim 16,
The metal powder is a glass characterized by being any one or more powders in the group consisting of Ag, Ag alloy, Cu, Cu alloy, Al, Al alloy, Sn, Sn alloy, Fe, and Fe alloy. Composition paste. In the glass composition paste according to claim 16 or 17.
A glass composition paste characterized in that the volume content of the metal powder is 9 times or less the volume content of the glass composition. A glass composition paste containing a lead-free glass composition powder and a solvent.
_{The glass composition contains V 2} O ₅ and Ag ₂ O when the components are represented by oxides.
The solvent is an aqueous solvent and
The peak top intensity of the first coordination sphere in the glass composition in the radial structure function obtained by Fourier transforming the wide-area X-ray absorption fine structure of the K-edge of the vanadium component is a single V ₂ O ₅ crystal. A glass composition paste characterized by being greater than the peak top strength of the first coordination sphere in. In the glass composition paste according to claim 19.
A glass composition paste characterized in that the peak top strength of the glass composition is 1.2 times or more the peak top strength of the single V ₂ O _{5 crystal.} In the glass composition paste according to claim 19 or 20
A glass composition paste characterized in that the transition point of the glass composition is 260 ° C. or lower. The glass composition paste according to any one of claims 19 to 21.
A glass composition paste characterized in that the liquid property of the glass composition paste is neutral or alkaline. The glass composition paste according to any one of claims 19 to 22.
The glass composition paste is a glass composition paste further containing a nonionic water-soluble thermoplastic resin as a resin binder. In the glass composition paste according to claim 23,
A glass composition paste, wherein the water-soluble thermoplastic resin is polyethylene oxide. In the glass composition paste according to claim 24,
A glass composition paste characterized by having a weight average molecular weight of the polyethylene oxide of 3,500,000 or more. The glass composition paste according to any one of claims 19 to 25.
The glass composition paste is a glass composition paste further containing a thermal expansion adjusting filler powder. In the glass composition paste according to claim 26,
Said thermal expansion adjustment filler _{powder, Zr 2 (WO 4) (} PO 4) 2, Li 2 O · Al 2 O 3 · 2SiO 2, 2MgO · 2Al 2 O 3 · 5SiO 2, 3Al 2 O 3 · 2SiO 2, A glass composition paste characterized by being one or more powders in the group consisting of SiO ₂ , Nb ₂ O _{5, and Si.} In the glass composition paste according to claim 26 or 27.
A glass composition paste characterized in that the volume content of the thermal expansion adjusting filler powder is 2.5 times or less the volume content of the glass composition. The glass composition paste according to any one of claims 19 to 25.
The glass composition paste is a glass composition paste further containing a metal powder. In the glass composition paste according to claim 29,
The metal powder is a glass characterized by being any one or more powders in the group consisting of Ag, Ag alloy, Cu, Cu alloy, Al, Al alloy, Sn, Sn alloy, Fe, and Fe alloy. Composition paste. In the glass composition paste according to claim 29 or 30,
A glass composition paste characterized in that the volume content of the metal powder is 9 times or less the volume content of the glass composition. A lead-free glass composition
When the components are expressed as oxides, they consist of three or more types of oxides.
_{Contains V 2} O ₅ and Ag ₂ O as the main ingredients,
Containing _{Te O 2} and / or Li ₂ O as the first optional component,
It contains one or more of the group consisting _{of K 2} O, MgO, P ₂ O ₅ , BaO, ZnO, and WO ₃ as the second optional component.
It contains one or more of the group consisting _{of Al 2} O ₃ , Fe ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Er ₂ O ₃ , and Yb ₂ O ₃ as the third optional component.
The molar% content of the main component is
Relational expression (1): 1/3 × [V ₂ O ₅ ] ≤ [Ag ₂ O] ≤ 2 × [V ₂ O ₅ ],
The filling,
When the first optional component is contained, the molar% content of the first optional component is
Relational expression (2): [V ₂ O ₅ ] + [Ag ₂ O] + [TeO ₂ ] ≧ 73,
Relational expression (3): [Li ₂ O] ≤ 1/2 x [Ag ₂ O],
Relational expression (4): [Ag ₂ O] + [Li ₂ O] ≤ 2 × [V ₂ O ₅ ],
Relational expression (5): 20 ≤ [V ₂ O ₅ ] ≤ 45,
Relational expression (6): 12 ≤ [Ag ₂ O] ≤ 45,
Relational expression (7): 25 ≤ [TeO ₂ ] ≤ 47, and relational expression (8): 0 <[Li ₂ O] ≤ 15,
The filling,
When the second optional component is contained, the molar% content of the second optional component is
Relational expression (9): 0 <[K ₂ O] + [MgO] + [P ₂ O ₅ ] + [BaO] + [WO ₃ ] + [ZnO] ≤ 17,
The filling,
When the third optional component is contained, the molar% content of the third optional component is
Relational expression (10): 0.3 ≤ [Al ₂ O ₃ ] + [Fe ₂ O ₃ ] + [Y ₂ O ₃ ] + [La ₂ O ₃ ] + [CeO ₂ ] + [Er ₂ O ₃ ] + [Yb ₂ O ₃ ] ≤ 7.5,
A glass composition characterized by satisfying. In the glass composition according to claim 32,
The peak top intensity of the first coordination sphere in the glass composition in the radial structure function obtained by Fourier transforming the wide-area X-ray absorption fine structure of the K-edge of the vanadium component is a single V ₂ O ₅ crystal. A glass composition characterized by being greater than the peak top intensity of the first coordination sphere in. In the glass composition according to claim 33,
A glass composition characterized in that the peak top intensity of the glass composition is 1.2 times or more the _{peak top intensity of the single V 2} O _{5 crystal.} The glass composition according to any one of claims 32 to 34.
A glass composition characterized in that the transition point of the glass composition is 260 ° C. or lower. The glass composition according to any one of claims 32 to 35.
The glass composition is a glass composition further containing a thermal expansion adjusting filler powder. In the glass composition according to claim 36,
Said thermal expansion adjustment filler _{powder, Zr 2 (WO 4) (} PO 4) 2, Li 2 O · Al 2 O 3 · 2SiO 2, 2MgO · 2Al 2 O 3 · 5SiO 2, 3Al 2 O 3 · 2SiO 2, A glass composition characterized by being one or more powders in the group consisting of SiO ₂ , Nb ₂ O _{5, and Si.} In the glass composition according to claim 36 or 37.
A glass composition characterized in that the volume content of the thermal expansion adjusting filler powder is 2.5 times or less the volume content of the glass phase in the glass composition. The glass composition according to any one of claims 32 to 35.
The glass composition is a glass composition further containing a metal powder. In the glass composition according to claim 39,
The metal powder is a glass characterized by being any one or more powders in the group consisting of Ag, Ag alloy, Cu, Cu alloy, Al, Al alloy, Sn, Sn alloy, Fe, and Fe alloy. Composition. In the glass composition according to claim 39 or 40.
A glass composition characterized in that the volume content of the metal powder is 9 times or less the volume content of the glass phase in the glass composition. A sealing structure having a sealing portion made of a glass material.
A sealing structure, wherein the glass material comprises the glass composition according to any one of claims 32 to 38. An electrical and electronic component with electrodes / wiring or heat conductive bonding layers made of glass material.
An electrical and electronic component, wherein the glass material comprises the glass composition according to any one of claims 32 to 35 and 39 to 41.

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