JP7028226B2 - Lead-free low melting point glass composition, low melting point glass composite material, glass paste and applied products - Google Patents

Description

The present invention relates to lead-free low melting point glass compositions, low melting point glass composite materials and applied products.

For vacuum-insulated double glazing panels, plasma display panels, organic EL display panels, display panels such as vacuum fluorescent displays, and electrical and electronic components such as crystal oscillators, IC ceramic packages, and semiconductor sensors, which are applied to window glass and the like. , Sealing, bonding and the like are performed by a low melting point glass composite material containing a low melting point glass composition and low thermal expansion filler particles. This low melting point glass composite is often applied in the form of a low melting point glass paste. The low melting point glass paste is applied to a base material by a screen printing method, a dispenser method, or the like, dried, and then fired to be applied to sealing, adhesion, or the like. At the time of sealing or bonding, the low melting point glass composition contained in the low melting point glass composite material or the low melting point glass paste softens and flows to be brought into close contact with the material to be sealed or the member to be bonded.

In addition, in many electrical and electronic components such as solar cell, image display device, laminated capacitor, crystal oscillator, LED (light emitting diode), and multilayer circuit board, low melting point glass composite containing low melting point glass composition and metal particles The material forms electrodes and wiring. The low melting point glass composite material is also used as a conductive joint for conducting conduction and a heat-dissipating joint for conducting heat. Even when forming electrodes, wiring, heat-dissipating joints, etc., the low-melting-point glass composition contained in the low-melting-point glass composite material or low-melting-point glass paste softens and flows, thereby sintering metal particles and forming a substrate. Make close contact.

As the low melting point glass composition contained in the above low melting point glass composite material and the low melting point glass paste, the PbO _- B ₂ O3 system low melting point glass composition containing a very large amount of lead oxide has been widely applied in the past. rice field. This PbO _- B ₂ O3 low melting point glass composition has a low softening point of 350 to 400 ° C., exhibits good softening fluidity at 400 to 450 ° C., and has relatively high chemical stability. ing.

However, in recent years, the trend of green procurement and green design has become stronger worldwide, and safer materials have been required. For example, in Europe, the European Union (EU) Directive (RoHS Directive) on restrictions on the use of specified hazardous substances in electronic and electrical equipment came into effect on July 1, 2006. In the RoHS Directive, lead, mercury, cadmium and hexavalent chromium are designated as prohibited substances. Therefore, it is practically difficult to use the above-mentioned PbO-B ₂ O ₃ system low melting point glass composition.

Therefore, the development of a new low melting point glass composition containing no lead is underway.

Patent Document 1 describes 100 parts by weight of a mixed powder consisting of V ₂ O ₅ : 52.5 to 57.5% by weight, TeO ₂ : 40 to 45% by weight, and Li ₂ O: 2.5 to 7.5% by weight. Discloses a method for producing crystalline moisture-sensitive glass from a starting material powder containing 8 to 12 parts by weight of Ag ₂ O. Patent Document 1 discloses that K2O: ₅ parts by weight or less may be blended with the above starting material powder.

Patent Document 2 contains Ag ₂ O, V ₂ O ₅ and TeO ₂ as main components, the total content is 75% by mass or more, and the balance is P ₂ O ₅ , BaO, K ₂ O, WO. _3. A lead-free glass composition containing one or more of Fe ₂ O ₃ , MnO ₂ , Sb ₂ O ₃ , and ZnO is disclosed. From Patent Document 2, this lead-free glass composition has a softening point of 320 ° C. or less obtained from the second endothermic peak temperature of differential thermal analysis (DTA), and the sample from which the desired result is obtained as an example has a softening point. It can be read that the temperature is 268 ° C or higher. Further, Patent Document 2 discloses a glass frit containing this lead-free glass composition, a sealing glass paste, a conductive glass paste, and an electric / electronic component using these.

Japanese Unexamined Patent Publication No. 61-2429227 Japanese Patent No. 5726698

In the Ag ₂ O-V ₂ O ₅ -TeO ₂ -Li ₂ O-based lead-free glass composition disclosed in Patent Document 1, the glass obtained by heating and firing is crystallized.

The Ag ₂ O-V ₂ O ₅ -TeO ₂ system lead-free glass composition disclosed in Patent Document 2 has a lower softening point than the conventional PbO-B ₂ O ₃ system low melting point glass composition. However, there is room for improvement in adhesiveness in order to improve the yield. Further, since a large amount of silver oxide (Ag ₂ O) is used for lowering the temperature, it is a problem in product application that the unit price of the raw material becomes very high.

An object of the present invention is to improve the adhesiveness, improve the yield of applied products, reduce the amount of silver oxide used, have a low softening point, soften and flow at a low temperature, and have a lead-free low melting point. The purpose is to provide a glass composition.

The lead-free low melting point glass composition of the present invention contains vanadium oxide, tellurium oxide, silver oxide and lithium oxide, and has BaO, WO ₃ , ZnO, K2 O _{, Fe 2 O 3 and Al 2 O 3 as additional components .} , La ₂ O ₃ , MgO, CeO ₂ , ZrO ₂ and Na ₂ O, including one or more selected from the group, and satisfying the following relational expression (1) in terms of oxide.

2 [V ₂ O ₅ ] ≧ [Ag ₂ O] + [R ₂ O]… (1)
(In the formula, [X] represents the content of component X, the unit of which is "mol%", and [R ₂ O] = [Li ₂ O] + [K ₂ O] + [Na ₂ O]. be.)

According to the present invention, the adhesiveness can be improved, the yield of the applied product can be improved, the amount of silver oxide used is reduced, the softening point is low, the softening flow is performed at a low temperature, and the lead-free low melting point is achieved. A glass composition can be provided.

It is a graph which shows the result of the typical differential thermal analysis (DTA) peculiar to glass. It is a schematic plan view which shows the vacuum insulation multi-layer glass panel of an Example. 2A is a cross-sectional view taken along the line AA of FIG. 2A. It is a schematic plan view which shows a part of the manufacturing process of the vacuum insulation double glazing panel of FIG. 2A. 3A is a cross-sectional view taken along the line AA of FIG. 3A. It is a schematic plan view which shows a part of the manufacturing process of the vacuum insulation double glazing panel of FIG. 2A. 4A is a cross-sectional view taken along the line AA of FIG. 4A. 2A is a schematic cross-sectional view showing a part of the manufacturing process of the vacuum-insulated double glazing panel of FIG. 2A. It is a sealing temperature profile in the manufacturing process of the vacuum insulation double glazing panel shown in FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the embodiments taken up here, and can be appropriately combined and improved without changing the gist.

(Glass composition)
In a so-called low melting point glass composition, in general, the lower the characteristic temperature such as the transition point, the yield point, and the softening point, the better the softening fluidity at a low temperature. On the other hand, if the characteristic temperature is lowered too much, the tendency to crystallize becomes large, and it becomes easy to crystallize during heating and firing. This crystallization is a factor that reduces the softening fluidity at low temperatures. Further, the lower the characteristic temperature of glass, the lower the chemical stability such as moisture resistance and acid resistance. Furthermore, the impact on the environmental load tends to increase. For example, in the conventional PbO _- B ₂ O3 system low melting point glass composition, the higher the harmful PbO content, the lower the characteristic temperature can be, but the crystallization tendency is large and the chemical stability is lowered, and further. The impact on the environmental load will also increase.

Although the glass composition is substantially lead-free, the present inventor has better softening fluidity at a lower temperature than the conventional PbO _- B ₂ O3 low melting point glass composition, and has good adhesiveness. We diligently investigated the glass composition, which is good and has good chemical stability. As a result, the present inventor has found that the above requirements are simultaneously satisfied in the novel lead-free glass composition, and completed the present invention. In particular, one that softens and flows at a temperature (less than 300 ° C.) sufficiently lower than that of the conventional PbO _- B ₂ O3 low melting point glass composition was obtained.

Specifically, the lead-free low melting point glass composition according to the present invention contains vanadium oxide, tellurium oxide, silver oxide and lithium oxide as main components, and the content of these main components is as follows in terms of oxide. The relational expression (1) is satisfied.

2 [V ₂ O ₅ ] ≧ [Ag ₂ O] + [R ₂ O]… (1)
Here, [R ₂ O] = [Li ₂ O] + [K ₂ O] + [Na ₂ O]. The content of oxide X is expressed as [X] (the same applies hereinafter). The unit is "mol%" (the same shall apply hereinafter). "Mol%" is calculated in terms of oxide as a ratio of the content of each component contained in the glass composition to the entire glass composition. Note that 2 [V ₂ O ₅ ] means 2 × [V ₂ O ₅ ], that is, twice [V ₂ O ₅ ].

Further, as an additional component, at _least one of BaO, WO ₃ , ZnO, K2 O, Fe ₂ O ₃ , Al ₂ O ₃ , La ₂ O ₃ , MgO, CeO ₂ , ZrO ₂ and Na ₂ O is used. include.

Here, "lead-free" in the present invention means that the lead (Pb) content is 1000 ppm or less, which is an allowable range in the RoHS Directive.

By adding an additional component, the crystallization tendency can be reduced.

In other words, the lead-free low melting point glass composition according to the present invention contains oxides of silver (Ag), tellurium (Te), vanadium (V) and lithium (Li) as main components, and barium (Ba) as an additional component. , Tungsten (W), Zinc (Zn), Potassium (K), Iron (Fe), Aluminum (Al), Yttrium (Y), Lantern (La), Magnesium (Mg), Cerium (Ce), Zirconium (Zr) And sodium (Na), erbium (Er), placeodim (Pr), yttrium (Yb), gallium (Ga), indium (In) and molybdenum (Mo), which are at least one kind of oxide.

Further, it is desirable that the lead-free low melting point glass composition according to the present invention satisfies the above relational formula (1) and the following relational formulas (2) and (3).

[TeO ₂ ]> [V ₂ O ₅ ]> [Ag ₂ O]… (2)
30 ≤ [TeO ₂ ] ≤ 50 ... (3)
By setting the composition range as described above, the softening point of the glass can be lowered to 300 ° C. or lower.

Further, the lead-free low melting point glass composition of the present invention has high chemical stability such as moisture resistance and acid resistance, even though it has a low softening point, and also complies with the RoHS Directive.

As will be described in detail in the explanation of FIG. 1 in the latter part, the present inventor compares the results of differential thermal analysis (DTA) with the temperature based on the definition by viscosity for the transition point, the yield point and the softening point of the glass. It was confirmed that the second heat absorption peak temperature by DTA was almost equal to the softening point measured as the temperature corresponding to the viscosity. Therefore, in the present specification, the second endothermic peak temperature by DTA is defined as "softening point T _s ".

The functions of the main components V ₂ O ₅ , TeO ₂ , Ag ₂ O and Li ₂ O in the lead-free low melting point glass composition of the present invention will be described below.

The glass structure of the V ₂ O ₅ -TeO ₂ -Ag ₂ O-Li ₂ O-based lead-free low-melting point glass composition of the present invention has a layered structure composed of V ₂ O ₅ and TeO ₂ , and Ag is between the layers. ₂ O exists in the form of Ag ⁺ and Li ₂ O exists in the form of Li ⁺ . Ag ₂ O is mixed to lower the characteristic temperature of the transition point, yield point, softening point, etc. and to improve the chemical stability. It is considered that the lowering of the characteristic temperature is due to the fact that Ag ⁺ enters between the layers of the layered structure composed of V ₂ O ₅ and Te O ₂ , and the interlayer force is weakened. Further, it is considered that the improvement of the chemical stability is due to the inclusion of Ag ⁺ between the layers and the prevention of the infiltration of water molecules and the like. Therefore, as the amount of Ag ⁺ existing between the layers increases, the characteristic temperature can be lowered and the chemical stability can be improved.

However, if the content of Ag ₂ O is too large, there arises a problem that metallic silver (Ag) is deposited during the production of glass and a problem that the crystallization tendency of the produced glass increases. In addition, Li ⁺ existing between layers together with Ag ⁺ has a great effect on suppressing or preventing crystallization, and further improving or improving adhesiveness and adhesion. Li ⁺ , which is a monovalent cation with a small ionic radius, moves easily in the layers when heated, and diffuses into the material to be sealed or the material to be bonded during sealing or bonding, resulting in high adhesion and adhesion. Is considered to be possible.

However, if the content of Li ₂ O is too large, the chemical stability such as moisture resistance and acid resistance will be deteriorated, so care must be taken regarding the content.

It is considered that Ag ⁺ and Li ⁺ existing between the layers are bound to _{V2 O 5 forming} a layered structure. Up to two Ag ⁺ and Li ⁺ can be put in the ionic state between the layers in the glass structure for one pentavalent vanadium ion (V ⁵⁺ ). If it exceeds this, there arises a problem that metallic silver (Ag) is deposited during the production of glass.

If Ag ₂ O as a glass component does not exist in the Ag ⁺ state between the layers in the glass structure, the desired effect of lowering the temperature cannot be obtained. Therefore, when increasing the number of Ag ⁺ and Li ⁺ introduced between layers, it is necessary to appropriately increase the content of V ₂ O ₅ in addition to increasing the content of Ag ₂ O and Li ₂ O. There is.

As described above, V ₂ O ₅ forming a layered structure is a glass component that plays an important role in introducing Ag ⁺ and Li ⁺ into the glass structure.

TeO ₂ is a vitrification component for vitrification, and glass cannot be formed unless TeO ₂ is contained. Further, when the content of TeO ₂ is small, it is difficult to reduce the crystallization tendency. On the other hand, if the content is large, the crystallization tendency can be reduced, but it is difficult to lower the characteristic temperature. Further, when the content of TeO ₂ is increased, the glass structure is no longer a layered structure for introducing Ag ⁺ and Li ⁺ .

Considering both the reduction of the crystallization tendency and the lowering of the characteristic temperature, it is preferable to contain 1 to 2 V ⁵⁺ for each tetravalent tellurium ion (Te ⁴⁺ ). As a specific content of TeO ₂ , 30 mol% or more and 50 mol% or less is effective.

Further, the content of Ag ₂ O is preferably 5 mol% or more and less than 30 mol%. That is, it is preferable that 5 ≦ [Ag ₂ O] <30.

The content of V ₂ O ₅ is preferably 10 mol% or more and less than 30 mol%. That is, it is preferable that 10 ≦ [V ₂ O ₅ ] <30.

LiO ₂ easily diffuses into the material to be joined at the time of joining, and has an effect of improving the adhesiveness. However, it is desirable that the amount of Li is 3 mol% or more and 20 mol% or less because the water resistance may decrease if too much is added.

In addition, other alkali metals and additional components are useful for controlling the diffusion of Li. As other alkali metals added for diffusion control, K and Na are desirable. When adding these, it is desirable to satisfy [Li ₂ O]> [K ₂ O] + [Na ₂ O]. Further, it is desirable that the total amount of alkali metals containing Li [Li ₂ O] + [K ₂ O] + [Na ₂ O] is 3 mol% or more and 20 mol% or less.

The content of the additional component is preferably 3.0 mol% or more and 16 mol% or less in terms of oxide. By setting the content of the additional component to 3.0 mol% or more, the effect of reducing the crystallization tendency can be sufficiently obtained. Further, by setting the content of the additional component to 16 mol% or less, it is possible to suppress an increase in the characteristic temperature and crystallization.

Further, the lead-free low melting point glass composition of the present invention has high chemical stability such as moisture resistance and acid resistance, and complies with the RoHS Directive, even though the softening point is lowered.

A low melting point glass composite material containing a lead-free low melting point glass composition and one or more of low thermal expansion filler particles, metal particles, and a resin, and a low melting point glass paste obtained by pasting the low melting point glass composite material. For application to sealed structures, electrical and electronic parts, painted parts and the like, it is preferable to use a glass composition having a small crystallization tendency and a lower softening point. That is, by using a glass composition having a small crystallization tendency and a lower softening point, the softening fluidity of the glass composite material or the glass paste at a low temperature is improved. However, in the conventional low melting point glass composition, lowering the softening point is often accompanied by lowering the crystallization start temperature.

In this specification, products manufactured by using a low melting point glass composite material such as a sealing structure, an electric / electronic part, and a painted part are collectively referred to as an "applied product".

(Measurement of density)
Each of the prepared lead-free low melting point glasses was roughly crushed with a stamp mill and then crushed with a jet mill to an under 45 μm. Using the glass powder, the density of each lead-free low melting point glass was measured by a pycnometer method in helium gas.

(Measurement of characteristic temperature)
The characteristic temperature of each lead-free low melting point glass was determined by performing differential thermal analysis (DTA) at a heating rate of 5 ° C./min in the air using the same glass powder used for the density measurement. Here, a macrocell type DTA device was used and high-purity alumina (α-Al ₂ O ₃ ) powder was used as a standard sample so that the characteristic points of the DTA curve peculiar to glass could be clearly detected.

FIG. 1 is an example of a typical DTA curve peculiar to glass. The horizontal axis represents the temperature of the standard sample, and the vertical axis represents the temperature difference (potential difference) between the glass sample to be measured and the standard sample.

In this figure, when the glass is heated at the above temperature rise rate, endothermic absorption starts from the transition point _Tg and reaches the yield point _Mg corresponding to the first endothermic peak temperature. Then, the temperature difference becomes small once, and then the temperature difference becomes large again, reaching the softening point _Ts corresponding to the second endothermic peak temperature.

When further heated, heat generation starts from the crystallization temperature T _cry and reaches the heat generation peak. This exothermic peak is due to crystallization, and the temperature at which the exotherm starts is called the crystallization temperature T _cry . Although not shown, the temperature corresponding to the exothermic peak is referred to as the crystallization peak temperature _Tcry-p . The transition point T _g is the start temperature of the first endothermic peak, and the yield point _Mg is the first endothermic peak temperature. Each characteristic temperature is usually obtained by the tangential method.

Strictly speaking, the transition point T _g , the yield point _Mg and the softening point T _s are defined by the viscosity of the glass. T _g is a temperature corresponding to 10 ^13.3 poise, _Mg is a temperature corresponding to 10 ^11.0 poise, and T _s is a temperature corresponding to 10 ^7.65 poise.

The crystallization tendency is determined from the difference (absolute value) between the softening point T _s and the crystallization temperature T _cry , and the height of the exothermic peak due to crystallization, that is, the calorific value thereof.

First, if the difference (absolute value) between the softening point T _s and the crystallization temperature T _cry is large, even if the glass reaches a temperature exceeding the softening point T _s , the glass is softened and flowed in a temperature range that does not reach T _cry . Will be easy. Further, if the calorific value at the time of crystallization is small, when the temperature reaches T _cry by heating at a constant temperature rise rate, an uncontrollable temperature rise due to the heat generation is unlikely to occur, so that the progress of crystallization Can be suppressed.

Therefore, it can be said that the high temperature of T _cry , that is, the increase of T _cry −T _s and the decrease of the calorific value of crystallization indicate the glass which is difficult to crystallize. That is, if glass that is determined to have a small crystallization tendency is used, it becomes easy to form a desired sealing portion or the like.

The firing temperature when sealing and adhering various parts and forming electrodes / wiring and conductive / heat-dissipating joints using a conventional low-melting point glass composition is the same as that of the low thermal expansion filler particles and metal particles contained. Although it is affected by the type, content and particle size, as well as firing conditions such as heating rate, atmosphere, and pressure, it is usually set to be about 30 to 50 ° C. higher than the softening point _Ts . At this firing temperature, the low melting point glass composition has good softening fluidity without crystallization.

However, the lead-free low melting point glass composition according to the present invention has significantly lower characteristic temperatures at the transition point T _g , yield point _Mg and softening point T _s than the conventional low melting point glass composition, and the temperature difference between them is small. .. Therefore, the viscosity gradient in this temperature range is large. Therefore, even if the firing temperature is near the softening point T _s , good softening fluidity can be obtained if the temperature is maintained. Further, even if the holding time is short, sufficient softening fluidity is generated at a temperature higher than T _s by about 20 to 30 ° C.

(Low melting point glass composite material and low melting point glass paste)
The low melting point glass composite material includes a lead-free low melting point glass composition according to the present invention, and one or more of low thermal expansion filler particles, metal particles and a resin.

Hereinafter, a low melting point glass composite material containing low thermal expansion filler particles, metal particles or a resin will be described.

The low melting point glass composite material containing the low thermal expansion filler particles preferably contains 35% by volume or more and less than 100% by volume of the lead-free low melting point glass composition, and contains 0% by volume or more and 65% by volume or less of the low thermal expansion filler particles. By setting the lead-free low melting point glass composition to 35% by volume or more or the low thermal expansion filler particles to 65% by volume or less, good softening fluidity and good adhesiveness and adhesion to the material to be sealed and the material to be adhered are obtained. Gender is obtained.

Zirconium tungrate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ) and β-eucryptite (Li ₂ O) are examples of the low thermal expansion filler particles mixed to achieve low thermal expansion of the low melting point glass composite material. -Al ₂ O _{3.2SiO 2} ), cordierite ( _2MgO · 2Al 2O 3.5SiO ₂ ), quartz glass (SiO ₂ ), niobium oxide _{(Nb 2O 5 ) and} silicon (Si) It is preferable to have. Low thermal expansion filler particles that are particularly effective for low thermal expansion of low melting point glass composite materials are zirconium tungate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ) or zirconium tungate phosphate (Zr ₂ (WO)). ₄ ) (PO ₄ ) ₂ ) is included, and the preferable content thereof is 30% by volume or more and 60% by volume or less.

The low melting point glass composite material containing metal particles preferably contains 10% by volume or more and 80% by volume or less of a lead-free low melting point glass composition, and 20% by volume or more and 90% by volume or less of metal particles. By setting the lead-free low melting point glass composition to 10% by volume or more or the metal particles to 90% by volume or less, sintering between the metal particles and adhesion and adhesion to the substrate are improved.

From the viewpoint of improving conductivity and heat dissipation, the metal particles include silver (Ag), silver alloy, copper (Cu), copper alloy, aluminum (Al), aluminum alloy, tin (Sn), and tin alloy. Is preferable. In particular, the metal particles effective for improving the conductivity and heat dissipation of the low melting point glass composite material of the present invention are silver (Ag) or aluminum (Al), and the preferable content thereof is 10 to 90% by volume. .. This is because the lead-free low melting point glass composition of the present invention can promote sintering of silver (Ag) particles and can remove a surface oxide film of aluminum (Al) particles.

The low melting point glass composite material containing a resin contains 5% by volume or more and less than 100% by volume of a lead-free low melting point glass composition, and contains more than 0% by volume and 95% by volume or less of a resin. By adjusting the lead-free low melting point glass composition of the present invention to 5% by volume or more or the resin to 95% by volume or less, the lead-free glass composition and the resin can be effectively combined.

The resin is preferably any one of epoxy resin, phenoxy resin, phenol resin, acrylic resin, urethane resin and fluororesin. By using these resins, the softening fluidity becomes good in the resin of the lead-free low melting point glass composition.

The low melting point glass paste contains a low melting point glass composite material containing the lead-free low melting point glass composition according to the present invention, and a solvent. As the solvent, dihydroterpineol, α-terpineol or carbitol acetate is preferably used. This is because these solvents are difficult to crystallize for the lead-free low melting point glass composition of the present invention. Further, the stability and coatability of the low melting point glass paste can be adjusted by adding a viscosity adjusting agent, a wetting agent, or the like as needed.

When sealing or bonding in a sealed structure using a low melting point glass composite material containing low thermal expansion filler particles or its low melting point glass paste, it is applied to the sealed part of the object to be sealed or the bonded part of the object to be adhered. It is preferable to dispose or apply a low melting point glass composite material or a low melting point glass paste and _bake the contained lead-free low melting point glass composition in a temperature range of about 20 ° C. higher than the softening point T _s .

Since the glass composite material and the glass paste of the present invention use a lead-free low melting point glass composition having a reduced tendency to crystallize and a low softening point, the softening fluidity at a low temperature is improved and the firing temperature is increased. The temperature can be lowered. As a result, it is possible to reduce the influence on the environmental load, reduce the thermal damage of the sealed structure (higher functionality), and improve the productivity (reduce tact). Further, since the lead-free low melting point glass composition of the present invention has good adhesiveness, adhesion and chemical stability, the reliability of the sealed structure can be ensured.

Further, when a low melting point glass composite material containing metal particles or a low melting point glass paste thereof is used to form an electrode / wiring or a conductive / heat dissipation joint in an electric / electronic component, the temperature is low at a predetermined location such as a base material. It is preferable to arrange or apply a melting point glass composite material or a low melting point glass paste and _bake the lead-free low melting point glass composition contained therein in a temperature range of about 20 ° C. higher than the softening point T _s . If the metal particles used are metals that are easily oxidized, it is desirable to set the firing atmosphere to an inert gas or vacuum in order to prevent the metal particles from oxidizing.

Since the low melting point glass composite material and the low melting point glass paste of the present invention use a lead-free low melting point glass composition having a reduced crystallization tendency and a low softening point, the softening fluidity at a low temperature is improved. , The firing temperature can be lowered. As a result, the formation temperature of the electrode / wiring and the conductive / heat-dissipating joint, that is, the firing temperature can be lowered. As a result, it is possible to reduce the influence on the environmental load, reduce the thermal damage of the electric / electronic parts (higher functionality), and improve the productivity (reduce the tact). Further, since the lead-free low melting point glass composition of the present invention has good adhesiveness, adhesion and chemical stability, the reliability of electrical and electronic parts can be ensured.

Further, when a low melting point glass composite material containing a resin or a low melting point glass paste is used to form a coating film on a painted part, metal, ceramics or glass is effective as a base material. A low melting point glass composite material or a low melting point glass paste is placed or applied to a predetermined portion of the base material, and the lead-free low melting point glass composition contained _therein is about 20 ° C. higher than the softening point T _s . Bake in the temperature range.

The low melting point glass composite material and the low melting point glass paste of the present invention have a reduced tendency to crystallize, and by using a lead-free low melting point glass composition having a low softening point, the softening fluidity at a low temperature is improved. The firing temperature can be lowered. As a result, it is possible to reduce the influence on the environmental load and improve the reliability of the coating film adhesion, heat resistance, chemical stability and the like of the painted parts.

(Sealing structure)
The low melting point glass composite material and the low melting point glass paste according to the present invention are vacuum-insulated double glazing panels, plasma display panels, organic EL display panels, display panels such as fluorescent display tubes, and crystals, which are applied to window glass and the like. It is suitably used for encapsulating a vibrator, an IC package, a package device such as a MEMS, and the like.

The sealing structure according to the present invention uses a glass plate, a circuit board, or the like, a low melting point glass composite material, or a low melting point glass paste.

The sealing structure may have an internal space separated from the outside. In this case, the boundary between the internal space and the outside may be formed by a sealing portion containing a low melting point glass composite material. The content of the lead-free low melting point glass composition contained in the low melting point glass composite material forming the sealing portion is preferably 40% by volume or more and less than 100% by volume. Further, it is effective to mix the low melting point glass composite material with the low thermal expansion filler particles. Further, instead of the low thermal expansion filler particles, soft metal particles may be mixed to relieve the residual stress of the sealing portion.

(Electrical and electronic parts)
The low melting point glass composite material and the low melting point glass paste according to the present invention are used for electrical and electronic components such as solar cells, image display devices, laminated capacitors, inductors, crystal transducers, light emitting diodes (LEDs), multilayer circuit boards, and semiconductor modules. It is suitably used for forming electrodes, wirings, conductive joints and heat-dissipating joints. In this case, the content of the metal particles contained in the low melting point glass composite material is preferably 50% by volume or more.

(Painted parts)
The low melting point glass composite material or the low melting point glass paste according to the present invention can also be used as a paint.

The painted component according to the present invention includes a member and a coating film formed by applying a paint to the surface of the member or the like. The members are metal, ceramics, glass and the like. The coating film contains a low melting point glass composite material according to the present invention.

A resin may be mixed with the low melting point glass composite material forming the coating film. It is effective that the content of the resin is 50% by volume or more. Suitable examples of painted parts include electric wires, vehicle bodies, airframes, washing machine tubs, toilet bowls, bathtub tiles and the like.

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

[Example 1]
In this example, a V ₂ O ₅ -TeO ₂ -Ag ₂ O-Li ₂ O-based lead-free glass composition was prepared, and the effect of the glass composition on the glass properties was investigated. As the glass characteristics, the vitrified state, characteristic temperature, thermal expansion characteristics, adhesiveness, salt water resistance and softening fluidity of the produced lead-free glass composition were evaluated.

(Preparation of lead-free glass composition)
Tables 1 and 2 show the compositions of the lead-free glass compositions S-01 to S-17 of Examples and the lead-free glass compositions C1 to C2 of Comparative Examples, and the characteristics of each lead-free glass composition. .. The lead-free glass compositions S-01 to S-17 of the examples are lead-free glass compositions containing V ₂ O ₅ , TeO ₂ , Ag ₂ O and Li ₂ O as main components and essential components.

The starting materials for the main components are V ₂ O ₅ and TeO ₂ manufactured by Shinko Kagaku Kogyo Co., Ltd., Ag ₂ O manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., and Li ₂ CO manufactured by High Purity Chemical Research Institute Co., Ltd. The powder of ₃ was used.

The starting materials for the additional components are BaCO ₃ , WO ₃ , ZnO, K ₂ CO ₃ , Fe ₂ O ₃ , Al ₂ O ₃ , La ₂ O ₃ , MgO, CeO ₂ , ZrO ₂ and Na ₂ CO ₃ . Powder was used. All of these are manufactured by High Purity Chemical Laboratory Co., Ltd.

Weighed, blended, mixed, and put into a quartz glass crucible so that each starting material powder weighed about 200 g in total. A quartz glass crucible containing a mixed powder of raw materials is installed in a glass melting furnace and heated to 700 to 750 ° C at a heating rate of about 10 ° C / min to make the composition of the melt in the quartz glass crucible uniform. It was held for 1 hour while stirring with an alumina rod. 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 S-01 to S-17 of Examples and C1 to C2 of Comparative Examples, respectively. Next, the prepared lead-free glass composition was pulverized to under 45 μm.

(Evaluation of vitrification state)
The vitrified states of the prepared lead-free glass compositions S-01 to S-17 and C1 to C2 were evaluated by using the glass powder and checking whether crystals were precipitated by X-ray diffraction. Including the comparative examples, no crystal precipitation was observed, and the vitrified state was good.

(Evaluation of characteristic temperature)
The characteristic temperatures of the prepared lead-free glass compositions S-01 to S-17 and C1 to C2 were evaluated by DTA using the glass powder. The macrocell type was used for DTA. About 500 mg of glass powder was placed in a macrocell and heated from room temperature to 320 ° C. at a heating rate of 5 ° C./min in the atmosphere to obtain a DTA curve as shown in FIG. From the obtained DTA curve, the transition point T _g , the yield point M _g , the softening point T _s , the crystallization temperature T _cry and the crystallization peak temperature T _cry-p were measured. The calorific value (μV) of the crystallization peak was also measured. From the measurement results, the temperature difference between T _cry and T _s (hereinafter, also referred to as "T _cry -T _s ") was calculated. The calorific value of the crystallization peak is also referred to as "T _cry-p calorific value".

(Measurement of coefficient of thermal expansion)
The prepared lead-free glass compositions S-01 to S-17 and C1 to C2 are heated in a temperature range of the transition point T _g to the yield point _Mg by DTA and slowly cooled to remove residual thermal strain, and 4 ×. It was processed into a 4 × 20 mm prism. Using this, the thermal expansion curve of each lead-free glass composition was measured with a thermal expansion meter at a heating rate of 5 ° C./min in the atmosphere. As a standard sample, a cylindrical quartz glass having a diameter of 5 × 20 mm was used.

As the thermal expansion characteristic, the coefficient of thermal expansion at 150 ° C. was adopted.

(Adhesion evaluation)
Two soda lime glass plates were used as the material to be joined. The glass plate size is 20 × 50 × t2.7 mm. The prepared lead-free glass compositions S-01 to S-17 and C1 to C2 were used, and the central portion of the glass plate was bonded in a cross shape, and then a load was applied to the glass on one side to peel off the glass plate. The load on the adhesive area when the two glass plates were peeled off was measured. The firing conditions at the time of bonding were 230 ° C.-30 minutes, 300 ° C.-30 minutes, a temperature rise of 6 ° C./min, and a temperature decrease of 2 ° C./min. The joint strength was evaluated by the average value of N number 10.

The bonding strengths of the lead-free glass compositions S-01 to S-17 and C1 to C2 used this time were 0.25 to 0.45 MPa. The bonding strength calculated from the value of the load that does not cause a problem in bonding is 0.3 MPa or more, and in the case of the bonding strength in this range, the adhesiveness is “◯”. When the bonding strength was 0.25 to 0.3 MPa, the adhesiveness was evaluated as “Δ”, and when the bonding strength was less than 0.25 MPa, the adhesiveness was evaluated as “×”.

All of the components satisfied the performance as an adhesive glass, but in the examples, higher adhesiveness was confirmed as compared with the comparative example. Therefore, in the glass of the example, the adhesiveness is high as compared with the comparative example, and the yield at the time of use is high.

(Evaluation of salt water resistance (salt spray test and salt water impregnation test))
In the salt spray test (according to Japanese Industrial Standards JIS Z 2371: 2015) in which salt water is sprayed onto the glass, no particular change was observed in the glass having any composition, and there was no difference between the examples. ..

As an accelerated test, each test piece was impregnated with 10% salt water at 40 ° C. for 120 hours, and a salt water impregnation test was performed.

Depending on the presence or absence of precipitates in the glass, those in which precipitation was observed as a whole are marked with "x", those with several precipitates are marked with "△", and those in which no precipitate was found are marked with "○". evaluated.

It was confirmed that the lead-free glass compositions S-16 and S-17 had no precipitation at all and had high salt water resistance. Therefore, it was found that when Ce, Fe and Al were used as additional components, they showed high salt water resistance.

(Evaluation of softening fluidity)
The softening fluidity of the prepared lead-free glass compositions S-01 to S-17 and C1 to C2 was evaluated by a button flow test of a powder compact prepared using the glass powder.

The powder compact was molded into a cylindrical shape having a diameter of 12 mm and a height of about 3 mm under the condition of 500 kg / cm ² using a mold and a hand press. Then, the powder compact is placed on a soda lime glass substrate, the powder compact is introduced into an electric furnace, and the temperature _rises from room temperature to 20 to 30 ° C. from room temperature at a temperature rise rate of 10 ° C./min in the air. It was heated to a high temperature and held for 30 minutes. Then, it was cooled in a furnace, and the softening fluidity and the crystallization state were evaluated.

Regarding the softening fluidity, it was judged as "pass" when it was clear that the sample of the powder compact was not only deformed but also liquefied and flowed, and then solidified in a glossy state. .. On the other hand, if the softening flow is devitrified (surface crystallization) or the softening flow is insufficient due to crystallization, it is judged as "failed".

A conventional leaded low melting point glass composition (84PbO-13B ₂ O ₃ -2SiO ₂ -1Al ₂ O ₎ having a transition point T _g of 313 ° C, a yield point Mg of 332 ° C and a softening point T _s of 386 ° C. When a similar button flow test was carried out at 430 ° C. ( ₃ % by mass), the softening fluidity was "passed". However, cracks were observed due to the large difference in thermal expansion from the soda lime glass substrate. The occurrence of this crack can be counteracted by mixing the low thermal expansion filler particles into the powder of the leaded low melting point glass composition.

(Evaluation of water resistance)
The water resistance was determined by HAST (High Accelerated Stress Test, high-speed accelerated life test) for 48 hours under the conditions of 120 ° C., 100% humidity and 2 atm, and the presence or absence of elution from the button sample. “○” indicates that there is no elution. “Δ” indicates a case where very slight elution is observed on the back surface. “X” indicates that elution is observed.

From the above, the effective glass composition contains Ag ₂ O, TeO ₂ , V ₂ O ₅ and Li ₂ O as main components. Further, as additional components, Ba ₂ O, Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Er ₂ O ₃ , Yb ₂ O ₃ , Al ₂ O ₃ , Ga ₂ O ₃ , In ₂ O ₃ , Fe ₂ O _3. Contains at least one of WO ₃ and MoO ₃ in a small amount. In particular, the content of the main component is mol%, and the content of Ag ₂ O> TeO ₂ ≧ V ₂ O ₅ , 2V ₂ O ₅ ≧ Ag ₂ O + R ₂ O, and TeO ₂ is 30 mol% or more and 50 mol% or less. Is preferable.

More preferably, the content of Ag ₂ O is 10 mol% or more and less than 25 mol%, and the content of V ₂ O ₅ is 18 mol% or more and less than 28 mol%. The content of the additional component is 3.0 mol% or more and 16.0 mol% or less in terms of the above oxides.

It has been confirmed that the lead-free glass composition using ZrO ₂ instead of CeO ₂ has the same characteristics as those containing CeO ₂ . Further, it has been confirmed that the lead-free glass composition using Na ₂ O instead of K ₂ O has the same characteristics as those containing K ₂ O.

In the following examples, the above-mentioned glass composite material and glass paste containing the lead-free glass composition of the present invention, and the sealing structure, electrical and electronic parts, and painted parts to which these glass composite materials and glass paste are applied are respectively. This will be described in detail.

[Example 2: Paste]
Hereinafter, a method of using the lead-free glass composition will be specifically described.

Example 2 is an example in which a glass composite material containing a lead-free glass composition and metal particles is used, and metal substrates of the same type or different types are bonded to each other. As the metal particles, silver (Ag), copper (Cu), aluminum (Al), tin (Sn) and the like can be used. Further, aluminum (Al), copper (Cu), nickel (Ni), iron (Fe) and the like can be used as the metal base material. A glass paste containing particles of a lead-free glass composition, metal particles, and a solvent is prepared, applied to a metal substrate such as aluminum (Al), dried, and pre-fired, and then the same or different metal substrates are combined. It can be joined by resistance welding.

Solder is frequently used to form conductive joints and heat-dissipating joints between metal substrates, but considering the differentiation from solder, it is used as metal particles contained in glass composite materials and their glass pastes. Ag particles and Al particles are effective. Further, with solder, it is difficult to perform good conductive bonding and heat dissipation bonding on a metal substrate or the like having a natural oxide film formed on the surface such as Al, but the glass composite material and its glass paste according to the present invention have difficulty in bonding. By the action of the lead-free glass composition of the present invention contained therein, it is possible to perform conductive bonding and heat dissipation bonding even with such a metal base material.

Further, the glass composite material or glass paste containing metal particles can also be used as a glass composite material or its glass paste if conductivity is allowed in the joint portion or the sealing portion. In that case, stress relaxation can be performed depending on the size and amount of the contained metal particles, and low-temperature bonding or low-temperature sealing can be performed.

[Example 3: Electrode wiring]
In this embodiment, an example of forming electrodes / wiring on various substrates by using a glass composite material containing the lead-free glass composition of the present invention and metal particles will be described. As the metal particles, silver (Ag), copper (Cu), aluminum (Al), tin (Sn) and the like can be used. Further, as the substrate, an alumina (Al ₂ O ₃ ) substrate, a borosilicate glass substrate, a silicon (Si) substrate, a ferrite substrate, a polyimide substrate and the like can be used. Electrodes / wiring can be formed by preparing a glass paste containing particles of a lead-free glass composition, metal particles, and a solvent, applying the mixture to various substrates, drying, and calcining.

Various known methods can be applied to form electrodes and wirings with a desired wiring pattern. For example, a conductive glass paste is used to apply a pattern on a substrate by a screen printing method, dried, and then heated. This makes it possible to form board wiring and electrodes.

[Example 4: Sealed structure]
In this embodiment, using two soda lime glass substrates and the glass composite material of the present invention, a double glazing panel for vacuum insulation is produced as one of the representative examples of the sealed structure according to the present invention. An example will be described.

FIG. 2A is a schematic plan view of the produced double glazing panel for vacuum insulation. Further, FIG. 2B is an enlarged view of the AA cross section in the vicinity of the sealing portion.

As shown in FIG. 2A, the double glazing panel for vacuum insulation is a glass substrate 15 such as soda lime glass and another glass substrate (reference numeral 16 in FIG. 2B) arranged so as to be stacked with a gap provided therein. It has a sealing portion 14 on the peripheral edge portion. A plurality of spacers 18 are two-dimensionally arranged at equal intervals between these substrates (15, 16). An exhaust hole 20 is formed in the glass substrate (16), and a vacuum pump (not shown) is used to exhaust air from the gap between the two substrates (15, 16) through the exhaust hole 20. ing. A cap 21 is attached to the exhaust hole 20.

As shown in FIG. 2B, there is a space portion 17 (the above gap) between the pair of glass substrates 15 and 16 having a sealing portion 14 on the outer peripheral portion (peripheral portion), and the space portion 17 is in a vacuum state. It is in. The glass composite material of the present invention is used for the sealing portion 14. This double glazing panel for vacuum insulation can be applied to window glass for building materials, window glass for vehicles, doors of commercial refrigerators and freezers, and the like.

In addition to containing the lead-free glass composition of the present invention, the glass composite material of the present invention used for the sealing portion 14 has a low coefficient of thermal expansion in order to match the coefficient of thermal expansion between the glass substrates 15 and 16. The filler particles are mixed. Since the heat resistance of the glass substrates 15 and 16 is about 500 ° C., it is necessary to form the sealing portion 14 below that temperature. Further, since the glass substrates 15 and 16 are easily damaged by rapid heating or rapid cooling, it is necessary to gradually heat and cool the sealing, and in order to improve the productivity of the double glazing panel for vacuum insulation, it is possible to improve the productivity. , Sealing at low temperature is required. Further, the glass substrates 15 and 16 are often air-cooled for security and safety. This air-cooling reinforcement forms a compression strengthening layer on the surfaces of the glass substrates 15 and 16, and the strengthening layer gradually decreases when heated at 300 ° C. or higher and disappears when heated at 400 ° C. or higher. For this reason as well, sealing at a lower temperature is strongly required.

In order to secure a space portion 17 in a vacuum state between the glass substrates 15 and 16, a plurality of spacers 18 are installed in the space portion 17. Further, in order to obtain the space portion 17 having an appropriate thickness, it is effective to introduce spherical beads 19 having a uniform particle size into the spacer 18 and the sealing portion 14. Further, the glass composite material of the present invention can be utilized for fixing the spacer 18 as in the sealing portion 14. In order to obtain the space portion 17 having a vacuum state, an exhaust hole 20 is formed in the glass substrate 16 in advance, and the space portion 17 is exhausted from the exhaust hole 20 using a vacuum pump. A cap 21 is attached after exhausting so that the degree of vacuum of the space 17 can be maintained. When applied as a window glass for building materials or a window glass for vehicles, a heat ray reflecting film 22 may be formed in advance on the inner surface of the glass substrate 15 by a vapor deposition method or the like.

(Manufacturing of vacuum insulated double glazing panel)
The method of manufacturing the vacuum-insulated double glazing panel of this embodiment will be described with reference to FIGS. 3A to 5.

FIG. 3A shows a state in which the sealing portion 14 and the spacer 18 are formed on the air-cooled reinforced soda lime glass substrate 16 constituting the vacuum-insulated double glazing panel shown in FIGS. 2A and 2B.

As shown in FIG. 3A, the above glass paste was prepared, applied to the outer peripheral portion (sealing portion 14) and the inner portion (spacer 18) of the air-cooled soda lime glass substrate 16 by the dispenser method, respectively, and at 150 ° C. in the atmosphere. dry. This is heated to 220 ° C. in the atmosphere at a heating rate of 5 ° C./min and held for 30 minutes, and the sealing portion 14 and the spacer 18 are attached to the air-cooled reinforced soda lime glass substrate 16.

FIG. 3B shows a cross section taken along the line AA of FIG. 3A.

As shown in FIG. 3B, the sealing portion 14 and the spacer 18 include spherical beads 19.

FIG. 4A shows the air-cooled reinforced soda lime glass substrate 15 constituting the vacuum-insulated double glazing panel shown in FIG. 2B.

4B is a sectional view taken along the line AA of FIG. 4A.

As shown in FIGS. 4A and 4B, a heat ray reflecting film 22 is formed on one side of the air-cooled soda lime glass substrate 15.

FIG. 5 shows the final step of the method for manufacturing the vacuum insulated double glazing panel shown in FIGS. 2A and 2B.

In FIG. 5, two air-cooled reinforced soda lime glass substrates 15 and 16 are opposed to each other, aligned, and fixed with a plurality of heat-resistant clips. This is heat-treated while being evacuated and sealed.

FIG. 6 shows the sealing temperature profile in the heat treatment of FIG.

As shown in FIG. 6, the panel is heated to a temperature 10 to 20 ° C. higher than the yield point _Mg (221 ° C.) of the lead-free glass composition S-12 at a heating rate of 5 ° C./min in the air and held for 30 minutes. While exhausting the inside from the exhaust hole 20 with a vacuum pump, heat the lead-free glass composition S-12 to a temperature 10 to 20 ° C higher than the softening point T _s (267 ° C) of the lead-free glass composition S-12 for 30 minutes at a heating rate of 5 ° C / min. Hold and seal.

As shown in FIG. 5, during the heat treatment, the sealing portion 14 and the spacer 18 are crushed by atmospheric pressure and adhere to the two air-cooled reinforced soda lime glass substrates 15 and 16. After that, the cap 21 is attached to the exhaust hole 20 to produce a vacuum-insulated double glazing panel.

In the vacuum-insulated double glazing panel to which the glass composite material of the present invention and the glass paste thereof are applied, a highly adhesive and highly reliable sealing portion can be obtained. Furthermore, by using the glass composite material of the present invention or the glass composite material thereof, the sealing temperature can be lowered, the productivity of the vacuum-insulated double glazing panel is improved, and the application of a soda lime glass substrate to which air-cooling is strengthened. It can also greatly contribute to such things.

Similar to the vacuum-insulated double glazing panel, it can be effectively applied to a sealing structure other than the vacuum-insulated double glazing panel, such as an electric / electronic component such as a display panel or a solar cell.

Based on the above, by applying the lead-free glass composition of the present invention and a glass composite material containing metal particles or low thermal expansion filler particles or a glass paste thereof to a conductive joint or a sealing portion, the influence on the environmental load is considered. After that, it was found that a highly reliable crystal transducer package could be obtained. In this embodiment, an example of application to a crystal oscillator package has been described as one of the representative examples of the electric / electronic component and the sealing structure according to the present invention, but the glass composite material and the glass paste thereof according to the present invention have been described. It can be effectively applied not only to the crystal oscillator package but also to many electric / electronic parts and sealing structures having a conductive joint portion, a sealing portion, and a heat dissipation joint portion.

In the examples, the vacuum insulating multi-layer glass panel has been described as a representative example as the sealing structure and the electric / electronic component according to the present invention, but the present invention is not limited thereto, and various displays such as an LED display are used. Many sealed structures and electrical / electronics such as panels, solar cells, package devices such as crystal oscillator packages, image display devices, laminated capacitors, inductors, light emitting diodes, multilayer circuit boards, semiconductor modules, semiconductor sensors, semiconductor sensors, etc. It is self-evident that it is applicable to components.

14: Sealing part, 15, 16: Soda lime glass substrate, 17: Space part, 18: Spacer, 19: Spherical beads, 20: Exhaust hole, 21: Cap, 22: Heat ray reflecting film.

Claims (15)

Contains vanadium oxide, tellurium oxide, silver oxide and lithium oxide, and
One or _more selected from the group consisting of BaO, WO ₃ , ZnO, K2 O, Fe ₂ O ₃ , Al ₂ O ₃ , La ₂ O ₃ , MgO, CeO ₂ , ZrO ₂ and Na ₂ O as additional components. Including
A lead-free low melting point glass composition satisfying the following relational expressions (1) , (2) and (3) in terms of oxide.
2 [V ₂ O ₅ ] ≧ [Ag ₂ O] + [R ₂ O]… (1)
[TeO ₂ ]> [V ₂ O ₅ ]> [Ag ₂ O]… (2)
30 ≤ [TeO ₂ ] ≤ 50 ... (3)
(In the formula, [X] represents the content of component X, and its unit is "mol%" (the same applies hereinafter). [R ₂ O] = [Li ₂ O] + [K ₂ O] + [Na ₂ O].) The lead-free low melting point glass composition according to claim 1 , which satisfies the following relational formulas (4) and (5).
5 ≦ [Ag ₂ O] <30… (4)
10 ≦ [V ₂ O ₅ ] <30… (5) The lead-free low melting point glass composition according to claim 1 or 2 , wherein the content of the additional component is 3.0 mol% or more and 16 mol% or less in terms of oxide. The lead-free low melting point glass composition according to claim 3 , wherein the content of each metal element of the additional component is 6.0 mol% or less in terms of oxide. The lead-free low melting point glass composition according to any one of claims 1 to 4 .
A low melting point glass composite material comprising any one of low thermal expansion filler particles, metal particles and resins. Contains the low thermal expansion filler particles
The low thermal expansion filler particles include zirconium tungstate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), quartz glass (SiO ₂ ), zirconium silicate (ZrSiO ₄ ), alumina (Al ₂ O ₃ ), and mulite. The low melting point glass composite material according to claim 5 , which comprises any one of (3Al ₂ O _{3.2SiO 2} ) and niobium oxide (Nb ₂ O ₅ ). The content of the lead-free low melting point glass composition is 40% by volume or more and less than 100% by volume.
The low melting point glass composite material according to claim 6 , wherein the content of the low thermal expansion filler particles is more than 0% by volume and 60% by volume or less. The low thermal expansion filler particles contain zirconium tungrate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ) or zirconium tungrate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ).
The low melting point glass composite material according to claim 6 , wherein the content of the low thermal expansion filler particles is 30% by volume or more and 60% by volume or less. Including the metal particles
The low melting point glass composite material according to claim 5 , wherein the metal particles include any one of Au, Ag, Cu, Al and Sn. The content of the lead-free low melting point glass composition is 10% by volume or more and 80% by volume or less.
The low melting point glass composite material according to claim 9 , wherein the content of the metal particles is 20% by volume or more and 90% by volume or less. The metal particles contain Ag or Al and contain
The low melting point glass composite material according to claim 9 , wherein the content of the metal particles is 20% by volume or more and 90% by volume or less. Including the resin
The low melting point glass composite material according to claim 5 , wherein the resin contains any one of an epoxy resin, a phenoxy resin, a phenol resin, an acrylic resin, a urethane resin and a fluororesin. The content of the lead-free low melting point glass composition is 5% by volume or more and less than 100% by volume.
The low melting point glass composite material according to claim 12 , wherein the content of the resin is more than 0% by volume and 95% by volume or less. A glass paste containing the low melting point glass composite material according to any one of claims 5 to 13 and a solvent. An applied product produced by using the low melting point glass composite material according to any one of claims 5 to 13 .

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